Parametric study of temperature distribution in plasmon-assisted photocatalysis

Recently, there has been a growing interest in the usage of mm-scale composites of plasmonic nanoparticles for enhancing the rates of chemical reactions; the effect was shown recently to be predominantly associated with the elevated temperature caused by illumination. Here, we study the parametric dependence of the temperature distribution in these samples, and provide analytic expressions for simple cases. We show that since these systems are usually designed to absorb all the incoming light, the temperature distribution in them is weakly-dependent on the illumination spectrum, pulse duration, particle shape, size and density. Thus, changes in these parameters yield at most modest quantitative changes. We also show that the temperature distribution is linearly dependent on the beam radius and the thermal conductivity of the host. Finally, we study the sensitivity of the reaction rate to these parameters as a function of the activation energy and interpret various previous experimental reports. These results would simplify the optimization of photocatalysis experiments, as well as for other energy-related applications based on light harvesting for heat generation

The photothermal nonlinearity in plasmon-assisted photocatalysis

We show that the temperature rise in large ensembles of metal nanoparticles under intense illumination is dominated by the temperature dependence of the thermal conductivity of the host, rather than by the optical properties of the metal or the host. This dependence typically causes the temperature rise to become sublinear, with this photothermal nonlinear effect becoming unusually strong, reaching even several tens of percent. We then show that this can explain experimental observations in several recent plasmon-assisted photocatalysis experiments. This shows that any claim for dominance of non-thermal electrons in plasmon-assisted photocatalysis must account for this photothermal nonlinear mechanism

An electronic-based model of the optical nonlinearity of low-electron-density-Drude materials

Low electron density Drude (LEDD) materials such as indium tin oxide (ITO) are receiving considerable attention because of their combination of CMOS compatibility, unique epsilon-near-zero (ENZ) behavior, and giant ultrafast nonlinear thermo-optic response. However, the understanding of the electronic and optical response of LEDD materials is so far based on simplistic extensions of known models of noble metals, frequently without the inclusion of the interplay among the lower electron density, relatively high Debye energy, and the non-parabolic band structure. To bridge this knowledge gap, this work provides a complete understanding of the nonlinear electronic-thermal-optical response of LEDD materials. In particular, we rely on state-of-the-art electron dynamics modeling, as well as the newly derived time-dependent permittivity model for LEDD materials under optical pumping within the adiabatic approximation. We find that unlike noble metals, the electron temperatures can reach the Fermi temperature, in which case the effective chemical potential dramatically decreases and even becomes negative, thus, transiently converting the Drude metal into a semiconductor. We further show that the nonlinear optical response of LEDD materials originating from the changes to the real part of the permittivity is due to the generation of non-thermal electrons. This resolves the argument about the rise time of the permittivity and shows that it is instantaneous. In this vein, we show that referring to the LEDD permittivity as having a ``saturable'' nonlinearity is unsuitable since its permittivity dynamics does not originate from population inversion. Finally, we analyze the probe pulse dynamics and unlike previous work, we obtain a quantitative agreement with the results of recent experiments

The electronic and thermal response of low electron density Drude materials to ultrafast optical illumination

Many low electron density Drude (LEDD) materials such as transparent conductive oxide or nitrides have recently attracted interest as alternative plasmonic materials and future nonlinear optical materials. However, the rapidly growing number of experimental studies has so far not been supported by a systematic theory of the electronic, thermal and optical response of these materials. Here, we use the techniques previously derived in the context of noble metals to go beyond a simple electromagnetic modelling of low electron density Drude materials and provide an electron dynamics model for their electronic and thermal response. We find that the low electron density makes momentum conservation in electron-phonon interactions more important, more complex and more sensitive to the temperatures compared with noble metals; moreover, we find that electron-electron interactions are becoming more effective due to the weaker screening. Most importantly, we show that the low electron density makes the electron heat capacity much smaller than in noble metals, such that the electrons in LEDD materials tend to heat up much more and cool down faster compared to noble metals. While here we focus on indium tin oxide (ITO), our analytic results can be easily applied to any LEDD materials.Comment: Comments are welcome

Theory of Non-equilibrium "Hot" Carriers in Direct Band-gap Semiconductors Under Continuous Illumination

The interplay between the illuminated excitation of carriers and subsequent thermalization and recombination leads to the formation of non-equilibrium distributions for the "hot" carriers and to heating of both electrons, holes and phonons. In spite of the fundamental and practical importance of these processes, there is no theoretical framework which encompasses all of them and provides a clear prediction for the non-equilibrium carrier distributions. Here, a self-consistent theory accounting for the interplay between excitation, thermalization, and recombination in continuously-illuminated semiconductors is presented, enabling the calculation of non-equilibrium carrier distributions. We show that counter-intuitively, distributions deviate more from equilibrium under weak illumination than at high intensities. We mimic two experimental procedures to extract the carrier temperatures and show that they yield different dependence on illumination. Finally, we provide an accurate way to evaluate photoluminescence efficiency, which, unlike conventional models, predicts correctly the experimental results. These results provide a starting point towards examining how non-equilibrium features will affect properties hot-carrier based application.Comment: Version accepted in New Journal of Physic

The role of heat generation and fluid flow in plasmon-enhanced reduction-oxidation reactions

Recently, we have shown that thermal effects play a crucial role in speeding up the rate of bond-dissociation reactions. This was done by applying a simple temperature-shifted Arrhenius Law to the experimental data, corroborated with detailed account of the heat diffusion occurring within the relevant samples and identification of errors in the temperature measurements. Here, we provide three important extensions of our previous studies. First, we analyze thermal effects in reduction-oxidation (redox) reactions, where charge transfer is an integral part of the reaction. Second, we analyze not only the spatial distribution of the temperature, but also its temporal dynamics. Third, we also model the fluid convection and stirring. An analysis of two exemplary experimental studies allows us to show that thermal effects can explain the experimental data in one of experiments (Baumberg and coworkers), but not in the other (Jain and coworkers), showing that redox reactions are not necessarily driven by non-thermal charge carriers