In recent times there has been growing interest in Raman optical activity (ROA) for its label free detection of absolute configuration, conformation, and stereochemical structure in chiral biosamples and drug molecules. Since ROA signals are generally small, techniques such as stimulation by a probe beam can be used to enhance the signal strength. However, with a classical probe, the measurement precision is still fundamentally limited by its shot noise. To solve this problem we propose the use of two-mode squeezed vacuum and show that it can achieve sub-shot noise limited measurement sensitivity. Using quantum estimation theory, we derived the quantum Fisher information and the quantum Cramér-Rao bound (QCRB) for stimulated ROA measurement to quantify the precision enhancement. This improvement comes from photon-number correlations which suppress the intensity fluctuation common to both modes. We further show that balanced detection of the output intensity difference is a practical measurement scheme that approaches the QCRB and becomes optimal in the small-chirality limit. This opens a promising path toward more sensitive Raman chiroptical spectroscopy of weak and photosensitive samples.
In recent times there has been growing interest in Raman optical activity (ROA) for its label free detection of absolute configuration, conformation, and stereochemical structure in chiral biosamples and drug molecules. Since ROA signals are generally small, techniques such as stimulation by a probe beam can be used to enhance the signal strength. However, with a classical probe, the measurement precision is still fundamentally limited by its shot noise. To solve this problem we propose the use of two-mode squeezed vacuum and show that it can achieve sub-shot noise limited measurement sensitivity. Using quantum estimation theory, we derived the quantum Fisher information and the quantum Cramér-Rao bound (QCRB) for stimulated ROA measurement to quantify the precision enhancement. This improvement comes from photon-number correlations which suppress the intensity fluctuation common to both modes. We further show that balanced detection of the output intensity difference is a practical measurement scheme that approaches the QCRB and becomes optimal in the small-chirality limit. This opens a promising path toward more sensitive Raman chiroptical spectroscopy of weak and photosensitive samples.
Squeezed light has been applied in stimulated Raman scattering (SRS) spectroscopy [1] and microscopy [2] to break the shot-noise-limited sensitivity. The sub-shot-noise sensitivity achieved in quantum-enhanced SRS (QE-SRS) systems is advantageous for uncovering weak signals and achieving faster imaging speed, which attract the attention of biomedical scientists. To break the sensitivity of state-of-the-art SRS microscopes, the applied squeezed light power in QE-SRS systems should be high enough (>10mW). Recently, high-power picosecond-pulsed QE-SRS spectroscopy [3] based on balanced detection scheme [4] was reported, and a sensitivity that is comparable to state-of-the-art SRS microscopes was firstly demonstrated in QE-SRS microscopy based on the same scheme [5]. An important issue of QE-SRS based on balanced detection is the 3-dB additional noise, so >3-dB squeezing level is required to demonstrate an absolute sensitivity improvement compared with state-of-the-art SRS microscopes in single-photodiode detection scheme. However, it's hard to generate highly squeezed pulsed light because of the difficulty in temporal and spatial mode matching between squeezed vacuum (SQV) and local oscillator (LO). Here, we introduce QE-SRS in dual-polarization scheme, which can be implemented in high-power regime but is free from the 3-dB signal-to-noise ratio drawback.
Abstract The sensitivity of classical Raman spectroscopy methods, such as coherent anti-stokes Raman spectroscopy (CARS) or stimulated Raman spectroscopy (SRS), is ultimately limited by shot-noise from the stimulating fields. We present the complete theoretical analysis of a squeezing-enhanced version of Raman spectroscopy that overcomes the shot-noise limit of sensitivity with enhancement of the Raman signal and inherent background suppression, while remaining fully compatible with standard Raman spectroscopy methods. By incorporating the Raman sample between two phase-sensitive parametric amplifiers that squeeze the light along orthogonal quadrature axes, the typical intensity measurement of the Raman response is converted into a quantum-limited, super-sensitive estimation of phase. The resonant Raman response in the sample induces a phase shift to signal-idler frequency-pairs within the fingerprint spectrum of the molecule, resulting in amplification of the resonant Raman signal by the squeezing factor of the parametric amplifiers, whereas the non-resonant background is annihilated by destructive interference. Seeding the interferometer with classical coherent light stimulates the Raman signal further without increasing the background, effectively forming squeezing-enhanced versions of CARS and SRS, where the quantum enhancement is achieved on top of the classical stimulation.
The minimum possible uncertainty when estimating a parameter, in this case transmission, is bounded by the quantum Cramér-Rao bound (QCRB). This bound is independent of the measurement technique and as result can be used to quantify how close a measurement is to the optimal one for a given system and probing state, as an optimal measurement saturates the QCRB. The ability to perform transmission measurements through an optical system at the QCRB can lead to enhancements in the calibration of optimal states for interferometers, the characterization of high efficiency photodetectors, or the sensitivity of sensing devices based on transmission, such as plasmonic sensors or spectroscopy. We show theoretically that the ultimate sensitivity limit per photon in the estimation of transmission, achievable with Fock states or vacuum two-mode squeezed states (vTMSS), can be approached through the use of bright quantum states of light, such as bright single-mode squeezed states (bSMSS) or bright two-mode squeezed states (bTMSS). The use of bright quantum states has the advantage that they can be generated with a significantly larger number of photons, which leads to an absolute sensitivity that can be many orders of magnitude larger than the one achieved with Fock states or vTMSS. We identify a measurement strategy that saturates the QCRB for these bright quantum states and shown experimentally that transmission estimation at the QCRB can be achieved with bTMSS through optimized intensity difference measurements.
