Managed single-electron switch permits time-resolved excited-state spectroscopy of particular person molecules

Set-up and pattern preparation

Experiments have been carried out with a home-built atomic power microscope outfitted with a qPlus sensor³³ (resonance frequency, f₀ = 30.0 kHz; spring fixed, okay ≈ 1.8 kNm⁻¹; high quality issue, Q ≈ 1.9 × 10⁴) and a conductive Pt-Ir tip. The microscope was operated beneath ultrahigh vacuum (base stress, P < 10⁻¹⁰ mbar) at T ≈ 8 Ok in frequency-modulation mode, during which the frequency shift (Delta f) of the cantilever resonance is measured. The cantilever amplitude was 1 Å (2 Å peak-to-peak). AC-STM photographs¹⁰ have been taken in constant-height mode, at a diminished tip top as indicated by the destructive Δz values (tip-height change with respect to the set level).

As a pattern substrate, an Ag(111) single crystal was used that was ready by sputtering and annealing cycles (annealing temperature, T ≈ 600 °C). A thick NaCl movie (>20 ML) was grown on half of the pattern at a pattern temperature of roughly 80 °C. As well as, a sub-ML protection of NaCl was deposited on the whole floor at a pattern temperature of roughly 35 °C. The tip was ready by indentation into the remaining naked Ag(111) floor, presumably overlaying the tip apex with Ag. The measured molecules (pentacene and PTCDA) have been deposited in situ onto the pattern contained in the scan head at a temperature of roughly 8 Ok.

The a.c. voltage pulses have been generated by an arbitrary waveform generator (Pulse Streamer 8/2, Swabian Devices), mixed with the d.c. voltage, fed to the microscope head by a semi-rigid coaxial high-frequency cable (Coax Japan) and utilized to the steel substrate as a gate voltage ({V}_{{rm{G}}}). The high-frequency elements of the pulses of ({V}_{{rm{G}}}) result in spikes within the AFM sign due to the capacitive coupling between the pattern and the sensor electrodes. To compensate these spikes, we utilized the identical pulses with reverse polarity and adjustable magnitude to an electrode that additionally capacitively {couples} to the sensor electrodes. Reflections and resonances within the gate-voltage circuitry have been averted by impedance matching, absorptive cabling and limiting the bandwidth of the exterior circuit to roughly 50 MHz. Experimental checks confirmed no indication of extreme waveform distortions.

Spectroscopy pulse sequence and knowledge acquisition

The spectra proven in Figs. 2–4 and Supplementary Figs. 2–4 and 7–10 have been measured utilizing a voltage pulse sequence just like the one proven in Fig. 2a, as detailed within the captions of the figures.

To initialize within the D₀⁺ state, the set-pulse voltage and length have been chosen such that it reliably brings the molecule on this state. We selected, due to this fact, a set pulse with a voltage that exceeds the comfort power for the S₀ → D₀⁺ transition having a length that’s for much longer than the decay fixed of this transition. Particularly, a set-pulse voltage was chosen that’s 1 V decrease than the D₀⁺–S₀ degeneracy level, having a length of 33.4 µs (one cantilever interval). To initialize within the S₀ and T₁ states (for instance, in Fig. 4), the set-pulse sequence consists of two components: a pulse to deliver the molecule to D₀⁺ (the identical parameters are used as for the heartbeat used to initialize in D₀⁺) and one other pulse to subsequently deliver the molecule within the T₁ state. The second pulse is at −0.3 V (Fig. 4a,d, pentacene) (basically, it was set to V_read-out + 2.5 V for pentacene) or −1.8 V (Fig. 5d, PTCDA), respectively. Word that this pulse sequence has the identical impact because the set and sweep pulse for the info at −0.3 V in Fig. 3a or −1.8 V in Fig. 5a, respectively. The length of the second pulse determines the ratio of inhabitants of the T₁ and S₀ states, because the T₁ state will decay throughout this pulse to the S₀ state in keeping with its molecule-specific lifetime. On the finish of a 33.4 µs lengthy second pulse of the set-pulse sequence with V_set = −0.3 V, the T₁ and S₀ inhabitants is 0.51 ± 0.01 and 0.49 ± 0.01, respectively, in case of pentacene in Fig. 4. In contrast, the identical set-pulse size with V_set = −1.8 V provides a T₁ and S₀ inhabitants of 0.79 ± 0.01 and 0.21 ± 0.01, respectively, for PTCDA in Fig. 5d. Supplementary Fig. 3 reveals knowledge for pentacene with totally different preliminary populations of the T₁ and S₀ states. To this finish, pulse durations of 33.4 µs and 100.1 µs have been chosen.

