Mariusz Jancelewicz

Factors Affecting the Performance of Champion Silyl-Anchor Carbazole Dye Revealed in the Femtosecond to Second Studies of Complete ADEKA-1 Sensitized Solar Cells

Record laboratory efficiencies of dye-sensitized solar cells have been recently reported using an alkoxysilyl-anchor dye, ADEKA-1 (over 14 %). In this work we use time-resolved techniques to study the impact of key preparation factors (dye synthesis route, addition of co-adsorbent, use of cobalt-based electrolytes of different redox potential, creation of insulating Al2 O3 layers and molecule capping passivation of the electrode) on the partial charge separation efficiencies in ADEKA-1 solar cells. We have observed that unwanted fast recombination of electrons from titania to the dye, probably associated with the orientation of the dyes on the titania surface, plays a crucial role in the performance of the cells. This recombination, taking place on the sub-ns and ns time scales, is suppressed in the optimized dye synthesis methods and upon addition of the co-adsorbent. Capping treatment significantly reduces the charge recombination between titania and electrolyte, improving the electron lifetime from tens of ms to hundreds of ms, or even to single seconds. Similar increase in electron lifetime is observed for homogenous Al2 O3 over-layers on titania nanoparticles, however, in this case the total solar cells photocurrent is decreased due to smaller electron injection yield from the dye. Our studies should be important for a broader use of very promising silyl-anchor dyes and the further optimization and development of dye-sensitized solar cells.

Enhancement of optical and mechanical properties of Si nanopillars by ALD TiO2 coating

The mechanical and optical properties of Si and TiO2–Si nanopillars (NPl) were investigated. Mesoporous silicon NPl arrays were fabricated by metal-assisted chemical etching and nanosphere lithography, and then pillars were covered by TiO2 using the atomic layer deposition technique. We performed scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, reflectance, photoluminescence (PL) spectroscopy and nanoindentation to characterize the as-prepared and annealed TiO2–Si NPl. The main structural and mechanical parameters of TiO2–Si NPl (grain size, strain, critical load, elastic recovery and Youngs module) were calculated. Reflectance and PL spectroscopy were used to study the impact of morphology on optical properties of TiO2–Si NPl before and after annealing. It was established that the nanostructures of TiO2 penetrated inside the porous matrix of Si pillar improve the mechanical properties of TiO2–Si NPl. The results of nanoindentation study have shown that Youngs modulus of annealed TiO2–Si NPl is about three times higher than for the pure Si NPl.

Effects of Post-Assembly Molecular and Atomic Passivation of Sensitized Titania Surface: Dynamics of Electron Transfer Measured from Femtoseconds to Seconds

The dynamics of electron transfer at the dye-titania and titania-electrolyte interfaces is investigated in two post-sensitization processes: (i) atomic layer deposition of blocking alumina coating and (ii) hierarchical molecular multicapping. To measure the electron transfer dynamics, time-resolved spectroscopic methods (femtosecond transient absorption on the time scale from femtoseconds to nanoseconds and electrochemical impedance spectroscopy on the time scale from milliseconds to seconds) are applied to the complete dye-sensitized solar cells with cobalt-based electrolyte and champion ADEKA-1 dye (with silyl-anchor unit) or its popular carboxyl-anchor analogue, MK-2 dye. Both molecular capping and alumina blocking layers slow down the electron injection process (the average rate constant decreases from 1.1 ps-1 to 0.4 ps-1) and partial sub-nanosecond back electron transfer from titania to the dye (from ca. 10 ns-1 to 5 ns-1). Very small alumina layers (of 0.1 nm thickness) have the highest impact on reducing the rate constants of these electron transfer processes, and for the thicknesses greater than 0.3 nm the rate constants hardly change. In contrast, the electron recombination between titania and electrolyte, occurring on the millisecond time scale, starts to be significantly suppressed for the blocking layers of 0.3 nm or more in thickness (up to ca. 20 times for 0.5 nm thickness with respect to that for untreated sample), improving open circuit voltage and fill factor of the cells. The amplitude of the relative photocurrent (short circuit current per number of absorbed photons) is found to depend almost exclusively on the ultrafast and fast processes taking place in the first nanoseconds after dye excitation. The positive impact of coadsorbents on the solar cells performance for both ADEKA-1 and MK-2 is also studied.

Structural and optical properties of TiO2–Al2O3 nanolaminates produced by atomic layer deposition

Structural and optical properties of Al2O3/TiO2 nanolaminates fabricated by atomic layer deposition (ALD) were investigated. We performed Raman spectroscopy, transmission electron microscopy (TEM), X-Ray reflectivity (XRR), UV-Vis spectroscopy, and photoluminescence (PL) spectroscopy to characterize the Al2O3/TiO2 nanolaminates. The main structural and optical parameters of Al2O3/TiO2 nanolaminates were calculated. It was established that with decreasing of the layer thickness, the value of band gap energy increases due to the quantum size effect related to the reduction of the nanograins size. It was also shown that there is an interdiffusion layer at the Al2O3/TiO2 interface which plays a crucial role in explaining the optical properties of Al2O3/TiO2 nanolaminates. Correlation between structural and optical parameters was discussed.

Effect of annealing temperature on optical and electrical properties of metallophthalocyanine thin films deposited on silicon substrate

Abstract The cobalt phthalocyanine (CoPc) thin films (300 nm thick) deposited on n-type silicon substrate have been studied using micro-Raman spectroscopy, atomic force spectroscopy (AFM) and I-V measurement. The CoPc thin layers have been deposited at room temperature by the quasi-molecular beam evaporation technique. The micro-Raman spectra of CoPc thin films have been recorded in the spectral range of 1000 cm-1 to 1900 cm-1 using 488 nm excitation wavelength. Moreover, using surface Raman mapping it was possible to obtain information about polymorphic forms distribution (before and after annealing) of metallophthalocyanine (α and β form) from polarized Raman spectra. The I-V characteristics of the Au/CoPc/n-Si/Al Schottky barrier were also investigated. The obtained results showed that influence of the annealing process plays a crucial role in the ordering and electrical conductivity of the molecular structure of CoPc thin films deposited on n-type silicon substrate.