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Armbruster O, Pöhl H, Kautek W. Hot electron electrochemistry at silver activated by femtosecond laser pulses. Opto-Electron Adv 6, 220170 (2023). doi: 10.29026/oea.2023.220170
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Article Open Access
Hot electron electrochemistry at silver activated by femtosecond laser pulses
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Abstract
A silver microelectrode with a diameter of 30 µm in an aqueous K2SO4 electrolyte was irradiated with 55 fs and 213 fs laser pulses. This caused the emission of electrons which transiently charged the electrochemical double layer. The two applied pulse durations were significantly shorter than the electron-phonon relaxation time. The laser pulse durations had negligible impact on the emitted charge, which is incompatible with multiphoton emission. On the other hand, the observed dependence of emitted charge on laser fluence and electrode potential supports the thermionic emission mechanism.-
Keywords:
- hot electron emission /
- femtosecond laser /
- laser electrochemistry /
- silver electrode
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References
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Armbruster O, Pöhl H, Kautek W. Hot electron electrochemistry at silver activated by femtosecond laser pulses. Opto-Electron Adv 6, 220170 (2023). doi: 10.29026/oea.2023.220170
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Figure 1.
Calculated electron temperature Te of silver for various incident laser fluences F according to Equation (2) with γe = 62.8 J m−3 K−2, μ = 142 nm, and β = 0.15.
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Figure 2.
Block diagram of the laser-electrochemical system. μWE: silver working microelectrode; CE: platinum counter electrode; fs-CPO: femtosecond chirped pulse oscillator; E: laser pulse energy; τ: pulse duration; OBJ: microscope objective; R: 1 MΩ resistor; DAQ: digital-to-analog converter output; φ: applied electrode potential; HPA: high pass amplifier; Δφ: transient voltage signal; OSC: digital storage oscilloscope.
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Figure 3.
(a) Exemplary Δφ(t) transient voltage measurement averaged over 100 single laser pulses. τ = (55 ± 1) fs, F0 = (64 ± 7) mJ cm-2, ϕ = (–460 ± 40) mV vs. SHE. The inset enlarges the region around t = 0 and shows the extracted peak voltage change Δφ0 = (19.7 ± 0.1) mV. (b) Comparison of Δφ(t) transient voltage measurements recorded at various laser peak fluences F0.
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Figure 4.
Imaginary part X of an exemplary impedance measurement corresponding to the Δφ(t) transient in Fig. 3. The solid line shows the constant phase element fit.
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Figure 5.
Logarithmic plot of the emitted hot electron charge Q for two pulse durations, τ = (55 ± 1) fs (red circles) and τ = (213 ± 1) fs (blue stars), plotted over the applied electrode bias φ and peak laser fluence F0. The gray surface is calculated from Eq. (5) but for a constant factor with γe = 62.8 J m−3 K−2, μ = 142 nm, β = 0.15, and φ0 = 3.41 eV at 0 V vs. SHE.
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Figure 6.
Schematic electronic Fermi-Dirac distribution n on the metal and density of states (DOS) as function of the electronic energy ε of H3O+ and H0.
