From multi-photon to single molecule, the past several decades have witnessed a revolution in fluorescent microscopy. These techniques have revealed the inner working of cells and tissue and have relied on symbiotic advances in advanced molecular probes, light emitting molecules and particles, and novel instrumentation. More recently, researchers have begun to develop functional nanomaterials or materials that can response to their environment. In this talk, I will discuss some of our recent work in developing functional imaging agents for multi-wavelength and multi-photon live-cell imaging, focusing on recent molecular designs performed using density functional theory as well as in vitro studies.
Due to their high circulating intensities, ultra-high quality factor dielectric whispering-gallery mode resonators have enabled the development of low threshold Raman microlasers. Subsequently, other Raman-related phenomena, such as cascaded stimulated Raman scattering (CSRS) and stimulated anti-Stokes Raman scattering (SARS), were observed. While low threshold frequency conversion and generation have clear applications, CSRS and SARS have been limited by the low Raman gain. In this work, the surface of a silica resonator is modified with an organic monolayer, increasing the Raman gain. Up to four orders of CSRS is observed with sub-mW input power, and the SARS efficiency is improved by three orders of magnitude compared to previous studies with hybrid resonators.
Azobenzene is capable of reversibly switching its conformation upon the UV/Visible optical exposure due to its reversible trans/cis photoisomerization. By merging this organic material with conventional photonic devices, new architectures can be developed. In our study, we developed hybrid organic/inorganic whispering gallery mode microcavities consisting of a self-assembled 4-(4-diethylaminophenylazo)pyridine (Aazo) monolayer anchored on an integrated SiO2 optical microtoroid. As the Aazo monolayer changed conformations, the resonant wavelength was tuned. The surface density of Aazo was modified by introducing CH3 spacer molecules providing control over the magnitude of the shift. Owing to the uniformity of Aazo monolayer, cavity quality factors reached above 1 million in the near-IR range. Two optical lasers were simultaneously coupled into the Aazo-coated devices with a single waveguide. The 1300 nm laser is used to excite and monitor a single resonant wavelength of the cavity, and the 410 nm laser triggers the thermodynamically stable trans-Aazo to photoswitch to the thermodynamically unfavored cis-Aazo. When the Aazo photoswitches, the cavity resonant wavelength at near-IR wavelength shifts due to a change of refractive index in the Aazo layer. To revert the molecule back to trans-Aazo, a CO2 laser is used to heat the device system. Even after storage in air, the switching behavior is unchanged. Theoretical analyses are conducted based on density functional theory of the Aazo isomers combined with finite element method simulations of the optical mode. The theoretical results agree with the experimental findings.
Photoswitchable organic molecules can undergo reversible structural changes with an external light stimulus. These optically controlled molecules have been used in the development of “smart” polymers, optical writing of grating films, and even controllable in-vivo drug release. Being the simplest class of photoswitches in terms of structure, azobenzenes have become the most ubiquitous, well-characterized, and implemented organic molecular switch. Given their predictable response, they are ideally suited to create an all-optically controlled switch. However, fabricating a monolithic optical device comprised solely from azobenzene while maintaining the photoswitching functionality is challenging. In this work, we combine integrated photonics with optically switchable organic molecules to create an optically controlled integrated device. A silica toroidal resonant cavity is functionalized with a monolayer of an azobenzene derivative. After functionalization, the loaded cavity Q is above 105 . When 450 nm light is coupled into cavity resonance, the azobenzene isomerizes from trans-isomer to cis-isomer, inducing a refractive index change. Because the resonant wavelength of the cavity is governed by the index, the resonant wavelength changes in parallel. At the probe wavelength of 1300 nm, the wavelength shift is determined by the duration and intensity of the 450 nm light and the density of azobenzene functional groups on the device surface, providing multiple control mechanisms. Using this photoswitchable device, resonance frequency tuning as far as sixty percent of the cavity’s free spectral range in the near-IR is demonstrated. The kinetics of the tuning agree with spectroscopic and ellipsometry measurements coupled with finite element method calculations.
Optical resonant cavities form the foundation for a wide range of integrated optical components. While a high performance laser requires a high quality factor (Q) cavity, other types of devices, like modulators, rely on the cavity resonant wavelength being tunable. Numerous mechanisms based on the thermo-optic and electro-optic effects have been leveraged to create switchable or tunable devices; however, these are very power hungry and/or require complex control machinery. In the present work, we graft an air-stable, optically triggerable functional group to the surface of an ultra-high-Q optical cavity. The Aazobenzene functional group switches from trans to cis upon exposure to blue light, and it can be thermally triggered to revert to the initial trans state. Using a single tapered optical fiber waveguide, blue and near-IR light can be coupled into the device simultaneously. When the blue light interacts with the Aazo group, the resonant wavelength blue shifts. Upon exposure to a CO2 laser, the resonant wavelength returns to its initial position. Several different aspects of the device operation were investigated, including the kinetics of the switching, the effect of switching via a resonant or non-resonant optical field, and sterics of the switching. Notably, by tuning the surface density of the Aazo groups using a multi-material surface chemistry, it is possible to control the magnitude of the shift.
