Giant optical second- and third-order nonlinearities at a telecom wavelength.

A material platform that excels in both optical second- and third-order nonlinearities at a telecom wavelength is theoretically and experimentally demonstrated. In this TiN-based coupled metallic quantum well structure, electronic subbands are engineered to support doubly resonant inter-subband transitions for an exceptionally high second-order nonlinearity and provide single-photon transitions for a remarkable third-order nonlinearity within the 1400-1600 nm bandwidth. The second-order susceptibility χ(2) reaches 2840 pm/V at 1440 nm, while the Kerr coefficient n2 arrives at 2.8 × 10-10 cm2/W at 1460 nm. The achievement of simultaneous strong second- and third-order nonlinearities in one material at a telecom wavelength creates opportunities for multi-functional advanced applications in the field of nonlinear optics.

Multidimensional Widefield Infrared-Encoded Spontaneous Emission Microscopy: Distinguishing Chromophores by Ultrashort Infrared Pulses.

Photoluminescence (PL) imaging has broad applications in visualizing biological activities, detecting chemical species, and characterizing materials. However, the chemical information encoded in the PL images is often limited by the overlapping emission spectra of chromophores. Here, we report a PL microscopy based on the nonlinear interactions between mid-infrared and visible excitations on matters, which we termed MultiDimensional Widefield Infrared-encoded Spontaneous Emission (MD-WISE) microscopy. MD-WISE microscopy can distinguish chromophores that possess nearly identical emission spectra via conditions in a multidimensional space formed by three independent variables: the temporal delay between the infrared and the visible pulses (t), the wavelength of visible pulses (λvis), and the frequencies of the infrared pulses (ωIR). This method is enabled by two mechanisms: (1) modulating the optical absorption cross sections of molecular dyes by exciting specific vibrational functional groups and (2) reducing the PL quantum yield of semiconductor nanocrystals, which was achieved through strong field ionization of excitons. Importantly, MD-WISE microscopy operates under widefield imaging conditions with a field of view of tens of microns, other than the confocal configuration adopted by most nonlinear optical microscopies, which require focusing the optical beams tightly. By demonstrating the capacity of registering multidimensional information into PL images, MD-WISE microscopy has the potential of expanding the number of species and processes that can be simultaneously tracked in high-speed widefield imaging applications.

Multimodal Nonlinear Hyperspectral Chemical Imaging Using Line-Scanning Vibrational Sum-Frequency Generation Microscopy.

Vibrational sum-frequency generation (VSFG), a second-order nonlinear optical signal, has traditionally been used to study molecules at interfaces as a spectroscopy technique with a spatial resolution of ~100 µm. However, the spectroscopy is not sensitive to the heterogeneity of a sample. To study mesoscopically heterogeneous samples, we, along with others, pushed the resolution limit of VSFG spectroscopy down to ~1 µm level and constructed the VSFG microscope. This imaging technique not only can resolve sample morphologies through imaging, but also record a broadband VSFG spectrum at every pixel of the images. Being a second-order nonlinear optical technique, its selection rule enables the visualization of non-centrosymmetric or chiral self-assembled structures commonly found in biology, materials science, and bioengineering, among others. In this article, the audience will be guided through an inverted transmission design that allows for imaging unfixed samples. This work also showcases that VSFG microscopy can resolve chemical-specific geometric information of individual self-assembled sheets by combining it with a neural network function solver. Lastly, the images obtained under brightfield, SHG, and VSFG configurations of various samples briefly discuss the unique information revealed by VSFG imaging.

Imaging Orientation of a Single Molecular Hierarchical Self-Assembled Sheet: The Combined Power of a Vibrational Sum Frequency Generation Microscopy and Neural Network.