A cantilever oscillation amplitude of 1 Å (2 Å peak-to-peak) was chosen to optimize the signal-to-noise ratio for charge-state detection³⁴. The oscillation amplitude modulates the tip top and thereby induces variations within the tunnelling price and slight variations within the lever arm of the gate voltage. To attenuate these results, the voltage pulses have been synchronized with the cantilever oscillation interval, such that they began 2 µs earlier than the turn-around level at minimal tip–pattern distance. Moreover, the sweep pulses have been chosen to be brief, such that the whole sweep pulse happens across the level of minimal tip–pattern distance. If this was not potential, full cantilever-period pulses have been chosen. The ensuing minor affect of the cantilever’s oscillation amplitude on the excited-state spectroscopy knowledge was uncared for within the modelling and, therefore, within the becoming. For instance, neglecting the cantilever’s oscillation doubtless causes the deviation between the match and the info proven in Fig. 5a between voltages (1) and (2) for t_sweep = 3.3 µs (yellow curve).

The tip top was chosen by setting the decay of D₀⁺ into S₀ at a voltage of 1 V above the voltage akin to the degeneracy of the D₀⁺ and S₀ states to round 1.5 µs. This tip top is sufficiently giant to reduce tunnelling occasions between the 2 bistable states throughout the read-out section of the heartbeat sequence, which supplies a decrease restrict to the tip–pattern top. The higher restrict of the tip–pattern top is given by the requirement that the tunnelling charges ought to be a lot quicker than the slowest triplet decay price. Sometimes, these two necessities limit the potential tip–pattern heights to a small vary (lower than 2 Å) across the comparatively giant tip–pattern top used (estimated to be 9 Å; Supplementary Part 7).

The shortest sweep pulse length was then chosen such that on the largest V_sweep used, the read-out fraction within the D₀⁺ state was round 0.10. This allowed the remark of transitions at constructive voltages, resembling (6) in Fig. 3a. In contrast, an extended sweep pulse length is essential for the remark of transitions (7), (1) and (8). The longest pulse length was, due to this fact, sometimes set such that the fraction within the D₀⁺ state was near zero at a voltage of 1 V above the voltage akin to the degeneracy of the D₀⁺ and S₀ states. Two or three further sweep pulse durations have been chosen in between the decided shortest and longest pulse length to enhance the reliability of the becoming.

To find out the inhabitants within the two cost states throughout the read-out, the voltage pulse sequences have been sometimes repeated 8 instances per second for 80 s for each sweep voltage. The error bars have been derived because the s.d. of the binominal distribution (see beneath). The measurements have been carried out in constant-height mode. To appropriate for vertical drift, for instance, owing to piezo creep, the tip–pattern distance was sometimes reset each 15 min by shortly turning on the Δf-feedback. Lateral drift was corrected each hour by taking an AC-STM picture (equally as described in ref. ¹⁵) and cross-correlating it with an AC-STM picture taken in the beginning of the measurement.

Knowledge evaluation

For knowledge evaluation, set off pulses synchronized with the pump–probe voltage pulses have been used to establish the beginning of each read-out interval (dotted strains in Fig. 2c). The remaining impact of the capacitive coupling described above in addition to a potential excitation of the cantilever owing to the few µs sweep voltage pulses could cause spikes in the beginning of each read-out interval (not current for the info in Fig. 2c), which have been faraway from the info hint. Subsequently, each read-out interval was low-passed and it was decided if the averaged frequency shift throughout this interval was above or beneath the worth centred between the frequency shifts of the 2 cost states. Counting the variety of read-out intervals for which the frequency shift was above this worth and dividing it by the entire variety of intervals provides the read-out fraction within the cost state. For the steel ideas that we’ve used, the D₀⁺ and D₀⁻ states at all times had a much less destructive frequency shift in contrast with S₀ (on the respective read-out voltage).

Error bars

The uncertainty on the decided read-out fraction within the cost state is dominated by the statistical uncertainty. Due to the 2 potential outcomes (charged or impartial), the statistics of a binomial distribution apply (ref. ¹⁶). The s.d. on the counts in a charged state N_c is, due to this fact, given by

with N₀ being the counts within the impartial state. The error bars on the measured fractions within the charged state are then given by

the place the second time period within the numerator accounts for the discrete nature of N_c.