Dionysis Adamou, Lennart Hirsch, Taylor Shields, Seungjin Yoon, Adetunmise C. Dada, Jonathan M R Weaver, Daniele Faccio, Marco Peccianti, Lucia Caspani, Matteo Clerici
The time-resolved detection of mid- to far-infrared electric fields absorbed and emitted by molecules is among the most sensitive spectroscopic approaches and has the potential to transform sensing in fields such as security screening, quality control, and medical diagnostics. However, the sensitivity of the standard detection approach, which relies on encoding the far-infrared electric field into amplitude modulation of a visible or near-infrared probe laser pulse, is limited by the shot noise of the latter. This constraint cannot be overcome without using a quantum resource. Here, we show that this constraint can be overcome using a two-mode squeezed state. Quantum-correlated ultrashort pulses, generated by parametric down-conversion, enhance the sensitivity of far-infrared detection beyond the classical limit, achieving a twofold reduction in measured noise. This advancement paves the way for further development of ultrafast quantum metrology, moving toward quantum-enhanced time-resolved electric field spectroscopy with sensitivities beyond the standard quantum limit.
The time-resolved detection of mid- to far-infrared electric fields absorbed and emitted by molecules is among the most sensitive spectroscopic approaches and has the potential to transform sensing in fields such as security screening, quality control, and medical diagnostics. However, the sensitivity of the standard detection approach, which relies on encoding the far-infrared electric field into amplitude modulation of a visible or near-infrared probe laser pulse, is limited by the shot noise of the latter. This constraint cannot be overcome without using a quantum resource. Here, we show that this constraint can be overcome using a two-mode squeezed state. Quantum-correlated ultrashort pulses, generated by parametric down-conversion, enhance the sensitivity of far-infrared detection beyond the classical limit, achieving a twofold reduction in measured noise. This advancement paves the way for further development of ultrafast quantum metrology, moving toward quantum-enhanced time-resolved electric field spectroscopy with sensitivities beyond the standard quantum limit.
In conventional balanced-detection measurements, sensitivity can generally be improved by increasing the optical power. However, in many systems this approach reaches an upper bound beyond which increasing the probe power can damage the sample or degrade the measurement. In THz time-domain spectroscopy, this bound is set by nonlinear noise and measurement back-action. When this ceiling is reached by classical techniques, a potential avenue to improve the signal-to-noise ratio is by using quantum metrological resources. This work reports the development of a bright, ultrafast twin-beam source, exhibiting more than 6 dB of noise suppression up to microwatt optical power levels, together with an ultra-low-noise balanced photoreceiver with sub-shot-noise performance. Integrating these technologies into a THz-TDS system developed in collaboration with colleagues we demonstrate, for the first time to our knowledge, a measurable enhancement in sensitivity by harnessing quantum correlations when compared with a classical source under identical conditions. Although the implemented THz-TDS setup deviates from conventional polarimetric schemes, which typically achieve higher sensitivity, these results show that quantum methods can provide a sensitivity enhancement in field-resolved THz spectroscopy. Beyond this demonstration, the developed twin-beam source has clear potential for wider use as its brightness, stability and correlation strength make it an attractive candidate for ultrafast, differential transient absorption measurements.
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.
Recent years have seen the development of quantum sensing concepts utilizing nonlinear interferometers based on correlated photon pairs generated by spontaneous parametric down-conversion (SPDC). Using SPDC far from frequency degeneracy allows a “division of labor” between the mid-infrared photon for the strongest sample interaction and the correlated near-infrared photon for low-noise detection. The small number of photons provided by SPDC and the resulting inferior signal-to-noise ratio are, however, a limiting factor preventing the wide applicability of the novel sensing concept. Here, we demonstrate a nonlinear interferometer based on pump-enhanced SPDC with strongly improved emission rates while maintaining broadband spontaneous emission. For validation of the concept, we demonstrate high-resolution mid-infrared spectroscopy with near-infrared detection, showcasing improved accuracy. Although the number of mid-infrared photons is about five orders of magnitude smaller than in classical spectrometers, the sensitivity of the quantum spectrometer becomes comparable, marking an essential step toward real-world applications.
A time-domain approach to quantum electrodynamics is presented, covering the entire mid-infrared and terahertz frequency ranges. Ultrabroadband electro-optic sampling with few-femtosecond laser pulses allows direct detection of the vacuum fluctuations of the electric field in free space [1,2]. Besides the Planck and electric field fundamental constants, the variance of the ground state is determined solely by the inverse of the four-dimensional space-time volume over which a measurement or physical process integrates. Therefore, we can vary the contribution of multi-terahertz vacuum fluctuations and discriminate against the trivial shot noise due to the constant flux of near-infrared probe photons. Subcycle temporal resolution based on a nonlinear phase shift provides signals from purely virtual photons for accessing the ground-state wave function without amplification to finite intensity. Recently, we have succeeded in generation and analysis of mid-infrared squeezed transients with quantum noise patterns that are time-locked to the intensity envelope of the probe pulses. We find subcycle temporal positions with a noise level distinctly below the bare vacuum which serves as a direct reference. Delay times with increased differential noise indicate generation of highly correlated quantum fields by spontaneous parametric fluorescence. Our time-domain approach offers a generalized understanding of spontaneous emission processes as a consequence of local anomalies in the co-propagating reference frame modulating the quantum vacuum, in combination with the boundary conditions set by Heisenberg’s uncertainty principle. [1] C. Riek et al., Science 350, 420 (2015) [2] A. S. Moskalenko et al., Phys. Rev. Lett. 115, 263601 (2015)
Mid-infrared (MIR) detection remains challenging due to limited detector sensitivity and strong background noise. Frequency up-conversion enables MIR detection with visible-range detectors but suffers from limited robustness and additional noise generated in the nonlinear process. We demonstrate a quantum-enhanced MIR frequency up-conversion detection system that generates strongly non-degenerate, time-correlated photon pairs via spontaneous parametric down-conversion and detects MIR photons under severe loss and noise. With a 62 dB transmission loss and background noise 28 times higher than the detected signal, the quantum signal-to-noise ratio substantially surpasses that of classical photon counting. The system achieves stable signal retrieval under unpredictable noise fluctuations, highlighting its robustness in dynamically varying environments. These results establish a basis for practical sensing and imaging applications of quantum-enhanced MIR detection.
