Intracellular biocompatible hexagonal boron nitride quantum emitters as single-photon sources and barcodes.

Color centers in hexagonal boron nitride (hBN) have been emerging as a multifunctional platform for various optical applications including quantum information processing, quantum computing and imaging. Simultaneously, due to its biocompatibility and biodegradability hBN is a promising material for biomedical applications. In this work, we demonstrate single-photon emission from hBN color centers embedded inside live cells and their application to cellular barcoding. The generation and internalization of multiple color centers into cells was performed via simple and scalable procedure while keeping the cells unharmed. The emission from live cells was observed as multiple diffraction-limited spots, which exhibited excellent single-photon characteristics with high single-photon purity of 0.1 and superb emission stability without photobleaching or spectral shifts over several hours. Due to different emission wavelengths and peak widths of the color centers, they were employed as barcodes. We term them Quantum Photonic Barcodes (QPBs). Each QPB can exist in one out of 470 possible distinguishable states and a combination of a few QPBs per cell can be used to uniquely tag virtually an unlimited number of cells. The barcodes developed here offer some excellent properties, including ease of production by a single-step procedure, biocompatibility and biodegradability, emission stability, no photobleaching, small size and a huge number of unique barcodes. This work provides a basis for the use of hBN color centers for robust barcoding of cells and due to the single photon emission, presented concepts could in future be extended to quantum-limited sensing and super-resolution imaging.

Interferometric Fiber Optic Probe for Measurements of Cavitation Bubble Expansion Velocity and Bubble Oscillation Time.

Cavitation bubbles are used in medicine as a mechanism to generate shock waves. The study of cavitation bubble dynamics plays a crucial role in understanding and utilizing such phenomena for practical applications and purposes. Since the lifetime of cavitation bubbles is in the range of hundreds of microseconds and the radii are in the millimeter range, the observation of bubble dynamics requires complicated and expensive equipment. High-speed cameras or other optical techniques require transparent containers or at least a transparent optical window to access the region. Fiber optic probe tips are commonly used to monitor water pressure, density, and temperature, but no study has used a fiber tip sensor in an interferometric setup to measure cavitation bubble dynamics. We present how a fiber tip sensor system, originally intended as a hydrophone, can be used to track the expansion and contraction of cavitation bubbles. The measurement is based on interference between light reflected from the fiber tip surface and light reflected from the cavitation bubble itself. We used a continuous-wave laser to generate cavitation bubbles and a high-speed camera to validate our measurements. The shock wave resulting from the collapse of a bubble can also be measured with a delay in the order of 1 µs since the probe tip can be placed less than 1 mm away from the origin of the cavitation bubble. By combining the information on the bubble expansion velocity and the time of bubble collapse, the lifetime of a bubble can be estimated. The bubble expansion velocity is measured with a spatial resolution of 488 nm, half the wavelength of the measuring laser. Our results demonstrate an alternative method for monitoring bubble dynamics without the need for expensive equipment. The method is flexible and can be adapted to different environmental conditions, opening up new perspectives in many application areas.

Measurements of hair temperature avalanche effect with alexandrite and Nd:YAG hair removal lasers.

BACKGROUND AND OBJECTIVES: In this study, we investigate the photothermal response of human hair using a pulsed laser source employed in the hair removal treatment. The purpose is to understand the dynamics behind the most common clinical practice to better define the salient features that may contribute to the efficiency of the process. STUDY DESIGN/MATERIALS AND METHODS: Temperature changes of hair samples (dark brown color) from a human scalp (skin type Fitpatrick II) were measured by a thermal camera following irradiation with single and multiple neodymium: yttrium-aluminum-garnet (Nd:YAG) (1064 nm) and alexandrite (755 nm) laser pulses. Particularly, the hair was treated with an individual laser pulse of a sufficiently high fluence, or with a series of lower fluence laser pulses. We investigated the temperature increase in a broad range of fluence and number of pulses. From the data analysis we extrapolated important parameters such as thermal gain and threshold fluence that can be used for determining optimal parameters for the hair removal procedure. Our experimental investigations and hypothesis were supported by a numerical simulation of the light-matter interaction in a skin-hair model, and by optical transmittance measurements of the irradiated hair. RESULTS: An enhancement of the temperature response of the irradiated hair, that deviates from the linear behavior, is observed when hair is subjected to an individual laser pulse of a sufficiently high fluence or to a series of lower fluence laser pulses. Here, we defined the nonlinear and rapid temperature built-up as an avalanche effect. We estimated the threshold fluence at which this process takes place to be at 10 and 2.5 J/cm2 for 1064 and 755 nm laser wavelengths, respectively. The thermal gain expressed by the degree of the deviation from the linear behavior can be higher than 2 when low laser fluence and multiple laser pulses are applied (n = 50). The comparison of the calculated gain for the two different laser wavelengths and the number of pulses reveals a much higher efficiency when low fluence and multiple pulses are delivered. The avalanche effect manifests when the hair temperature exceeds 45°C. The enhanced temperature increase during the subsequent delivery of laser pulses could be ascribed to the temperature-induced changes in the hair's structural properties. Simulations of the hair temperature under Nd:YAG and alexandrite irradiation indicate that the avalanche phenomenon observed in the hair suspended in air may apply also to the hair located within the skin matrix. Namely, for the same fluence, similar temperature increase was obtained also for the hair located within the skin. CONCLUSION: The observed "avalanche" effect may contribute to the reported clinical efficacy of laser hair removal and may at least partially explain the observed efficacy of the brushing hair removal procedures where laser fluence is usually low. The repeated irradiation during the brushing procedure may lead to an avalanche-like gradual increase of the hair's thermal response resulting in sufficiently high final hair temperatures as required for effective hair reduction.

