Efficient Quadrature Squeezing from Biexcitonic Parametric Gain in Atomically Thin Semiconductors.

Modification of electromagnetic quantum fluctuations in the form of quadrature squeezing is a central quantum resource, which can be generated from nonlinear optical processes. Such a process is facilitated by coherent two-photon excitation of the strongly bound biexciton in atomically thin semiconductors. We show theoretically that interfacing an atomically thin semiconductor with an optical cavity makes it possible to harness this two-photon resonance and use the biexcitonic parametric gain to generate squeezed light with input power an order of magnitude below current state-of-the-art devices with conventional third-order nonlinear materials that rely on far off-resonant nonlinearities. Furthermore, the squeezing bandwidth is found to be in the range of several meV. These results identify atomically thin semiconductors as a promising candidate for on-chip squeezed-light sources.

Enhanced TEMPO Algorithm for Quantum Path Integrals with Off-Diagonal System-Bath Coupling: Applications to Photonic Quantum Networks.

Multitime system correlation functions are relevant in various areas of physics and science, dealing with system-bath interaction including spectroscopy and quantum optics, where many of these schemes include an off-diagonal system bath interaction. Here we extend the enhanced time-evolving matrix product operator (eTEMPO) algorithm for quantum path integrals using tensor networks [Phys. Rev. Lett. 123, 240602 (2019)PRLTAO0031-900710.1103/PhysRevLett.123.240602 to open quantum systems with off-diagonal coupling beyond a single two level system. We exemplify the approach on a coupled cavity waveguide system with spatially separated quantum two-state emitters, though many other applications in material science are possible, including entangled photon propagation, photosynthesis spectroscopy, and on-chip quantum optics with realistic dissipation.

Fermi's Golden Rule for Spontaneous Emission in Absorptive and Amplifying Media.

We demonstrate a fundamental breakdown of the photonic spontaneous emission (SE) formula derived from Fermi's golden rule, in absorptive and amplifying media, where one assumes the SE rate scales with the local photon density of states, an approach often used in more complex, semiclassical nanophotonics simulations. Using a rigorous quantization of the macroscopic Maxwell equations in the presence of arbitrary linear media, we derive a corrected Fermi's golden rule and master equation for a quantum two-level system (TLS) that yields a quantum pumping term and a modified decay rate that is net positive. We show rigorous numerical results of the temporal dynamics of the TLS for an example of two coupled microdisk resonators, forming a gain-loss medium, and demonstrate the clear failure of the commonly adopted formulas based solely on the local density of states.

Quantization of Quasinormal Modes for Open Cavities and Plasmonic Cavity Quantum Electrodynamics.

We introduce a second quantization scheme based on quasinormal modes, which are the dissipative modes of leaky optical cavities and plasmonic resonators with complex eigenfrequencies. The theory enables the construction of multiplasmon or multiphoton Fock states for arbitrary three-dimensional dissipative resonators and gives a solid understanding to the limits of phenomenological dissipative Jaynes-Cummings models. In the general case, we show how different quasinormal modes interfere through an off-diagonal mode coupling and demonstrate how these results affect cavity-modified spontaneous emission. To illustrate the practical application of the theory, we show examples using a gold nanorod dimer and a hybrid dielectric-metal cavity structure.

Size-dependent exciton substructure in CdSe nanoplatelets and its relation to photoluminescence dynamics.

CdSe nanoplatelets can be synthesized with different lateral sizes; very small nanoplatelets have almost quantum dot like features (almost discrete exciton states), while very large ones are expected to have properties of colloidal quantum wells (exciton continuum). However, nanoplatelets can be in an intermediate confinement regime with a rich substructure of excitons, which is neither quantum dot like nor an ideal 2D exciton. In this manuscript, we discuss the experimental transition energies and relaxation dynamics of exciton states in CdSe platelets with varying lateral dimensions and compare them with a microscopic theoretical model including exciton-phonon scattering. The model takes special care of the interplay of confinement and Coulomb coupling in the intermediate regime showing strong changes with respect to simple weak or strong confinement models by solving the full four dimensional lateral factorization free exciton wavefunction. Depending on the platelet size broad resonances previously attributed to just ground and excited states are actually composed of a rich substructure of several exciton states in their temporal dynamics. We show that these factorization free exciton states can explain the spectral features observed in photoluminescence experiments. Furthermore we demonstrate that the interplay of exciton bright and dark states provides principle insights into the overall temporal relaxation dynamics, and allows tuning of the exciton cooling via lateral platelet size. Our results and theoretical approach are directly relevant for understanding e.g. the size tuneability of lasing, excitonic cooling dynamics or light harvesting applications in these and similar 2D systems of finite lateral size.