On-chip Kerr frequency combs have attracted significant attention because of their compact footprint and numerous applications. While many integrated material systems are being investigated for generating the on-chip Kerr frequency combs, so far only silica devices have achieved quality factors above 100 million, which is important for decreasing the threshold and power consumption of the system. However, as an intrinsic property of silica, the hydroxyl groups present on the surface of the devices will attract water molecules in the air, which decreases the quality factor of the devices. To maintain the performance of the frequency combs, methods like putting the devices in nitrogen purged boxes or building covers for the system are proposed, which would largely increase the complexity of the system. Here we studied another material system, silicon oxynitride microtoroids, whose quality factors can achieve and stay constant at more than 100 million because of the lack of the hydroxyl groups on the surface. Kerr frequency combs are generated from the SiOxNy microtoroids with normal dispersion with avoided mode crossing. Thresholds as low as 280 μW are achieved as a result of the high quality factor. The comb spectrum remains the same for the same pump power over the nine day period after fabrication, which indicates that the performance of the frequency combs remains constant despite the silicon oxynitride devices being stored in ambient atmosphere without any special treatment the whole time.
Photoswitchable organic molecules can undergo reversible structural changes, with an external light stimulus. These
special molecules have found uses in the development of “smart”polymers, optical writing of grating films, and even
controllable in-vivo drug release. Traditional photoswitchable small molecules include azobenzenes, spiropyrans,
diarylethenes, and a whole host of their derivatives. These classes of molecules can either photoisomerize or undergo
reversible ring opening, respectively. Being the simplest class of photoswitches in terms of structure, azobenzenes have
become the most ubiquitous, well-characterized, and implemented organic molecular switch. In this work, an
azobenzene derivative is utilized and covalently attached to the surface of a silica microtoroidal optical resonator and is
used to tune the resonance around fifty percent of the cavity’s free spectral range. An evanescently coupled 1300nm
laser is used as the probe wavelength to monitor the trans-cis isomerization initiated by a 450nm laser source which is
also coupled into the device. Results and kinetics are compared to UV-Vis spectroscopy and ellipsometry, and the tuning
sensitivity is compared to other established methods in the literature.
Recent advances in optical materials have enabled the development of a wide range of integrated photonic devices from high speed modulators to frequency combs. With low optical loss over a wide wavelength range and environmental stability in ambient environments for several weeks, silicon oxynitride (SiOxNy) shows potential in many of these applications. However, unlike many classic optical materials, the thermo-optic response (dn/dT) in both the visible and near-IR is poorly characterized, limiting researcher’s ability to accurately model device performance. Here, we leverage the intrinsic thermal response of resonant cavities to measure the dn/dT of SiOxNy with a 12.7:1 and 4:1 oxygen to nitrogen ratio based on EDX measurements. The thermo-optic coefficient is measured in the visible and near-IR and compared with SiO2. The refractive indices of the silicon oxynitride films were also measured using spectroscopic ellipsometry. Based on an analysis of the O:N ratio and a comparison with both SiO2 and Si3N4, an expression for the dependence of the dn/dT on the stoichiometric ratio is developed.
Whispering gallery mode optical resonators integrated on silicon have demonstrated low threshold Raman lasers. One of the primary reasons for their success is their ultra-high quality factors (Q) which result in an amplification of the circulating optical field. Therefore, to date, the key research focus has been on maintaining high Q factors, as that determines the lasing threshold and linewidth. However, equally important criteria are lasing efficiency and wavelength. These parameters are governed by the material, not the cavity Q. Therefore, to fully address this challenge, it is necessary to develop new materials. We have synthesized a suite of metal-doped silica and small molecules to enable the development of higher performance Raman lasers. The efficiencies and thresholds of many of these devices surpass the previous work. Specifically, the silica sol-gel lasers are doped with metal nanoparticles (eg Ti, Zr) and are fabricated using conventional micro/nanofabrication methods. The intercalation of the metal in the silica matrix increases the silica Raman gain coefficient by changing the polarizability of the material. We have also made a new suite of small molecules that intrinsically have increased Raman gain values. By grafting the materials to the device surface, the overall Raman gain of the device is increased. These approaches enable two different strategies of improving the Raman efficiency and threshold of microcavity-based lasers.