Ultrasonic photoacoustic emitter of graphene-nanocomposites film on a flexible substrate.

Photoacoustic devices generating high-amplitude and high-frequency ultrasounds are attractive candidates for medical therapies and on-chip bio-applications. Here, we report the photoacoustic response of graphene nanoflakes - Polydimethylsiloxane composite. A protocol was developed to obtain well-dispersed graphene into the polymer, without the need for surface functionalization, at different weight percentages successively spin-coated onto a Polydimethylsiloxane substrate. We found that the photoacoustic amplitude scales up with optical absorption reaching 11 MPa at ∼ 228 mJ/cm2 laser fluence. We observed a deviation of the pressure amplitude from the linearity increasing the laser fluence, which indicates a decrease of the Grüneisen parameter. Spatial confinement of high amplitude (> 40 MPa, laser fluence > 55 mJ/cm2) and high frequency (Bw-6db ∼ 21.5 MHz) ultrasound was achieved by embedding the freestanding film in an optical lens. The acoustic gain promotes the formation of cavitation microbubbles for moderate fluence in water and in tissue-mimicking material. Our results pave the way for novel photoacoustic medical devices and integrated components.

Amplification of high-intensity pressure waves and cavitation in water using a multi-pulsed laser excitation and black-TiOx optoacoustic lens.

A method for amplification of high-intensity pressure waves generated with a multi-pulsed Nd:YAG laser coupled with a black-TiOx optoacoustic lens in the water is presented and characterized. The investigation was focused on determining how the multi-pulsed laser excitation with delays between 50 µs and 400 µs influences the dynamics of the bubbles formed by a laser-induced breakdown on the upper surface of the lens, the acoustic cavitation in the focal region of the lens, and the high-intensity pressure waves generation. A needle hydrophone and a high-speed camera were used to analyze the spatial distribution and time-dependent development of the above-mentioned phenomena. Our results show how different delays (td ) of the laser pulses influence optoacoustic dynamics. When td is equal to or greater than the bubble oscillation time, acoustic cavitation cloud size increases 10-fold after the fourth laser pulse, while the pressure amplitude increases by more than 75%. A quasi-deterministic creation of cavitation due to consecutive transient pressure waves is also discussed. This is relevant for localized ablative laser therapy.

Towards personalized and versatile monitoring of temperature fields within heterogeneous tissues during laser therapies.

Advancements in medical laser technology have paved the way for its widespread acceptance in a variety of treatments and procedures. Selectively targeting particular tissue structures with minimally invasive procedures limits the damage to surrounding tissue and allows for reduced post-procedural downtime. In many treatments that are hyperthermia-based, the efficiency depends on the achieved temperature within the targeted tissues. Current approaches for monitoring subdermal temperature distributions are either invasive, complex, or offer inadequate spatial resolution. Numerical studies are often therapy-tailored and source tissue parameters from the literature, lacking versatility and a tissue-specific approach. Here, we show a protocol that estimates the temperature distribution within the tissue based on a thermographic recording of its surface temperature evolution. It couples a time-dependent matching algorithm and thermal-diffusion-based model, while recognizing tissue-specific characteristics yielded by a fast calibration process. The protocol was employed during hyperthermic laser treatment performed ex-vivo on a heterogeneous porcine tissue, and in-vivo on a human subject. In both cases the calibrated thermal parameters correlate with the range of values reported by other studies. The matching algorithm sufficiently reproduced the temperature dynamics of heterogeneous tissue. The estimated temperature distributions within ex-vivo tissue were validated by simultaneous reference measurements, and the ones estimated in-vivo reveal a distribution trend that correlates well with similar studies. The presented method is versatile, supported by the protocol for tissue-specific tailoring, and can readily be implemented for temperature monitoring of various hyperthermia-based procedures by means of recording the surface temperature evolution with a miniature thermal camera implemented within a handheld laser scanner or similar.