Deconvolution of optical multidimensional coherent spectra.

Optical coherent multidimensional spectroscopy is a powerful technique for unraveling complex and congested spectra by spreading them across multiple dimensions, removing the effects of inhomogeneity, and revealing underlying correlations. As the technique matures, the focus is shifting from understanding the technique itself to using it to probe the underlying dynamics in the system being studied. However, these dynamics can be difficult to discern because they are convolved with the nonlinear optical response of the system. Inspired by methods used to deblur images, we present a method for deconvolving the underlying dynamics from the optical response. To demonstrate the method, we extract the many-particle diffusion Green's functions for excitons in a semiconductor quantum well from two-dimensional coherent spectra.

Quantized pseudomodes for plasmonic cavity QED.

We present a quantized pseudomode theory for solving system-level cavity quantum electrodynamics with quantum emitters coupled to plasmonic resonators. Exploiting the Green function response of a silver nanoparticle and an exact solution for the input-output coupling, we study the non-Markovian coupling regimes of multi-mode vacuum Rabi oscillations and coherently pumped multi-photon resonances from the higher lying ladder states of collective plasmon modes. The nonlinear pumping regime also facilitates pronounced population inversion of a single two-level atom through multiphoton resonances dominated by dark plasmons.

PsiQuaSP-A library for efficient computation of symmetric open quantum systems.

In a recent publication we showed that permutation symmetry reduces the numerical complexity of Lindblad quantum master equations for identical multi-level systems from exponential to polynomial scaling. This is important for open system dynamics including realistic system bath interactions and dephasing in, for instance, the Dicke model, multi-Λ system setups etc. Here we present an object-oriented C++ library that allows to setup and solve arbitrary quantum optical Lindblad master equations, especially those that are permutationally symmetric in the multi-level systems. PsiQuaSP (Permutation symmetry for identical Quantum Systems Package) uses the PETSc package for sparse linear algebra methods and differential equations as basis. The aim of PsiQuaSP is to provide flexible, storage efficient and scalable code while being as user friendly as possible. It is easily applied to many quantum optical or quantum information systems with more than one multi-level system. We first review the basics of the permutation symmetry for multi-level systems in quantum master equations. The application of PsiQuaSP to quantum dynamical problems is illustrated with several typical, simple examples of open quantum optical systems.

Neutral and charged inter-valley biexcitons in monolayer MoSe2.

In atomically thin transition metal dichalcogenides (TMDs), reduced dielectric screening of the Coulomb interaction leads to strongly correlated many-body states, including excitons and trions, that dominate the optical properties. Higher-order states, such as bound biexcitons, are possible but are difficult to identify unambiguously using linear optical spectroscopy methods. Here, we implement polarization-resolved two-dimensional coherent spectroscopy (2DCS) to unravel the complex optical response of monolayer MoSe2 and identify multiple higher-order correlated states. Decisive signatures of neutral and charged inter-valley biexcitons appear in cross-polarized two-dimensional spectra as distinct resonances with respective ∼20 and ∼5 meV binding energies-similar to recent calculations using variational and Monte Carlo methods. A theoretical model considering the valley-dependent optical selection rules reveals the quantum pathways that give rise to these states. Inter-valley biexcitons identified here, comprising of neutral and charged excitons from different valleys, offer new opportunities for developing ultrathin biexciton lasers and polarization-entangled photon sources.

Cavity assisted emission of single, paired and heralded photons from a single quantum dot device.

