Absorption spectroscopy is one of the most widely used spectroscopic methods. The signal-to-noise ratio in conventional absorption spectroscopy is ultimately limited by the shot noise, which arises from the statistical property of the light used for the measurement. Here we show that the noise in absorption spectra can be suppressed below the shot-noise limit when entangled photon pairs are used for the light source. By combining broadband entangled photon pairs and multichannel detection, we realize the acquisition of sub-shot-noise absorption spectra in the entire visible wavelength. Furthermore, we demonstrate the strength of sub-shot-noise absorption spectroscopy for the identification and quantification of chemical species, which are two primary aims of absorption spectroscopy. For highly diluted binary mixture solutions, sub-shot-noise absorption spectroscopy enables us to determine the concentration of each chemical species with precision beyond the limit of conventional absorption spectroscopy. That is, sub-shot-noise absorption spectroscopy achieves superresolution in concentration measurements.
Absorption spectroscopy is one of the most widely used spectroscopic methods. The signal-to-noise ratio in conventional absorption spectroscopy is ultimately limited by the shot noise, which arises from the statistical property of the light used for the measurement. Here we show that the noise in absorption spectra can be suppressed below the shot-noise limit when entangled photon pairs are used for the light source. By combining broadband entangled photon pairs and multichannel detection, we realize the acquisition of sub-shot-noise absorption spectra in the entire visible wavelength. Furthermore, we demonstrate the strength of sub-shot-noise absorption spectroscopy for the identification and quantification of chemical species, which are two primary aims of absorption spectroscopy. For highly diluted binary mixture solutions, sub-shot-noise absorption spectroscopy enables us to determine the concentration of each chemical species with precision beyond the limit of conventional absorption spectroscopy. That is, sub-shot-noise absorption spectroscopy achieves superresolution in concentration measurements.
Quantum light, such as entangled photon pairs, is a special state of light that cannot be described by classical electrodynamics. Owing to its exotic nonclassical properties, the use of quantum light can open up a new possibility for spectroscopy that cannot be realized by a classical light source. Recently, using entangled photon pairs as the light source, we demonstrated ultrasensitive absorption spectroscopy with quantum-enhanced sensitivity [1]. This novel approach allows us to obtain absorption spectra with a noise level suppressed below the shot-noise limit, which is a fundamental and unavoidable limit in conventional absorption spectroscopy. In this presentation, we will discuss two applications of this sub-shot-noise absorption spectroscopy.
Absorption spectroscopy is routinely used to characterise chemical and biological samples. For the state-of-the-art in laser absorption spectroscopy, precision is theoretically limited by shot-noise due to the fundamental Poisson-distribution of photon number in laser radiation. In practice, the shot-noise limit can only be achieved when all other sources of noise are eliminated. Here, we use wavelength-correlated and tuneable photon pairs to demonstrate how absorption spectroscopy can be performed with precision beyond the shot-noise limit and near the ultimate quantum limit by using the optimal probe for absorption measurement—single photons. We present a practically realisable scheme, which we characterise both the precision and accuracy of by measuring the response of a control feature. We demonstrate that the technique can successfully probe liquid samples and using two spectrally similar types of haemoglobin we show that obtaining a given precision in resolution requires fewer heralded single probe photons compared to using an idealised laser.
The optical shot-noise limit of a laser beam represents the classical limit in precision and signal to noise ratio achievable in optical sensors and imaging systems. It is known that quantum states of light, such as squeezed light and quantum correlated twin beams can be used to enhance precision and signal to noise ratio to beyond this limit. This promises optical sensors with fundamentally superior performance to the state of the art. While quantum-enhanced signal to noise ratio has been demonstrated with macroscopic powers of squeezed probe beam, demonstrations of quantum enhanced precision have remained at extremely low powers of light (femto-Watts). Here we will give examples where increasing SNR with quantum light is not sufficient to increase precision and we will review proof of principle experiments that have demonstrated sub shot noise precision, including for absorption spectroscopy and imaging. We will also report our efforts to achieve this sub-shot-noise precision performance for transmission measurement with ~0.1mW of average probe power, equating to ~10W peak power in a pulsed experiment. Time permitting, we will discuss how integrated optics and integrated electronics enables 10s GHz bandwidth in the detection of squeezed light, for integrated quantum sensor technology.
