The combination of single particle detection and ultrafast laser pulses is an instrumental method to track dynamics at the femtosecond time scale in single molecules, quantum dots and plasmonic nanoparticles. Optimal control of the extremely short-lived coherences of these individual systems has so far remained elusive, yet its successful implementation would enable arbitrary external manipulation of otherwise inaccessible nanoscale dynamics. In ensemble measurements, such control is often achieved by resorting to a closed-loop optimization strategy, where the spectral phase of a broadband laser field is iteratively optimized. This scheme needs long measurement times and strong signals to converge to the optimal solution. This requirement is in conflict with the nature of single emitters whose signals are weak and unstable. Here we demonstrate an effective closed-loop optimization strategy capable of addressing single quantum dots at room temperature, using as feedback observable the two-photon photoluminescence induced by a phase-controlled broadband femtosecond laser. Crucial to the optimization loop is the use of a deterministic and robust-against-noise search algorithm converging to the theoretically predicted solution in a reduced amount of steps, even when operating at the few-photon level. Full optimization of the single dot luminescence is obtained within ~100 trials, with a typical integration time of 100 ms per trial. These times are faster than the typical photobleaching times in single molecules at room temperature. Our results show the suitability of the novel approach to perform closed-loop optimizations on single molecules, thus extending the available experimental toolbox to the active control of nanoscale coherences. Femtosecond laser control allows to harness short-lived coherences and study molecular ultrafast dynamics. Translating such coherent-control schemes from the ensemble to single molecules is challenging due to signal fluctuation and photo-dissociation. Now, Nicolò Accanto and Pablo de Roque from ICFO - the Institute of Photonic Sciences in Barcelona, and colleagues, have reduced the time needed to perform closed-loop optimisations. By employing a new simple deterministic algorithm, and assuming simple optimisation landscapes, they accomplished a phase-only optimisation of the two-photon photoluminescence of a single quantum dot. Combining this rapid feedback process within the search algorithm with a sensitive microscopy technique, they were able to optimise on signals even at the few-photon level, enabling the coherent control of individual quantum-dots at room temperature in a matter of seconds - a speedup critical for capturing details of biomolecular interactions, for instance.
The combination of single particle detection and ultrafast laser pulses is an instrumental method to track dynamics at the femtosecond time scale in single molecules, quantum dots and plasmonic nanoparticles. Optimal control of the extremely short-lived coherences of these individual systems has so far remained elusive, yet its successful implementation would enable arbitrary external manipulation of otherwise inaccessible nanoscale dynamics. In ensemble measurements, such control is often achieved by resorting to a closed-loop optimization strategy, where the spectral phase of a broadband laser field is iteratively optimized. This scheme needs long measurement times and strong signals to converge to the optimal solution. This requirement is in conflict with the nature of single emitters whose signals are weak and unstable. Here we demonstrate an effective closed-loop optimization strategy capable of addressing single quantum dots at room temperature, using as feedback observable the two-photon photoluminescence induced by a phase-controlled broadband femtosecond laser. Crucial to the optimization loop is the use of a deterministic and robust-against-noise search algorithm converging to the theoretically predicted solution in a reduced amount of steps, even when operating at the few-photon level. Full optimization of the single dot luminescence is obtained within ~100 trials, with a typical integration time of 100 ms per trial. These times are faster than the typical photobleaching times in single molecules at room temperature. Our results show the suitability of the novel approach to perform closed-loop optimizations on single molecules, thus extending the available experimental toolbox to the active control of nanoscale coherences. Femtosecond laser control allows to harness short-lived coherences and study molecular ultrafast dynamics. Translating such coherent-control schemes from the ensemble to single molecules is challenging due to signal fluctuation and photo-dissociation. Now, Nicolò Accanto and Pablo de Roque from ICFO - the Institute of Photonic Sciences in Barcelona, and colleagues, have reduced the time needed to perform closed-loop optimisations. By employing a new simple deterministic algorithm, and assuming simple optimisation landscapes, they accomplished a phase-only optimisation of the two-photon photoluminescence of a single quantum dot. Combining this rapid feedback process within the search algorithm with a sensitive microscopy technique, they were able to optimise on signals even at the few-photon level, enabling the coherent control of individual quantum-dots at room temperature in a matter of seconds - a speedup critical for capturing details of biomolecular interactions, for instance.
