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Experimental characterization techniques for plasmon-assisted chemistry

Abstract

Plasmon-assisted chemistry is the result of a complex interplay between electromagnetic near fields, heat and charge transfer on the nanoscale. The disentanglement of their roles is non-trivial. Therefore, a thorough knowledge of the chemical, structural and spectral properties of the plasmonic/molecular system being used is required. Specific techniques are needed to fully characterize optical near fields, temperature and hot carriers with spatial, energetic and/or temporal resolution. The timescales for all relevant physical and chemical processes can range from a few femtoseconds to milliseconds, which necessitates the use of time-resolved techniques for monitoring the underlying dynamics. In this Review, we focus on experimental techniques to tackle these challenges. We further outline the difficulties when going from the ensemble level to single-particle measurements. Finally, a thorough understanding of plasmon-assisted chemistry also requires a substantial joint experimental and theoretical effort.

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Fig. 1: Length scales and timescales in plasmon-assisted chemistry.
Fig. 2: Elementary steps/processes and associated timescales.
Fig. 3: Experimental techniques for probing the local electric field.
Fig. 4: Photoelectrochemical techniques to study charge-transfer processes.
Fig. 5: Solid-state techniques to measure photocurrent in plasmonic systems.
Fig. 6: Techniques to measure temperature in plasmon-assisted chemistry.
Fig. 7: Challenges and opportunities in plasmonic catalysis.

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Acknowledgements

S.A.M. and E.C. acknowledge funding and support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy (EXC2089/1-390776260), the Bavarian programme Solar Energies go Hybrid (SolTech) and the Center for NanoScience (CeNS). E.C. acknowledges support from the European Commission through the ERC Starting Grant CATALIGHT (802989). S.A.M. acknowledges the Lee-Lucas Chair in Physics. S.S. acknowledges funding and support from the DFG within the Collaborative Research Center ‘Non-equilibrium dynamics of condensed matter in the time domain’ (CRC 1242, project no. 278162697, project A04) and the project SCHL 594/17-1 (project no. 410889534).

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Glossary

Activation barrier

Corresponds to the energy needed for a chemical reaction to occur, since it is the energy difference between the activated complex/transition state and the reactants along the path of lowest energy on the potential energy surface. Referred to as Ea.

Rate constant

A measure for the speed of a chemical reaction (not to be mixed up with the reaction speed dc/dt itself) and it is a constant value for a given reaction temperature. Referred to as k.

Potential energy surface

Describes the potential energy of the system as a function of the positions of the nuclei and is normally used to visualize the relevant reaction coordinates for the progression from reactants via the transition state(s) to products.

Vibrational pumping

Significant increase in the population of higher excited vibrational states that may even exceed that of the vibrational ground state — such a non-equilibrium situation is, therefore, different from a thermal equilibrium described by the Boltzmann statistics.

Superlinear dependency

In the case of plasmon-assisted reactions, it means that, upon increasing the power of the incident light, the corresponding reaction rate grows in a nonlinear fashion, i.e. faster than linear.

Electron-beam lithography

A method frequently used in microconductor and semiconductor technology for structuring surfaces using electron-sensitive films.

Haber–Bosch process

Main industrial production process for the large-scale synthesis of ammonia from nitrogen and hydrogen at ca. 200 bar and ca. 450 °C using iron-based catalysts. Ammonia is a basic compound for the synthesis of many important chemicals, with relevance for fertilizers, plastics and synthetic fibres.

Wave vector

Describes the propagation direction of light as an electromagnetic wave and its value is inversely proportional to the wavelength.

Quantum cascade laser

Semiconductor-based lasers relying on intersubband transitions, normally emitting in the infrared spectral region. Laser-based infrared spectroscopy offers several advantages over conventional Fourier transform infrared spectroscopy using incoherent thermal electromagnetic radiation.

Optical parametric oscillator

By means of second-order nonlinear optical interaction, an optical parametric oscillator converts an input laser wave with a given frequency into two output waves of lower frequency. In this laser, the optical gain is produced in a parametric crystal rather than by a population inversion; tunability is achieved by orienting the nonlinear crystal with respect to the axis of an optical resonator. Therefore, optical parametric oscillators are widely exploited in modern laser spectroscopy.

Ohmic contacts

A common junction between a metal and a semiconductor with low electrical resistance, frequently employed in semiconductor physics/technology.

Schottky barriers

At a semiconductor–metal interface, the Schottky barrier is the energy difference between the valence (or conduction) band edge of the semiconductor and the Fermi energy of the metal.

Tunnel barriers

In this context, describes the potential barrier formed between two metals separated by a thin insulator, with the system acting as a tunnel junction that the electronic wave packet can tunnel through.

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Cortés, E., Grzeschik, R., Maier, S.A. et al. Experimental characterization techniques for plasmon-assisted chemistry. Nat Rev Chem 6, 259–274 (2022). https://doi.org/10.1038/s41570-022-00368-8

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