Large Absorption Cross Section Research Articles

Fabrication of an erbium–ytterbium-doped waveguide amplifier at communication wavelengths for integrated optics applications

Erbium–ytterbium-doped waveguide amplifiers provide a considerable gain at telecom wavelengths, low noise, nonlinearity, and compatibility with optical networks, making it an outstanding amplification module for telecommunication systems. This study reports on the fabrication of an optical waveguide amplifier for integrated optics. The signal can be amplified by using rare-earth dopings such as erbium (Er), which works at telecommunication wavelengths, i.e., 1.55 μm. Er-doped phosphate glass waveguides can be deposited using the sol–gel method, which is convenient for preparing active films on several substrates. The Er concentration was 1–2 × 1020/cm3. The confinement and the gain of the waveguide can be increased by reducing the width of the waveguide to 0.5 μm. In such a case, more than 1dB net gain can be achieved without additional pump power. The other material used as a dopant in optical amplifiers is ytterbium (Yb). For Er energy levels, a more significant pump intensity is necessary for inversion due to the limited absorption cross-section. This issue is solved by including a substance with a large absorption cross-section that transfers energy to Er. The Ag–Na ion exchange process is then used to fabricate the buried waveguide. In such a process, ions trade between the core material and the molten salt. Then, the waveguide is immersed in the molten salt. The fabricated waveguide has low loss, and a net gain of around 2 dB at a wavelength of approximately 1.55 μm in Er:Yb:Al: phospho silicate glass is achieved. The focus of the research is on the fabrication procedure (materials and methods) of the waveguide.

Research and Design of Aggregation-Induced Phosphorescent Materials for Time-Resolved Two-Photon Excited Luminescence Imaging.

Pure organic two-photon excited room temperature phosphorescent (RTP) materials have attracted great attention for time-resolved imaging due to their long emission lifetime and high resolution. The materials with an aromatic carbonyl group exhibit aggregation-induced emission (AIE) and RTP characteristics simultaneously. Here, we deeply explored the nature of aggregation-induced phosphorescence (AIP), especially the relationship between molecular configuration and optical properties. It was found that aggregation effect can suppress geometrical vibrations and regulate energy difference between S1 and T1. The aromatic carbonyl group plays significant roles in changing electronic configuration, resulting in large Stokes shift and spin-orbit coupling. It also leads to small transition dipole moment, decreasing two-photon absorption cross section and radiative decay rate. To improve two-photon absorption properties, we further designed a π-conjugated compound with large two-photon absorption cross section in the biological window (36.40 GM/656 nm) and AIP characteristics, which is a potential material in the application of time-resolved two-photon excited imaging.

Near-infrared emission of erbium-doped noncytotoxic calcium aluminate

The main goal of this project is to lay the foundation for the use of calcium aluminate doped with Er3+ as a biological marker because the luminescence results showed that this combination can be excited in the first biological window (λ = 808 nm) and relatively less emision intensity in the third biological window (λ = 1550 nm). The simple combustion method was used to create samples of pure calcium dialuminate doped with Er3+ at 0.01, 0.05, 0.1, and 0.2 M %. A fine white powder (in the case of the pure matrix) and pinkish color after doping of the order of microns were obtained from the synthesis process. The data showed that the absorption band around 800 nm (4I9/2) had a larger absorption cross-section than the absorption cross-section typically reported for Er3+.

Small-sized Ag nanoparticle stacked films promoted by sustainedly released surfactants for plasmonic broadband super absorption

