Single quantum emitters play a fundamental role in the development of quantum technologies such as quantum repeaters, and quantum information processing. Isolating individual molecules with stable optical emission is an essential step for these applications, specially for those molecules that present large coherence times at room temperature. Among them, vanadium-oxide phthalocyanine (VOPc) molecules stand out as promising candidates due to their large coherence times measured in ensemble. However, the optical properties of individual molecules have not yet been reported. Here we show that single VOPc molecules with stable optical properties at room temperature can be isolated. We find that the optical response of the molecule under laser illumination of different polarization agrees well with a system having pyramidal C$_{4v}$ symmetry. Furthermore, the molecule reveals a non-radiative transition rate that depends on the excitation wavelength when its lifetime is interrogated. We provide theoretical calculations that support our experimental findings and provide insight to the role of phonons and internal electronic structure of the molecule. These results demonstrate that this single paramagnetic molecule can function as a single quantum emitter while displaying optical stability under ambient conditions to have their intrinsic properties investigated.
Single quantum emitters play a fundamental role in the development of quantum technologies such as quantum repeaters, and quantum information processing. Isolating individual molecules with stable optical emission is an essential step for these applications, specially for those molecules that present large coherence times at room temperature. Among them, vanadium-oxide phthalocyanine (VOPc) molecules stand out as promising candidates due to their large coherence times measured in ensemble. However, the optical properties of individual molecules have not yet been reported. Here we show that single VOPc molecules with stable optical properties at room temperature can be isolated. We find that the optical response of the molecule under laser illumination of different polarization agrees well with a system having pyramidal C4v symmetry. Furthermore, the molecule reveals a non-radiative transition rate that depends on the excitation wavelength when its lifetime is interrogated. We provide theoretical calculations that support our experimental findings and provide insight to the role of phonons and internal electronic structure of the molecule. These results demonstrate that this single paramagnetic molecule can function as a single quantum emitter while displaying optical stability under ambient conditions to have their intrinsic properties investigated.
Single quantum emitters play a fundamental role in the development of quantum technologies such as quantum repeaters, and quantum information processing. Isolating individual molecules with stable optical emission is an essential step for these applications, especially for those molecules that present large coherence times at room temperature. Among them, vanadium-oxide phthalocyanine (VOPc) molecules stand out as promising candidates due to the large coherence times of their ground state electronic spin, which are on the order of microseconds when measured in the ensemble. However, the optical properties of such VOPc molecules at the single emitter level have not yet been reported. Here we show that single VOPc molecules with stable optical properties at room temperature can be isolated. We find that the optical response of the molecule under laser illumination of different polarizations agrees well with a system having pyramidal C 4 v symmetry. Furthermore, we provide theoretical calculations that support our experimental findings and provide insight into the role of phonons and the internal electronic structure of the molecule. These results demonstrate that this single paramagnetic molecule can function as a single quantum emitter while displaying optical stability under ambient conditions to have their intrinsic properties investigated.
ingle luminescent molecules provide a unique approach in the development of quantum technologies utilizing single photon sources. This includes quantum metrology by using a molecule’s sensitivity of its emission and magnetic properties to the local environment. In this thesis, we present our investigation of the optical properties of several different classes of luminescent molecules. We begin by providing some theoretical background of single quantum emitters as well as a brief description of the experimental methodologies and equipment. Next, we present an optical investigation of an ensemble of iron phthalocyanines molecules. This molecule possesses a ground state triplet, which is a desirable property for optically active spin qubits, but has a very weak optical emission. Diffraction limited spots displayed photo-instability in the form of blinking and irreversible bleaching. In ensemble form however, their optical stability allowed us to identify a possible Raman peak where we calculated the associated phonon frequency. Next, we present our single molecule study of vanadium phthalocyanine. This molecule has been documented as displaying very long spin coherence times even at room temperatures. We confirmed the presence of a single molecule by measuring the second order correlation function. Additionally, we looked at the intensity and spectral response as a function of the excitation laser polarization. The spectrum was fitted to a two Gaussian function, which may correspond to the two dipole transitions as suggested by theoretical calculations. Lastly, we looked at the optical properties of rare earth europium complexes known for having very sharp optical transitions in the emission spectrum, with each having varying levels of sensitivity to the local environment. Motivated by techniques to investigate non-radiative decay channels, we looked at the optical response of four different europium complexes under two 1 µs pulses of 515 nm laser separated by 1 µs. Each displayed a very different results and allowed us to identify the best candidates for single molecule studies. Finally, we looked at the emission spectrum as well as the optical response under a 6 µs long pulse using time-correlation single photon spectroscopy.
Organic chemistry offers the potential to synthesize individual molecules for specific tasks in quantum information processing. One of their striking properties is the emission of single photons with nearly ideal coherence. Here, we implement Ramsey spectroscopy to measure the electronic state coherence of a single molecule. Conventionally, the emitter’s coherence is characterized by saturation or intensity auto-correlation measurements. However, both methods are under the steady influence of continuous interaction with the excitation laser. This influence can be eliminated by using a pump–probe sequence of two optical pulses to observe the decoherence. We have measured a near-transform-limited decoherence time of 17.6 ns, while the radiative lifetime is 10.1 ns. We also perform frequency-detuned excitation, gaining richer insights into the dephasing behavior of the molecule. The experiments exhibit that optical Ramsey spectroscopy is a promising tool for measuring the emitter’s coherence properties.