Circular dichroism (CD), which detects differential absorption with left- and right-circularly polarized light, is widely used for characterizing molecular chirality. Despite its similarity to absorption spectroscopy, CD spectroscopy typically requires a significantly longer time to acquire a spectrum due to the low intensity of the CD signal. The CD measurements can be accelerated if the noise level in the spectra can be reduced, which facilitates the detection of the weak CD signal. Here we show that such noise suppression is indeed possible using entangled photon pairs as the light source. By taking advantage of the photon number correlation of entangled photon pairs, we suppressed the noise contained in the CD spectra by 30% below the shot-noise limit which is a fundamental limit in conventional CD measurements. As a consequence, sub-shot-noise CD spectroscopy developed in this study is capable of characterizing the molecular chirality twice as fast as conventional CD spectroscopy.
Absorption spectroscopy has long been hailed as an absolute necessity for detecting the properties of complex chemical and biological samples. While conventional spectroscopy using classical light is severely limited by shot noise and lacks robustness against experimental imperfections, quantum light offers an avenue to perform absorption spectroscopy with provable advantages in the technical operations and the measurement precision. Here, we present an experimental approach to implement entanglement-based absorption spectroscopy with the assistance of Hong-Ou-Mandel interference. Since the temporal interference fringe is determined by the spectrum pattern, a maximum-likelihood decision is sufficient for revealing the relevant quantum information about the absorptive properties of the test samples. These experimental results may significantly facilitate the use of quantum interferometric spectroscopy to practical applications, which may be particularly relevant for photon-sensitive biological and chemical samples.
The application of quantum states of light such as entangled photons, for example, created by parametric down conversion, has experienced tremendous progress in the almost 40 years since their first experimental realization. Initially, they were employed in the investigation of the foundations of quantum physics, such as the violation of Bell's inequalities and studies of quantum entanglement. They later emerged as basic platforms for quantum communication protocols and, in the recent experiments on single-photon interactions, in photonic quantum computation. These applications aim at the controlled manipulation of the photonic degrees of freedom, and therefore rely on simple models of matter, where the analysis is simpler. Furthermore, quantum imaging with entangled light can achieve enhanced resolution, and quantum metrology can overcome the shot noise limit for classical light. This Account focuses on an entirely different emerging class of applications using quantum light as a powerful spectroscopic tool to reveal novel information about complex molecules. These applications utilize two appealing properties of quantum light: its distinct intensity fluctuations and its nonclassical bandwidth properties. These give rise to new and surprising behavior of nonlinear optical signals. Nonclassical intensity fluctuations can enhance nonlinear optical signals relative to linear absorption. For instance, the two-photon absorption of entangled photon pairs scales linearly (rather than quadratically) in the photon flux, just like a single photon absorption. This enables nonlinear quantum spectroscopy of photosensitive, for example, biological, samples at low light intensities. We will discuss how the two-photon absorption cross section becomes a function of the photonic quantum state, which can be manipulated by properties of the entangled photon pairs. In addition, the quantum correlations in entangled photon states further influence the nonlinear signals in a variety of ways. Apart from affecting the signal's scaling with intensity, they also constitute an entirely new approach to shaping and controlling excitation pathways in molecular aggregates in a way that cannot be achieved with shaped classical pulses. This is because between the two absorption events in entangled two-photon absorption, the light and material system are entangled. Classical constraints for the simultaneous time and frequency resolution can thus be circumvented, since the two are not Fourier conjugates. Here we review the simplest manifestation of quantum light spectroscopy, two-photon absorption spectroscopy with entangled photons. This will allow us to discuss exemplarily the impact of quantum properties of light on a nonlinear optical signal and explore the opportunities for future applications.