Large-area, highly absorptive films stacked of uniform Ag nanoparticles (AgNPs) with sub-20 nm size were fabricated by magnetron sputtering at the presence of adhesive tape, during which O-containing compounds were sustainedly released from the adhesive glue that acted as gaseous surfactants to promote the nucleation and simultaneously suppress the coalescence of the AgNPs. Plasmonic absorbers of metal-insulator-metal (MIM) configuration with a gradient-thickness insulator layer were constructed by conformally depositing such small-sized AgNP stacked films (S-AgSFs) on alumina templates with V-shaped nanopores. The broadband optical impedance matching of this novel MIM structure enables broadband light absorption from ultraviolet to near-infrared region, by working together with the large absorption cross-section, strong interparticle plasmon coupling of closely stacking small-sized AgNPs, and the light-trapping effect of the porous template. The average absorbance reaches 96.8 % in the visible region and 86.7 % in the 200–1600 nm range, respectively, showing the great potential of this absorber for applications in antireflection, solar energy harvesting and utilizing, etc. This adhesive-tape-assisted physical vapor deposition approach is simple, cost-effective, and can be applied to various types of substrates, which will enrich the fabrication strategy of metal nanostructures with effectively controlled geometries and optical properties.

Facile synthesis of ultrabright luminogens with specific lipid droplets targeting feature for in vivo two-photon fluorescence retina imaging

The application of fluorescent probes for in vivo retinal imaging is of great importance, which could provide direct and crucial imaging evidence for a better understanding of common eye diseases. Herein, a group of bright organic luminogens with typical electron-donating (D) and electron-accepting (A) structures (abbreviated as LDs-BDM, LDs-BTM, and LDs-BHM) was synthesized through a simple single-step reaction. They were found to be efficient solid-state emitters with high fluorescence quantum yields of above 70% (e.g., 83.7% for LDs-BTM). Their light-emission properties could be tuned by the modulation of π-conjugation effect with methoxy groups at different substituent positions. Their resulting fluorescent nanoparticles (NPs) were demonstrated as specific lipid droplets (LDs) targeting probes with high brightness, good biocompatibility, and satisfactory photostability. LDs-BTM NPs with a large two-photon absorption cross section (σ2 = 249 GM) were further utilized as ultrabright two-photon fluorescence (2PF) nanoprobes for in vivo retina imaging of live zebrafish by NIR excitation at an ultralow concentration (0.5 µmol/L). Integrated histological structures at the tissue level and corresponding fine details at the cellular level of the embryonic retina of live zebrafish were clearly demonstrated. This is the first report of using ultrabright LDs-targeting nanoprobes to accurately measure fine details in the retina with 2PF microscopic technique. These good results are anticipated to open up a new avenue in the development of efficient 2PF emitters for non-invasive bioimaging of living animals.

Cyano-substituted stilbene (CSS)-based conjugated polymers: Photophysical properties exploration and applications in photodynamic therapy

Conjugated polymers (CPs) have attracted great attention due to their excellent optical properties (such as large absorption cross section, signal amplification, high photostability etc.). As representative electron acceptors and organic small molecules which are easy to be synthesized and modified, cyano-substituted stilbene (CSS) derivatives are widely used to construct photoelectrical materials. Despite donor-acceptor (D-A) conjugated polymers based on CSS have been applied in sensing and super-resolution imaging, systematic studies about the effects of different CSS structures on the photophysical properties of CPs have rarely been reported. Therefore, we have synthesized a series of D-A conjugated polymer nanoparticles (CP NPs) based on different CSS units, and found that the photophysical properties of CP NPs including the bandgap and ΔES-T were closely associated with the structure of CSS derivatives. Moreover, the introduction of tetraphenylethylene (TPE) can relieve the aggregation-caused quenching (ACQ) effects of CSS conjugated polymers to varying degrees. The theoretical calculation further corroborated that by regulating the number and distribution of cyanide groups in the repeating units, the stronger D-A strength resulted in a redshift in the emission spectrum and the more efficient capacity of total ROS (1O2, O2•− and •OH) generation. We then selected CP6-TAT NPs, with the near infrared (NIR) emission and best ФPS, to characterize its performance in photodynamic therapy (PDT). It was revealed that CP6-TAT NPs can be regarded as an ideal candidate for PDT. The results provided a new reference for regulating the structure-effect relationship of CPs and a comprehensive method for constructing photosensitizers based on CPs.