In this work, we determined the tilt angles of molecular units in hierarchical self-assembled materials on a single-sheet level, which were not available previously. This was achieved by developing a fast line-scanning vibrational sum frequency generation (VSFG) hyperspectral imaging technique in combination with neural network analysis. Rapid VSFG imaging enabled polarization resolved images on a single sheet level to be measured quickly, circumventing technical challenges due to long-term optical instability. The polarization resolved hyperspectral images were then used to extract the supramolecular tilt angle of a self-assembly through a set of spectra-tilt angle relationships which were solved through neural network analysis. This unique combination of both novel techniques offers a new pathway to resolve molecular level structural information on self-assembled materials. Understanding these properties can further drive self-assembly design from a bottom-up approach for applications in biomimetic and drug delivery research.

Water Capture Mechanisms at Zeolitic Imidazolate Framework Interfaces.

Water capture mechanisms of zeolitic imidazolate framework ZIF-90 are revealed by differentiating the water clustering and the center pore filling step, using vibrational sum-frequency generation spectroscopy (VSFG) at a one-micron spatial resolution and state-of-the-art molecular dynamics (MD) simulations. Through spectral line shape comparison between VSFG and IR spectra, the relative humidity dependence of VSFG intensity, and MD simulations, based on MB-pol, we found water clustering and center pore filling happen nearly simultaneously within each pore, with water filling the other pores sequentially. The integration of nonlinear optics with MD simulations provides critical mechanistic insights into the pore filling mechanism and suggests that the relative strength of the hydrogen bonds governs the water uptake mechanisms. This molecular-level detailed mechanism can inform the rational optimization of metal-organic frameworks for water harvesting.

Spatially dependent H-bond dynamics at interfaces of water/biomimetic self-assembled lattice materials.

Understanding hydrogen-bond interactions in self-assembled lattice materials is crucial for preparing such materials, but the role of hydrogen bonds (H bonds) remains unclear. To gain insight into H-bond interactions at the materials' intrinsic spatial scale, we investigated ultrafast H-bond dynamics between water and biomimetic self-assembled lattice materials (composed of sodium dodecyl sulfate and ß-cyclodextrin) in a spatially resolved manner. To accomplish this, we developed an infrared pump, vibrational sum-frequency generation (VSFG) probe hyperspectral microscope. With this hyperspectral imaging method, we were able to observe that the primary and secondary OH groups of ß-cyclodextrin exhibit markedly different dynamics, suggesting distinct H-bond environments, despite being separated by only a few angstroms. We also observed another ultrafast dynamic reflecting a weakening and restoring of H bonds between bound water and the secondary OH of ß-cyclodextrin, which exhibited spatial uniformity within self-assembled domains, but heterogeneity between domains. The restoration dynamics further suggest heterogeneous hydration among the self-assembly domains. The ultrafast nature and meso- and microscopic ordering of H-bond dynamics could contribute to the flexibility and crystallinity of the material--two critically important factors for crystalline lattice self-assemblies--shedding light on engineering intermolecular interactions for self-assembled lattice materials.

Local Ordering of Lattice Self-Assembled SDS@2ß-CD Materials and Adsorbed Water Revealed by Vibrational Sum Frequency Generation Microscope.

VSFG (vibrational sum frequency generation) microscopy was used to study the SDS@2ß-CD system, a synthetic capsid-like self-assembled material. We found because of strong hydrogen-bond interactions between water and the assemblies, water molecules are template to adopt the local mesoscopic ordering of the self-assemblies, which allows VSFG to probe water on nonflat interfaces. We show that the origin of the VSFG signal from the self-assembly is a combination of individual molecular chirality and highly coordinated ordering of the self-assembly, which gives rise of anisotropic signals, e.g., under SSS polarization. A similar strategy could be applied to other self-assembled materials composed by molecules without inversion symmetry. Using an imaging process, VSFG spectra of different self-assembly sheets were spatially resolved. We found heterogeneity among different domains, which can be attributed to variations in the hydration level of different domains. Since the SDS@2ß-CD system is a synthetic lattice self-assembly, such heterogeneity could also exist in other natural lattice assemblies such as a virus and tubulin.