The fascinating nature of light has driven many discoveries in physics, from the theory of special relativity to quantum mechanics. As a carrier of information, light is at the core of high-speed communication over the internet and facilitates the study of numerous physical properties of materials by the interaction of light and matter. Advances in generating and detecting ultrashort light pulses enabled the spectroscopic investigation of matter with unprecedented detail. Meanwhile, the development of more precise and sensitive measurements, leveraging quantum properties of light, has expanded the experimental frontiers of the physical world. Naturally, the question arises: Could the combination of these two breakthroughs push the frontiers even further? A promising candidate to achieve this combination is electro-optic sampling, an electromagnetic-field measurement comprising an up-conversion and a phase-space measurement based on homodyne detection. While it is predominantly used in classical terahertz time-domain spectroscopy, the high sensitivity and spatio-temporal resolution of electro-optic sampling recently enabled the detection of vacuum fluctuations in the ground state of the electromagnetic field by probing an adjustable space-time volume. Yet, the generation and characterization of more intricate quantum pulses on ultrafast timescales is still challenging, especially in the terahertz frequencies. Exploiting the quantum properties of a light pulse over a broad frequency range requires sophisticated knowledge about the prepared quantum pulse as well as the measurement setup at use. However, Heisenberg's uncertainty relation fundamentally prevents the complete determination of an arbitrary quantum state from a single measurement. Instead, the quantum state has to be reconstructed from the statistics of many measurements — a process known as quantum state tomography. In this thesis, we establish the theoretical foundations for a comprehensive tomographic reconstruction of pulsed quantum states of light, encompassing both the statistics and dynamics of the state. Additionally, we introduce tools to simplify the description of the nonlinear interaction underlying electro-optic sampling and in turn the tomography setups presented here. As a first step, we investigate the application of electro-optic sampling to the time-local reconstruction of various pulsed quantum states of light on ultrafast timescales. We identify two types of noise, which impact the quality of the reconstruction: shot noise, arising from the nonlinear interaction in electro-optic sampling, and thermal noise, due to the localization of the (correlated) quantum state within a small space-time volume during the measurement. To improve the reconstruction, we propose to use a strong probe pulse, suppressing the shot noise, and to select an appropriate detection frequency band, reducing thermal noise. Thus, the proposed tomography enables the characterization of quantum states in terahertz frequency range on ultrafast timescales. However, the time-local nature of the measurement imposes a trade-off between the reconstruction of the quantum state in phase space and the time domain. In a second step, we propose a reconstruction method based on two-time field-correlation measurement, which we call correlation tomography, able to overcome the restriction to time-local states. While the tomography of quantum states in an optimal pulse basis has been demonstrated, it requires prior knowledge about the temporal structure of the quantum state. We introduce an algorithm for reconstructing high-dimensional multimode Gaussian quantum states, which are completely characterized by the covariance matrix of the quadratures of fully distinguishable pulses. The reconstruction is achieved by orthogonalizing the overlapping time windows of the correlation measurement in post-processing. We compare a homodyne-based implementation to electro-optic sampling and develop an optimization scheme for the latter, to mitigate the shot noise in the non-perturbative regime of strong nonlinear interactions. Furthermore, we derive the full-counting statistics of the field-correlation measurement and theoretically demonstrate the reconstruction of pulsed Fock states. This opens an avenue to the full tomography of highly multimode non-Gaussian states. In the third and last step, we derive a formalism to simplify the description of the up-conversion required in electro-optic sampling. If a pulsed quantum states is up-converted and localized in a small space-time region, the transformation of the localized modes during the nonlinear interaction corresponds to an open quantum system, rendering the standard tools of quantum optics inapplicable. By introducing the generalized Bloch-Messiah decomposition, we simplify the input-output relation of the nonlinear interaction to a set of effective modes relevant for subsequent processing, such as detection. Using this framework, we derive an analytic phase-space input-output relation for the nonlinear interaction of pulsed quantum states, applicable to open quantum systems. We study the resulting dynamics using two example input states: a Fock state and a two-mode squeezed state. Based on the von Neumann entropy of the output state, we develop an intuitive understanding of the generalized Bloch-Messiah decomposition. The rich structure of pulsed quantum states of light can be a powerful resource, but also challenging to operate with, in theory as well as in experiment. The characterization methods and theoretical tools developed in this thesis, tailored to pulsed quantum light and the nonlinear interaction thereof, can pave the way to the application of this resource to fundamental research as well as quantum technologies.