Growth and Spectral Properties of Er3+ and Yb3+ Co-Doped Bismuth Silicate Single Crystal

Rare-earth-doped bismuth silicate (Bi4Si3O12, BSO) crystal is a multifunctional material for scintillation, LED, and laser applications. In the present study, Er3+ and Yb3+ ions co-doped bismuth silicate crystals were grown by a modified vertical Bridgman method, and their spectral properties were investigated for the first time. Transparent Er/Yb: BSO single crystal up to Φ 25 mm × 30 mm was obtained. The segregation coefficient of the Er/Yb: BSO crystal was measured to be 0.96 for Er3+ ions and 0.91 for Yb3+ ions. Absorption and fluorescence spectra had been recorded in the range of 200–1700 nm. The absorption cross section was calculated to be 6.96 × 10−20 cm2 at 976 nm with the full width at half maximum (FWHM) of 8 nm, and the emission cross section was 0.9771 × 10−20 cm2 at 1543 nm with FWHM of 16 nm. The fluorescence decay curve was measured at 976 nm excitation. By linear fitting, the fluorescence lifetime of the upper 4I13/2 level of Er3+ was 8.464 ms at room temperature. Compared with Er3+ ion-doped bismuth silicate crystal (Er: BSO), the Er/Yb: BSO crystal has a wider FWHM and larger absorption cross section. The results indicate that the Er/Yb: BSO crystal is a potential lasing crystal.

Persistent and Efficient Multimodal Imaging for Tyrosinase Based on Two-Photon Excited Fluorescent and Room-Temperature Phosphorescent Probes.

Tyrosinase is crucial to regulate the metabolism of phenol derivatives, playing an important role in the biosynthesis of melanin pigments, whereas an abnormal level of tyrosinase would lead to severe diseases. It is rather necessary to develop a sensitive and selective imaging tool to assess the level of tyrosinase in vivo. We thoroughly researched the luminous mechanism of the existing TPTYR probe and provided design strategies to improve its two-photon excited fluorescence properties. The designed probes benza2-TPTYR and product benza2-TPTYR-coumarin have large two-photon absorption cross sections at the NIR spectral region (41 GM/706 nm, 71 GM/852 nm), while benza2-TPTYR-coumarin possesses easily distinguishable spectrum in the visible region and a high fluorescence efficiency (ΦF = 0.27). What is more, novel two-photon excited multimodal imaging based on the pure organic small molecule benza1-TPTYR-coumarin (61 GM/936 nm) is proposed first, simultaneously possessing strong instantaneous fluorescent (563.79 nm) and persistent room-temperature phosphorescent emissions (767.68 nm, 0.54 ms).

Lipid droplets imaging with three-photon microscopy

Lipid droplets (LDs) participate in many physiological processes, the abnormality of which will cause chronic diseases and pathologies such as diabetes and obesity. It is crucial to monitor the distribution of LDs at high spatial resolution and large depth. Herein, we carried three-photon imaging of LDs in fat liver. Owing to the large three-photon absorption cross-section of the luminogen named NAP-CF3 ([Formula: see text][Formula: see text]cm6 s2), three-photon fluorescence fat liver imaging reached the largest depth of 80[Formula: see text][Formula: see text]m. Fat liver diagnosis was successfully carried out with excellent performance, providing great potential for LDs-associated pathologies research.

Charge Delocalization and Vibronic Couplings in Quadrupolar Squaraine Dyes.