The photon emission into different spatial directions of a quantum dot in a micropillar cavity is theoretically analyzed. We propose two types of photon emission statistics from a single quantum light device: (i) single photon emission into the axial, strong coupling direction and a two-photon emission into the lateral, weak coupling direction, as well as (ii) the simultaneous use of both emission directions for the temporally ordered generation of two photons within a defined time-bin constituting a heralded single photon source. Our results open up exciting perspectives for solid state based quantum light sources, which can be generalized to any quantum emitter-microcavity system featuring spatially distinct emission channels between the resonator and unconfined modes.

Metal-Semiconductor Nanoparticle Hybrids Formed by Self-Organization: A Platform to Address Exciton-Plasmon Coupling.

Hybrid nanosystems composed of excitonic and plasmonic constituents can have different properties than the sum of of the two constituents, due to the exciton-plasmon interaction. Here, we report on a flexible model system based on colloidal nanoparticles that can form hybrid combinations by self-organization. The system allows us to tune the interparticle distance and to combine nanoparticles of different sizes and thus enables a systematic investigation of the exciton-plasmon coupling by a combination of optical spectroscopy and quantum-optical theory. We experimentally observe a strong influence of the energy difference between exciton and plasmon, as well as an interplay of nanoparticle size and distance on the coupling. We develop a full quantum theory for the luminescence dynamics and discuss the experimental results in terms of the Purcell effect. As the theory describes excitation as well as coherent and incoherent emission, we also consider possible quantum optical effects. We find a good agreement of the observed and the calculated luminescence dynamics induced by the Purcell effect. This also suggests that the self-organized hybrid system can be used as platform to address quantum optical effects.

Two-dimensional double-quantum spectra reveal collective resonances in an atomic vapor.

We report the observation of double-quantum coherence signals in a gas of potassium atoms at twice the frequency of the one-quantum coherences. Since a single atom does not have a state at the corresponding energy, this observation must be attributed to a collective resonance involving multiple atoms. These resonances are induced by weak interatomic dipole-dipole interactions, which means that the atoms cannot be treated in isolation, even at a low density of 10(12) cm(-3).

Line narrowing of excited-state transitions in nonlinear polarization spectroscopy: application to water-soluble chlorophyll-binding protein.

The homogeneous linewidth of dye aggregates like photosynthetic light-harvesting complexes contains important information about energy transfer and relaxation times that is, however, masked by inhomogeneous broadening caused by static disorder. Whereas there exist line narrowing techniques for the study of low-energy exciton states, the homogeneous linewidth of the high-energy states is not so easy to decipher. Here we present a microscopic theory for nonlinear polarization spectroscopy in the frequency domain that contains a dynamic aggregate selection revealing the homogeneous linewidth of these states. The theory is applied to the water-soluble chlorophyll-binding protein for which the high-energy exciton state was predicted to exhibit a sub-100-fs lifetime.

Tunable plasmon coupling in distance-controlled gold nanoparticles.

Plasmons are resonant excitations in metallic films and nanoparticles. For small enough static distances of metal nanoparticles, additional plasmon-coupled modes appear as a collective excitation between the nanoparticles. Here we show, by combining poly(N-isopropylacrylamide) micro- and nanospheres and Au nanoparticles, how to design a system that allows controllably and reversibly switching on and off, and tuning the plasmon-coupled mode.

Distance-dependent electron transfer rate of immobilized redox proteins: a statistical physics approach.

The electron transfer kinetics of redox proteins adsorbed on metal electrodes coated with self-assembled monolayers (SAMs) of mercaptanes shows an unusual distance-dependence. For thick SAMs, the experimentally measured electron transfer rate constant k{exp} obeys the behavior predicted by Marcus theory [R. A. Marcus and N. Sutin, Biochim. Biophys. Acta 811, 265 (1985)], whereas for thin SAMs, k{exp} remains virtually constant [Z. Q. Feng, J. Chem. Soc., Faraday Trans. 93, 1367 (1997)]. In this work, we present a simple theoretical model system for the redox protein cytochrome c electrostatically bound to a SAM-coated electrode. A statistical average of the electron tunneling rate is calculated by accounting for all possible orientations of the model protein. This approach, which takes into account the electric field dependent orientational distribution, allows for a satisfactory description of the "saturation" regime in the high electric field limit. It further predicts a nonexponential behavior of the average electron transfer processes that may be experimentally checked by extending kinetic experiments to shorter sampling times, i.e., 1/k{exp}. For a comprehensive description of the overall kinetics in the saturation regime at sampling times of the order of <<1/k{exp}, it is essential to consider the dynamics of protein reorientation, which is not implemented in the present model.