As a result of their ability to amplify input light, ultra-high quality factor (Q) whispering gallery mode optical resonators have found numerous applications spanning from basic science through applied technology. Because the Q is critical to the device’s utility, an ever-present challenge revolves around maintaining the Q factor over long timescales in ambient environments. The counter-approach is to increase the nonlinear coefficient of relevance to compensate for Q degradation. In the present work, we strive to accomplish both, in parallel. For example, one of the primary routes for Q degradation in silica cavities is the formation of water monolayers. By changing the surface functional groups, we can inhibit this process, thus stabilizing the Q above 100 million in ambient environments. In parallel, using a machine learning strategy, we have intelligently designed, synthesized, and verified the next generation of small molecules to enable ultra-low threshold and high efficiency Raman lasing. The molecules are verified using the silica microcavity as a testbed cavity. However, the fundamental design strategy is translatable to other whispering gallery mode cavities.
High quality whispering gallery mode resonators can greatly enhance the optical field by trapping the light through total internal reflection, which makes these resonators a promising platform for many areas of research, including optical sensing, frequency combs, Raman lasing and cavity QED. Among these resonators, silica microtoroidal resonators are widely used because of their ability to be integrated and to achieve ultrahigh quality factors (above 100 million). However, quality factors of traditional silica toroids gradually decrease over time because there is an intrinsic layer of hydroxyl groups on the silica surface. This layer of hydroxyl groups attracts water molecules in the atmosphere and results in high optical losses. This property of silica degrades the behavior and limits the applications of the integrated silica toroids. In this work, we address this limitation by fabricating integrated microtoroids from silicon oxynitride. The surface of silicon oxynitride has a mixture of hydroxyl groups and fluorine groups. This mixture prevents the formation of a layer of water molecules that causes the optical losses. Our experiments demonstrate that the quality factors of the silicon oxynitride toroids exceed 100 million, and these values are maintained for over two weeks without controlling the storage conditions. As a comparison, quality factors of traditional silica toroids fabricated and stored under same conditions decayed by approximately an order of magnitude over the same duration.
High and ultra-quality factor (Q) optical resonators have been used in numerous applications, ranging from biodetection and gyroscopes to nonlinear optics. In the majority of the measurements, the fundamental optical mode is used as it is easy to predict its behavior and subsequent response. However, there are numerous other modes which could give improved performance or offer alternative measurement opportunities. For example, by using a mode located farther from the device surface, the optical field becomes less susceptible to changes in the environment. However, selectively exciting a pre-determined, non-fundamental mode or, alternatively, creating a “designer” mode which has one’s ideal properties is extremely challenging. One approach which will be presented is based on engineering a gradient refractive index (GRIN) cavity. We use a silica ultra-high-Q toroidal cavity as a starting platform device. On top of this structure, we can controllably deposit, layer or grow different materials of different refractive indices, with nm-scale precision, creating resonators with a GRIN region co-located with the optical field. Slight adjustments in the thicknesses or indices of the films result in large changes in the mode which is most easily excited. Even in this architected structure, we have maintained Q>1 million. Using this approach, we have demonstrated the ability to tune the properties of the device. For example, we have changed the thermal response and the UV response of a device by over an order of magnitude.
Silica and silica-doped high quality factor (Q) optical resonators have demonstrated ultra-low threshold lasers based on numerous mechanisms (eg rare earth dopants, Raman). To date, the key focus has been on maintaining a high Q, as that determines the lasing threshold and linewidth. However, equally important criteria are lasing efficiency and wavelength. These parameters are governed by the material, not the cavity Q. Therefore, to fully address this challenge, it is necessary to develop new materials. We have synthesized a suite of silica and polymeric materials with nanoparticle and rare-earth dopants to enable the development of microcavity lasers with emission from the near-IR to the UV. Additionally, the efficiencies and thresholds of many of these devices surpass the previous work. Specifically, the silica sol-gel lasers are co- and tri-doped with metal nanoparticles (eg Ti, Al) and rare-earth materials (eg Yb, Nb, Tm) and are fabricated using conventional micro/nanofabrication methods. The intercalation of the metal in the silica matrix reduces the clustering of the rare-earth ions and reduces the phonon energy of the glass, improving efficiency and overall device performance. Additionally, the silica Raman gain coefficient is enhanced due to the inclusion of the metal nanoparticles, which results in a lower threshold and a higher efficiency silica Raman laser. Finally, we have synthesized several polymer films doped with metal (eg Au, Ag) nanoparticles and deposited them on the surface of our microcavity devices. By pumping on the plasmonic resonant wavelength of the particle, we are able to achieve plasmonic-enhanced upconversion lasing.
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