Squaraines are prototypical quadrupolar charge-transfer chromophores that have recently attracted much attention as building blocks for solution-processed photovoltaics, fluorescent probes with large two-photon absorption cross sections, and aggregates with large circular dichroism. Their optical properties are often rationalized in terms of phenomenological essential state models, considering the coupling of two zwitterionic excited states to a neutral ground state. As a result, optical transitions to the lowest S1 excited state are one-photon allowed, whereas the next higher S2 state can only be accessed by two-photon transitions. A further implication of these models is a substantial reduction of vibronic coupling to the ubiquitous high-frequency vinyl-stretching modes of organic materials. Here, we combine time-resolved vibrational spectroscopy, two-dimensional electronic spectroscopy, and quantum-chemical simulations to test and rationalize these predictions for nonaggregated molecules. We find small Huang-Rhys factors below 0.01 for the high-frequency, 1500 cm-1 modes in particular, as well as a noticeable reduction for those of lower frequency modes in general for the electronic S0 → S1 transition. The two-photon allowed state S2 is well separated energetically from S1 and has weak vibronic signatures as well. Thus, the resulting pronounced concentration of the oscillator strength in a narrow region relevant to the lowest electronic transition makes squaraines and their aggregates exceptionally interesting for strong and ultrastrong coupling of excitons to localized light modes in external resonators with chiral properties that can largely be controlled by the molecular architecture.

Absolute [formula omitted]He polarimetry for a double-chambered cell using transmission of thermal neutrons

We present an absolute 3He polarimetry method based on thermal neutron transmission for a double-chambered cell. This method utilizes the fact that a 3He nucleus has a large absorption cross section and a spin dependence for thermal neutrons. The cell had a pumping chamber and a target chamber. Polarized 3He gas was produced in the pumping chamber by SEOP and then diffused into the target chamber. The 3He polarization in the target chamber was determined by comparing the neutron transmissions with the polarized and unpolarized targets. The measurement was performed at the RIKEN Accelerator-Driven Compact Neutron Source. The 3He polarization in the target chamber was determined with a statistical error of 1.8% and systematic uncertainty of 0.6%. This method can be used to obtain high-precision data of spin observables in few-nucleon scattering for the investigation of nuclear forces.

Substituent Effects on the Electronic Spectroscopy of Four-Carbon Criegee Intermediates.

Atmospheric ozonolysis of biogenic and anthropogenic alkenes generates zwitterionic carbonyl oxide intermediates (R1R2C═O+O-), known as Criegee intermediates, with different structural motifs and conformations. This study reports a systematic laboratory study of substituent effects on the electronic spectroscopy of four-carbon Criegee intermediates (CIs) with methyl-ethyl (MECI) and isopropyl (IPCI) groups, which are isomers produced in ozonolysis of asymmetric branched alkenes. The four-carbon CIs are separately generated by an alternative synthetic route, and spectroscopically characterized on the strong π* ← π transition associated with the carbonyl oxide group in a pulsed supersonic expansion with VUV photoionization at 118 nm and UV-induced depletion of the m/z 88 signal. The resultant broad and unstructured UV spectral features for MECI and IPCI are peaked at ca. 320 and 330 nm, respectively, with large absorption cross-sections of ca. 10-17 cm2. Comparisons are made with the four-carbon CIs formed in isoprene ozonolysis, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide), which have the same backbone connectivity as MECI and IPCI but have extended conjugation across the vinyl and carbonyl groups. A remarkable 50 nm shift of the peak absorption to longer wavelength is observed for MVK-oxide and MACR-oxide compared to MECI and IPCI, respectively. Vertical excitation energies computed theoretically agree well with the experimental findings, confirming that the spectral shifts are caused by the extended π conjugation in the isoprene-derived Criegee intermediates.

Synthesis, spectroscopic characterization, one and two-photon absorption properties of β-β linked BODIPY dimers

Five β-β linked BODIPY dimers (d1-d5) with different electron-donating/withdrawing groups at the meso-position were synthesized through improved synthetic methods. All compounds were characterized by 1H and 13C NMR and HRMS. The single crystal X-ray analyses indicate that d4 and d5 display a linear coplanar conformation with two linked BODIPY moiety. Their photophysical and electrochemical properties have been investigated by UV–vis absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy, two-photon excited spectroscopy and cyclic voltammetry. The β-β linked BODIPY dimers exhibit a prominent red shift from the visible region to the red/near-infrared region of their absorption and emission spectra, large Stokes shifts and moderate two-photon absorption cross section σ2 with different groups at the meso-position.