In optical microscopy, as in any biological measurement performed with light, there is a compromise between increasing power to improve resolution and decreasing power to prevent photodamage to the biological structure. Quantum optics allows this compromise to be overcome, enabling improved precision without increased illumination intensity. This thesis demonstrates, for the first time, absolute quantum advantage in microscopy, with a specific focus on Stimulated Raman Scattering (SRS) microscopy.SRS microscopy is a powerful tool widely used in many fields, especially in biomedical sciences. It uses a two-photon process where the light is downshifted in frequency by being absorbed and subsequently inelastically scattered by the intrinsic molecular vibrations in the sample. Each element or molecule has a different response, allowing selective imaging of biological systems. SRS microscopy is particularly useful because it is label-free (no addition of dyes, beads or any implanted tracer), meaning that imaging contrast is achieved without modification of, or interference with, the specimen. Here I present our newly built state-of-the-art shot-noise limited SRS microscope. I also characterize the Raman microscope, describe the developped imaging system and show SRS spectroscopy and imaging of both polystyrene beads and living yeast cells.The quantisation of light introduces a fundamental uncertainty, or quantum noise, in both the amplitude and phase quadratures of an optical field. A squeezed state of light is a state of the optical field where the uncertainty of one of these quadratures is reduced below the quantum noise. Therefore, it provides an approach to reduce the noise level below this quantum noise limit and consequently increases measured signal-to-noise ratio. Here I describe the concepts involved in this technique and present our newly built light squeezer. I characterize the squeezing and show up to -1.3 dB of noise floor reduction for a 6 picosecond pulsed laser, which is the pulse duration that maximises the Raman interaction.In this thesis we apply squeezed states of light in SRS, developping a quantum-enhanced micro- scope. Our SRS Raman intensity noise is ∆I/I ≈ 10^(−7) and the measured quantum efficiency of the built photodiode is η = 72%. In this proof of principle we show a reduction of the noise floor of at least 13% below the quantum noise limit for Raman imaging of polystyrene beads and living yeast cells. This enhancement allowed us to resolve the cell membrane where with conventional microscope would be unresolvable. It also allowed sub-micron spatial resolution. The improved image contrast and reduced imaging time, while avoiding photodamage in the sample, surpasses the current state-of-the-art Raman microscopes and opens opportunities for new discoveries in biophysics.
Quantum correlations offer the possibility of surpassing classical limits in optical measurements, but their integration into nonlinear vibrational spectroscopy has remained largely unexplored. Here, we introduce a quantum-enhanced implementation of coherent Raman spectroscopy that employs broadband squeezed-light detection to interrogate relative intensity correlations between Stokes and anti-Stokes fields generated in an ultrafast four-wave-mixing process. By exploiting nonclassical correlations between these fields, we suppress the nonresonant background and enhance the signal-to-noise performance in both temporal and spectral domains, enabling detection sensitivities beyond the classical shot-noise limit. Importantly, the quantum advantage demonstrated here does not arise solely from improved detection statistics. Rather, it originates from microscopic intermolecular correlations mediated by cascaded exchange of a virtual photon between molecular pairs. This mechanism establishes a fundamentally distinct and significant pathway for information extraction in vibrational spectroscopy, providing access to structural and dynamical observables that are intrinsically inaccessible by conventional classical Raman techniques. Numerical simulations illustrate the power of the technique by resolving intradimer [Formula: see text] bond splitting in cyclobutane thymine dimers following ultraviolet excitation, highlighting its potential for probing ultrafast photochemical processes with quantum-limited sensitivity and for label-free biomedical optical sensing and imaging.
The measurement of circular dichroism (CD) has widely been exploited to distinguish the different enantiomers of chiral structures. It has been applied to natural materials (e.g., molecules) as well as to artificial materials (e.g., nanophotonic structures). However, especially for chiral molecules the signal level is very low and increasing the signal-to-noise ratio is of paramount importance to either shorten the necessary measurement time or to lower the minimum detectable molecule concentration. As one solution to this problem, we propose here to use quantum states of light in CD sensing to reduce the noise below the shot noise level encountered when using coherent states of light. Through a multiparameter estimation approach, we identify the ultimate quantum limit of the precision in CD sensing, allowing for general schemes including additional ancillary modes. We show that the ultimate quantum limit can be achieved by various optimal schemes. These include using a pair of Fock-state probes in a direct sensing configuration and pairs of twin beams in an ancilla-assisted sensing configuration, for both of which photon number-resolved detection is shown to be the optimal measurement. These optimal schemes offer a significant quantum enhancement even in the presence of some additional system loss. The near optimality of a scheme using a single twin beam in a direct sensing configuration is also shown for cases where the actual CD signal is very small. Alternative optimal schemes involving single-photon sources and detectors are also proposed. This work paves the way for further investigations of quantum metrological techniques in chirality sensing.