Single photons are highly desirable for encoding, sending and processing quantum information. Suitable engineering of single quantum emitters and their environment can lead to a reliable single photon source and to mediated photon-photon interactions, essential assets for quantum communication and computation purposes. Dye molecules, our chosen single quantum emitter, have attracted much attention in recent years due to their high photostability and narrow emission lines. In this thesis I present a detailed analysis of the optical properties of single dibenzoterrylene molecules in an anthracene matrix. Single photon emission is demonstrated at room and cryogenic temperatures. In the latter case, an analysis of the second-order correlation function of the emission of a single molecule is studied at various temperatures. The data agree with a full solution of the optical Bloch equations over a wide range of temperature, and provide some insight into the dephasing process of the molecules. I then present a technique for integrating single dye molecules with nano-photonic devices. These are hybrid plasmonic waveguides, designed to guide light and to enhance the interaction with a single emitter by a tight confinement of the waveguide mode. Single molecules are deposited over the waveguides and a first evidence of coupling is presented. I conclude with proposed improvements to the optical setup and to the deposition methods. Finally, I present another type of integrated device, where the light matter interaction is enhanced by inserting single quantum emitters into coupled optical resonators. The theoretical description for the case of resonant two-photon absorption from single atoms in coupled photonic crystal cavities is developed. I conclude by proposing a possible realisation of this system, and describing the first steps towards the fabrication of such a device.
Optical interfaces that connect long-lived spin qubits to photons are a central requirement for quantum networking and distributed quantum information processing. Currently, solid-state atomic defects are leading candidates due to their inherent spin and optical coherence. Building on these advancements, synthetically tailored molecular systems represent a fundamental change in the field, utilizing precise atomic control and consistent bottom-up assembly. However, the lack of a robust spin-photon interface combining bright fluorescence, high spectral stability, and the persistent spin lifetimes inherent to ground-state systems has prohibited the detection of individual molecular qubits. Here we show that a triplet ground state carbene molecule, embedded within a structurally matched host crystal, functions as a robust spin-photon interface with single-molecule addressability. The system exhibits narrow zero-phonon lines, spectral stability over more than an hour, spin-selective optical transitions and single-molecule optically detected magnetic resonance. Coherent control yields millisecond-scale dynamical-decoupling coherence and tens-of-milliseconds spin relaxation at a temperature of 4.5 K. These results establish molecular qubits as a viable platform for single-emitter quantum optics while preserving the advantages of bottom-up chemical design and processable materials.
The generation of non-classical states of light [1] is an important scientific challenge with many potential applications. For example, squeezed states of light [2] have generated much interest in the past decade, because measurements can be performed with noise levels that are lower than those available with classical light. A particularly novel non-classical source of light is a triggered single-photon source: a source that has the property to emit with a high degree of certainty one (and only one) photon at a user-specified time. Such a deterministic source of single photons can be important for quantum information processing [3], quantum cryptography [4] and certain quantum computation problems [5]. A single quantum emitter such as a molecule or an atom is a good potential source because it can emit only one photon at a time. The emitted light is antibunched [6, 7] and consists of single photons separated by random time intervals, which depend on the excited state lifetime and on the pumping rate. Thus triggered emission of single photons can be obtained with controlled excitation of a single emitter. The first demonstration of a single photons source [8] using a single molecule in a solid is based on a rapid adiabatic passage method [9] to excite the molecule. In the effective spin picture, the Bloch vector follows the driving magnetic field adiabatically if the laser-molecule frequency detuning is swept slowly through the resonance. Since the passage inverts the field, the system goes from the ground to the excited state. From this fluorescent state the molecule can emit only a single photon. The molecular resonance is swept by Stark effect at fixed laser frequency. This is done easily by applying a radio frequency electric field to the molecule. The results showed photon states with statistics that differ radically from those of coherent states. But this method requires cryogenic temperatures (2K) since narrow zero phonon lines are needed for the adiabatic following. At room temperature a source of triggered single photons based on the concept of pulsed optical excitation of a single highly fluorescent molecule has been demonstrated [10]. A short pulse of green laser light pumps the molecule from the ground state to a vibronically excited level of the first electronic excited state. After fast (ps) relaxation to the lowest electronic excited state, the molecule subsequently emits a single photon. A frequency-doubled mode-locked Nd-YAG laser is used to pump highly stable single terrylene molecules contained in a p-terphenyl molecular crystal where they are protected from exposure to diffusing quenchers (such as oxygen). The result shows that the photons are emitted after the laser pulses at times separated by the laser repetition time within the lifetime of terrylene in p-terphenyl. Since the pump pulse width is very short compared to the fluorescence lifetime, the probability of two (or more) photon emission per pulse is always zero. At the maximum laser power, 90% of the laser pulses lead to a single photon emission. The parameters of this source (repetition rate and single photon generation probability) were limited only by the laser system used; nevertheless, this performance already surpasses that of previous work. The high performance combined with the vanishing two photon emission probability and the simplicity of this source suggests that it can be considered for a variety of quantum optical experiments and for secure quantum cryptography [11]. Semiconductor quantum dots (QD) are other potential systems for single photon generation [12]. QDs are often referred to as “artificial atoms” because many of their optical properties, such as ultranarrow transitions, arise from discrete, atomic-like energy levels [13, 14]. To reinforce this analogy a study of the photon antibunching in this system was needed. QDs differ from atoms and molecules since the creation of multiple excitons is possible in QDs. Consequently, if two electron-hole pairs can radiatively recombine, the simultaneous emission of two photons from a QD is then possible. Thus different regimes of photon statistics were expected because the probability of multiple exciton creation depends on excitation intensity. The fluorescence intensity correlation function of a single CdSe quantum dot has been investigated [15] using a coincidence setup (start-stop experiment). A strong photon antibunching has been observed over a large range of intensities (0.1-100 kW/cm2). The lack of coincidence at zero time delay indicates a highly efficient Auger ionization process [16], which suppresses multi-photon emission in these colloidal quantum dots. This result shows that room temperature single photon sources can be achieved with colloidal nanoparticles.