Ultrafast pulses allow observation of molecular dynamics with femtosecond time resolution through pump probe experiments. However, averaging over an ensemble of molecules tends to wash out phase sensitive information, necessary to probe quantum effects, due to the intrinsic inhomogeneity in molecular conformations, orientations and interactions that lead to unique potential energy landscapes for each molecule. It is therefore important to go beyond the ensemble average when looking at quantum dynamics of organic systems at room temperature, and resolve the behaviour of specific molecules on an individual basis. In this thesis, we show the creation, manipulation and observation of ultrafast coherent effects in single molecules at room temperature, and resolve a certain measure of environmental influence on the specific dynamics of each molecule. Moreover, we apply this insight to investigate a functional light harvesting biosystem, and lay the basis for a technique that has the time and space resolution required to observe these systems in vivo. In chapter 1, we introduce the concepts and techniques the research in this thesis is built on. In chapter 2, we treat the possibility of controlling ultrafast pulses at the high-NA diffraction limit, and come to conclusions about the procedure to follow there that hold for all pulse-shaping experiments. We show in proof of principle experiments that we can control the ultrafast characteristics of optical pulses in nanometric excitation volumes. In chapters 3 and 4 we report the creation, detection and control of ultrafast quantum dynamics in single organic molecules at room temperature. We show that manipulation of superposition states is possible in these systems within a coherence dephasing time of ~50 fs. This leads to the first observation of rabi-oscillations in room temperature single molecules, to ultrafast operation of an organic qubit, and to the creation of non-stationary superposition states (vibrational wavepackets). We probe the influence of the local environment on the composition and dynamics of these wavepackets and show we can optimize the state preparation protocol for each individual molecule in its own nanoenvironment, leading to high fidelity coherent control. In these chapters we lay out the proof of principle work of detecting the quantumdynamics of a complex system in interaction with its environment at room temperature. In chapter 5 we discuss application of these techniques to the investigation of long lived coherence in photosynthetic systems. We show that electronic coherence between different rings of the LH2 system persists to time scales of 100s of femtoseconds at room temperature. Moreover we show that the energy transfer pathways in LH2 adapt to environmentally induced changes in the molecule and that the nature of the transfer remains coherent for each pathway, providing strong evidence that coherent energy transfer is the optimum process for energy transfer in photosynthesis. Finally, in chapter 6 we take the technical development one step further and report on the creation of a framework based on plasmonic antennas that allows for control of the amplitude-phase characteristics in nanometric sized hotspot fields. We show for the first time that the ultrafast characteristics of plasmonic hotspots can directly be engineered through design of the plasmonic system and experimentally demonstrate two much-anticipated examples: a sub-diffraction resolution phase shaper and an ultrafast plasmonic switch for pump probe experiments. The results presented in this thesis form the first creation and observation of ultrafast coherent dynamics in individual molecular systems at room temperature. This is a necessary step to be able to do true quantum tomography in complex systems, resolve the influence of the environment on molecular dynamics, and investigate the physics that determines evolutionary optimization and functionality in biomolecules.
Quantum technologies are widely expected to bring a revolution in communications and information technologies in the coming decade allowing, for example, un-paralleled levels of secure communications. For quantum communication, photonic quantum effects have played a central role, but most photonic solutions and systems based on light-matter interaction also require cryogenic environments. Strong coupling of light and matter at the single emitter level is a fundamental quantum resource offering deterministic energy exchange between single photons and a two-level system, and the possibility to achieve single-photon nonlinearities via the anharmonicity of the Jaynes-Cummings ladder. Until recently, however, the conditions for achieving strong-coupling were most commonly met at cryogenic temperatures such that de-coherence processes are suppressed. As a major step forward, we have recently demonstrated room-temperature strong coupling of single molecules [1] and single quantum dots [2] to ultra-confined light fields in plasmonic resonators at ambient conditions. The fact that strong-coupling conditions may be reached at room temperature is of immense interest because it represents a clear route to a practical implementation and use of quantum behaviour in nanophotonic systems and its application in bio-sensing [3]. The talk will discuss how nanoplasmonics can be an enabler of ultrafast room-temperature quantum nanophotonic networks via strong coupling and ultrafast quantum dynamics [4]. We will highlight the physics associated with recently demonstrated room-temperature strong coupling of single molecules in a plasmonic nano-cavity [1] and near-field generated strong coupling of single quantum dots [2] and single quantum emitter Dicke enhancement [5] paving the road towards single-photon quantum nonlinearities. The presentation will also explain near-field enhanced single-photon emission in near-zero index materials [6] and ultrafast multi-partite quantum entanglement [7]. This provides the foundation for unprecedented control over photon number, single photon dynamics, and dynamic multi-photon coherence. These properties are all imperative for the development of next-generation, nanoscale building blocks in ambient-temperature photonic quantum communication technologies.