(Digital Presentation) Characterization of Ultrafast Dynamics of Refractory Metal Nanoparticles of Interest as Photocatalysts

Plasmonic noble metal nanoparticles are of interest as photocatalysts for several reasons, including a very large absorption cross section and the creation of a greatly enhanced evanescent electromagnetic field at the surface of the nanoparticles when excited at the plasmon resonance. Furthermore, the plasmon resonance is tunable over a wide wavelength range as a function of the size, shape, and composition of the nanoparticles. When these properties are combined with the known photocatalytic activity of noble metals for technologically important targets such as solar fuels, it is not surprising that these nanoparticle systems are widely studied. Noble metals do, however, possess a weakness in that they can be easily melted upon photoexcitation, due to the fact that noble metals dissipate absorbed photon energy efficiently through ultrafast electron-phonon coupling, in roughly one picosecond, to produce heat. As a result, the study of new classes of plasmonic materials, such as refractory metals, with much higher melting points than noble metals is growing rapidly. While there are still challenges in the size-selective synthesis of refractory metal nanoparticles, characterization efforts on these materials are of strong interest. We report here a study on the time-resolved spectroscopy of electron-phonon coupling in refractory metal nanoparticles. There are very significant variations in the efficiency and time-scales of electron-phonon coupling in refractory metal nanoparticles as compared to noble metal nanoparticles. Furthermore, due to the fact that many refractory metals are oxidized under ambient conditions to create a thin oxide layer on the surface of the nanoparticles, these materials also demonstrate dynamics related to electron injection from the metal to the oxide layer that noble metals do not show. Far from being a negative, the added electron injection dynamics offer new opportunities for photocatalysis that we discuss. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

Aggregation-induced emission nanoprobe assisted ultra-deep through-skull three-photon mouse brain imaging

Optical microscopy has enabled in vivo monitoring of brain structures and functions with high spatial resolution. However, the strong optical scattering in turbid brain tissue and skull impedes the observation of microvasculature and neuronal structures at a large depth. Herein, we proposed a strategy to overcome the influence induced by the high scattering effect of both skull and brain tissue via the combination of skull optical clearing (SOC) technique and three-photon fluorescence microscopy (3PM). The visible-NIR-II compatible skull optical clearing agents (VNSOCA) we applied reduced the skull scattering and water absorption in long wavelength by refractive index matching and H2O replacement to D2O respectively. 3PM with the excitation in the 1300-nm window reached 1.5 mm cerebrovascular imaging depth in cranial window assisted by a kind of bright aggregation-induced emission (AIE) nanoprobe we developed with a large three-photon absorption cross section. Combining the two advanced technologies together, we achieved so far the largest cerebrovascular imaging depth of 1.0 mm and neuronal imaging depth of> 700 µm through intact mouse skull. Dual-channel through-skull imaging of both brain vessels and neurons was also successfully realized, giving an opportunity of non-invasively monitoring the deep brain structures and functions at single-cell level simultaneously.

Aggregation-Induced Emission in Phenothiazine-Based Fluorophores: An Insight into the Excited State and Aggregate Formation Mechanism

In this study, we report evidence for emissive aggregates of push–pull phenothiazine and phenothiazine dioxide derivatives produced both in water dispersions and in the solid state, highly promising for applications in both biology and material science. An insightful investigation of the aggregation-induced emission (AIE) mechanism was carried out via time-resolved spectroscopies, with nanosecond and femtosecond temporal resolution, coupled with advanced data analysis. Our steady-state and time-resolved spectroscopic results unambiguously show that a significant AIE behavior is activated by the restriction of intramolecular rotations for the phenothiazine derivatives. Investigation of the nonlinear optical properties also revealed that aggregates exhibit notable emission upon two-photon excitation. In particular, the phenothiazine dioxide-based aggregates exhibit remarkable fluorescence efficiencies and large two-photon absorption cross sections, as well as the capability to be internalized in HeLa cells exerting no cytotoxic effect. These aggregate species thus prove to be promising as novel fluorophores for bioimaging.