Antibunching of thermal radiation by a room-temperature phonon bath: a numerically solvable model for a strongly interacting light-matter-reservoir system.

Progress in semiconductor technology introduces a new platform for quantum optics studies in solid state: a quantum dot strongly coupled to a cavity mode. We present a numerically solvable model for the combined electron, photon, and phonon dynamics. For a cavity mode prepared in a Fock state, the model reproduces the Jaynes-Cumming solution and interaction with a phonon bath leads to a higher value for the intensity-intensity correlation function: g;(2)(0). In contrast, for an initial thermal photon distribution, the phonon-bath interaction gives a counterintuitive reduction in g;(2)(0), resulting in the classical photon distribution evolving into a nonclassical one.

Image dipoles approach to the local field enhancement in nanostructured Ag-Au hybrid devices.

We have investigated the plasmonic enhancement in the radiation field at various nanostructured multilayer devices that may be applied in surface enhanced Raman spectroscopy. We apply an image dipole method to describe the effect of surface morphology on the field enhancement in a quasistatic limit. In particular, we compare the performance of a nanostructured silver surface and a layered silver-gold hybrid device. It is found that localized surface plasmon states provide a high field enhancement in silver-gold hybrid devices, where symmetry breaking due to surface defects is a supporting factor. These results are compared to those obtained for multishell nanoparticles of spherical symmetry. Calculated enhancement factors are discussed on the background of recent experimental data.

Ultrafast double-quantum-coherence spectroscopy of excitons with entangled photons.

We calculate the four-wave-mixing signal of excitons generated at k(4) = k(1) + k(2) - k(3) by two pulsed entangled photon pairs (k(1), k(2))and(k(3), k(4)), where all four modes are chronologically ordered. Entangled photons offer an unusual combination of bandwidths and temporal resolution not possible by classical beams. Contributions from different resonances can be selected by varying the parameters of the photon wave function. The signal scales linearly rather than quadratically with the laser field intensity, which allows performance of the measurements at low powers.

Few-photon model of the optical emission of semiconductor quantum dots.

The Jaynes-Cummings model provides a well established theoretical framework for single electron two level systems in a radiation field. Similar exactly solvable models for semiconductor light emitters such as quantum dots dominated by many particle interactions are not known. We access these systems by a generalized cluster expansion, the photon-probability cluster expansion: a reliable approach for few-photon dynamics in many body electron systems. As a first application, we discuss vacuum Rabi oscillations and show that their amplitude determines the number of electrons in the quantum dot.

Novel Au-Ag hybrid device for electrochemical SE(R)R spectroscopy in a wide potential and spectral range.

A nanostructured gold-silver-hybrid electrode for SER spectroelectrochemistry was developed which advantageously combines the electrochemical properties and chemical stability of Au and the strong surface enhancement of (resonance) Raman scattering by Ag. The layered device consists of a massive nanoscopically rough Ag electrode, a thin (2 nm) organic layer, and a ca. 20 nm thick Au film that may be coated by self-assembled monolayers for protein adsorption. The SERR-spectroscopic and electrochemical performance of this device is demonstrated using the heme protein cytochrome c as a benchmark model system, thereby extending, for the first time, SE(R)R studies of molecules on Au surfaces to excitation in the violet spectral range. The enhancement factor is only slightly lower than for Ag electrodes which can be rationalized in terms of an efficient transfer of plasmon resonance excitation from the Ag to the Au coating. This mechanism, which requires a thin dielectric layer between the two metals, is supported by theoretical calculations.