Coherent control, a central concept in physics and chemistry, has sparked significant interest due to its ability to fine-tune interference effects in atoms and individual molecules for applications ranging from light-harvesting complexes to molecular qubits. However, precise characterization of the system's dissipative dynamics is required for its implementation, especially at high temperature. In a quantum control experiment, this means learning system-bath parameters and driving coupling strengths. Here, we demonstrate how to infer key physical parameters of a single molecule driven by spectrally modulated pulses at room temperature. We develop and compare two computational approaches based on two-photon absorption photoluminescence signals: an optimization-based minimization scheme and a feed-forward neural network. The robustness of our approach highlights the importance of reliable parameter estimation in designing effective coherent control protocols. Our results have direct applications in ultrafast spectroscopy, quantum materials and technology.
Semiconductor quantum dots have been featured in a number of proposals for quantum computing because of the advantages afforded by confinement on the nanoscale, such as well separated, discrete energy levels and ease of optical manipulation. In addition, they can leverage established semiconductor fabrication techniques and, like the quantum dots used in this work, can be designed to match the telecommunication band, improving the scalability and potential integration of the platform into existing technologies. This thesis work applied optical pulse engineering to manipulate exciton qubits in self-assembled InAs quantum dots. Optimal quantum control theory was used to design pulse shapes that implement high fidelity single-qubit and two-qubit operations, with constraints on the numerical optimization that ensure that the pulses can be accurately implemented using a commercial 4f pulse shaper. In the case of single-qubit operations, the results showed that two uncoupled qubits can be manipulated in parallel using a single phase-shaped laser pulse, provided their optoelectronic properties are sufficiently different. It was demonstrated that targeted differences in inversion and phase between the qubits can be achieved on an ultrafast timescale with high fidelity. In the case of two-qubit operations, the controlled-rotation gate was optimized using amplitude-only and phase-only pulse shaping schemes. The shaped pulses for both schemes were shown to produce higher fidelity operations. The ability to implement robust state inversion on short timescales is particularly useful for technologies such as ultrafast optical switches, single-photon sources, and entangled-photon sources. This work has demonstrated state inversion in a single InAs quantum dot via adiabatic rapid passage using linearly chirped laser pulses. The achieved gate times were an order of magnitude shorter than previous demonstrations. Theoretical predictions of the dependence of the inversion efficiency of the exciton on the sign of the pulse chirp were also verified experimentally, allowing for the identification of phonon-mediated dephasing as the dominant source of decoherence.
Coherent control, a central concept in physics and chemistry, has sparked significant interest due to its ability to fine-tune interference effects in atoms and individual molecules for applications ranging from light-harvesting complexes to molecular qubits. However, precise characterization of the system's dissipative dynamics is required for its implementation, especially at high temperatures. In a quantum control experiment, this means learning system-bath parameters and driving coupling strengths. Here, we demonstrate how to infer key physical parameters of a single molecule driven by spectrally modulated pulses at room temperature. We develop and compare two computational approaches based on two-photon absorption photoluminescence signals: an optimization-based minimization scheme and a feed-forward neural network. The robustness of our approach highlights the importance of reliable parameter estimation in designing effective coherent control protocols. Our results have direct applications in ultrafast spectroscopy, quantum materials, and technology.
Since its first development and applications in the early 1990s, single molecule detection demonstrated to be a powerful tool for a wide range of studies, ranging from biophysics to quantum optics. However, this approach has been limited so far to species with high fluorescence quantum yield. Over the past few years, we have developed extinction detection and spectroscopy as an alternative to fluorescence for investigating single nano-objects such as metallic nanoparticles, viruses, dye molecules, and quantum dots [1-5]. The contrast mechanism at work in this coherent scheme can be understood as the interference between the incident beam and the light scattered by the nano-object. We showed that the sensitivity of this technique can be pushed to detect single semiconductor nanocrystals at room temperature and measured the absorption cross section of a single quantum dot before and after photobleaching as well as during the on and off photo-blinking times [4]. Here, I will concentrate on the recent improvements of such technique which allowed the direct detection and imaging of a single molecule by optical absorption at room temperature [6, 7]. Through a transmission microscopy setup in an index-matched configuration we were able to suppress the background scattering and shot-noise fluctuations below the part per million. Additionally, by means of three distinct approaches, the residual background fluctuations produced by the environment could be suppressed to about 1 × 10 -6 RMS. This allowed us to recover the extinction/absorption dip produced by a single molecule (Terrylene Diimide, TDI) on an impinging laser beam which can be evaluated to be about 3 × 10 -6 . Thanks to these background-subtraction methods, which allowed to extract the pure absorption signal, we could also exactly determine exactly the absorption cross section of TDI [7], which turned to be in good agreement with an evaluation made upon the ensemble cross-section. In this framework, we also demonstrated that spectroscopy at the single molecule level is within reach [7]. This simple contrast technique will allow interrogating a large class of nano-object and studying the photophysics of all the species which do not fluoresce or do so with very low quantum efficiency.