A potent luminogen with NIR-IIb excitable AIE features for ultradeep brain vascular and hemodynamic three-photon imaging

Three-photon excited fluorescence microscopy (3PEFM) has emerged as a promising protocol for visualizing deep-brain vasculature and hemodynamics. However, the current situation is still far from satisfactory, due to small excitation action cross-section and short excitation wavelength of those previously reported 3PEFM luminogens. Herein, we manipulated molecular engineering by subtly regulating structural planarization/twisting to achieve ingenious integration of large three-photon absorption cross-section, high fluorescence quantum yield, ultralong near-infrared IIb excitation, and aggregation-induced emission features. The resulting molecule, namely DPCZ-BT, exhibited as high as 50.6% of fluorescence quantum yield and as large as 2.0 × 10−81 cm6s2/photon2 of three-photon absorption cross-section, which can be excited by 1665 nm fs laser and presents a recorded penetration depth of 1860 μm for deep-brain vascular structural imaging with high spatiotemporal resolution and signal-to-background ratio. Moreover, DPCZ-BT having good photostability and excellent biocompatibility is capable of impressively approaching 1600 μm depth in monitoring red blood cells flow velocity with extraordinary clarity for hemodynamics.

Self-assembly synthesis of flower-like gold nanoparticles for photothermal treatment of cancer

Polymyxin E (PE) could be used as a soft template, because of its characteristics of self-assembly and ability of metal ions reduction. Here, PE induced gold nanoflowers (PE@AuNFs) were successfully synthesized by seed growth method. PE@AuNFs had anisotropy, large absorption cross section, and large surface plasmon resonance (LSPR) peak, resulting in high photothermal conversion efficiency of 34.9%. Moreover, the cell viability of PE@AuNFs for HeLa cells was 19% under near-infrared light irradiation, while cell viability of 15 nm citrate capped gold nanoparticles (SC@AuNPs) was 83%. PE@AuNFs showed good antibacterial effect with laser irradiation. Furthermore, the excellent inhibition efficacy of PE@AuNFs also was demonstrated in U14 tumor-bearing mice in vivo. Taken together, the flower-shaped PE@AuNFs prepared by this new method had good biocompatibility and outstanding near-infrared photothermal treatment effect, indicating their great potential in photothermal therapy.

Rapid screening of up-conversion luminescence phosphors with host containing Yb3+ by 980 nm laser radiation

Rapid screening of up-conversion luminescence (UCL) phosphors with host containing Yb3+ by 980 nm laser radiation was demonstrated, and Yb1.9W3O12:0.1Er3+ and Yb2.9Al5O12:0.1Er3+ phosphors had been successfully prepared by 208.44 W/cm2 of 980 nm laser radiation for 2 s, which is originated from Yb3+ with large absorption cross section around 980 nm. Yb1.9W3O12:0.1Er3+ and Yb2.9Al5O12:0.1Er3+ phosphors emit green and red UCL with the naked eye, respectively. This method can also quickly screen out Er3+ quenching concentration value. And the results of this method are proved to be accurate, which are consistent with that of solid state sintered pure phase samples. The method can be widely applied to prepare and screen other materials by using the light absorption of certain element in the host and choosing laser wavelength as the same with light absorption.

Two-Photon Excited Fluorescent 3,3'-Diamino-5,5'-Diboryl-2,2'-Bithienyls Featuring a Quadrupolar Structure.

The quest for fluorophores exhibiting large two-photon absorption cross sections and high fluorescence efficiency is an important topic. Two 2,2'-bithienyl derivatives are disclosed which contain two N,N-disubstituted amino and two dimesitylboryl groups at 3,3'- and 5,5'-positions, respectively. Despite the great steric effect of amino groups, the bithienyl skeleton still adopts a coplanar geometry. Herein, they are characterized by a quadrupolar structure and display good fluorescence efficiency and large two-photon absorption cross sections up to 473 GM.