Non-contact monitoring of the depth temperature profile for medical laser scanning technologies.

Medical treatments such as high-intensity focused ultrasound, hyperthermic laser lipolysis or radiofrequency are employed as a minimally invasive alternatives for targeted tissue therapies. The increased temperature of the tissue triggers various thermal effects and leads to an unavoidable damage. As targeted tissues are generally located below the surface, various approaches are utilized to prevent skin layers from overheating and irreparable thermal damages. These procedures are often accompanied by cooling systems and protective layers accounting for a non-trivial detection of the subsurface temperature peak. Here, we show a temperature peak estimation method based on infrared thermography recording of the surface temperature evolution coupled with a thermal-diffusion-based model and a time-dependent data matching algorithm. The performance of the newly developed method was further showcased by employing hyperthermic laser lipolysis on an ex-vivo porcine fat tissue. Deviations of the estimated peak temperature remained below 1 °C, as validated by simultaneous measurement of depth temperature field within the tissue. Reconstruction of the depth profile shows a good reproducibility of the real temperature distribution with a small deviation of the peak temperature position. A thermal camera in combination with the time-dependent matching bears the scope for non-contact monitoring of the depth temperature profile as fast as 30 s. The latest demand for miniaturization of thermal cameras provides the possibility to embed the model in portable thermal scanners or medical laser technologies for improving safety and efficiency.

Harnessing Exciton-Exciton Annihilation in Two-Dimensional Semiconductors.

Strong many-body interactions in two-dimensional (2D) semiconductors give rise to efficient exciton-exciton annihilation (EEA). This process is expected to result in the generation of unbound high energy carriers. Here, we report an unconventional photoresponse of van der Waals heterostructure devices resulting from efficient EEA. Our heterostructures, which consist of monolayer transition metal dichalcogenide (TMD), hexagonal boron nitride (hBN), and few-layer graphene, exhibit photocurrent when photoexcited carriers possess sufficient energy to overcome the high energy barrier of hBN. Interestingly, we find that the device exhibits moderate photocurrent quantum efficiency even when the semiconducting TMD layer is excited at its ground exciton resonance despite the high exciton binding energy and large transport barrier. Using ab initio calculations, we show that EEA yields highly energetic electrons and holes with unevenly distributed energies depending on the scattering condition. Our findings highlight the dominant role of EEA in determining the photoresponse of 2D semiconductor optoelectronic devices.

Controlled Aqueous Synthesis of 2D Hybrid Perovskites with Bright Room-Temperature Long-Lived Luminescence.

Recently, some organic-inorganic hybrid perovskites (OIHPs) have been reported to exhibit strong subgap broadband luminescence. While the origin of such luminescence has been proposed by several groups, a strategy to prepare OIHP with the desired subgap emission properties has remained elusive. Here, we report controlled synthesis of a broadband-emitting single-crystal 2D OIHP with an average quantum yield of >80 %. We demonstrate that the intensity of broadband emission can be tuned by controlling the excess iodine ion concentration during the synthesis in hydroiodic acid. We show that the emitters exhibit characteristics of localized defects such as limited mobility and saturation at high excitation power. Using density functional theory calculations, we show that bond-state iodine interstitials are responsible for the observed long-lived luminescence.

Monolayer black phosphorus by sequential wet-chemical surface oxidation.

We report a straightforward chemical methodology for controlling the thickness of black phosphorus flakes down to the monolayer limit by layer-by-layer oxidation and thinning, using water as solubilizing agent. Moreover, the oxidation process can be stopped at will by two different passivation procedures, namely the non-covalent functionalization with perylene diimide chromophores, which prevents the photooxidation, or by using a protective ionic liquid layer. The obtained flakes preserve their electronic properties as demonstrated by fabricating a BP field-effect transistor (FET). This work paves the way for the preparation of BP devices with controlled thickness.

Suppressed Out-of-Plane Polarizability of Free Excitons in Monolayer WSe2.

Monolayer semiconductors are atomically thin quantum wells with strong confinement of electrons in a two-dimensional (2D) plane. Here, we experimentally study the out-of-plane polarizability of excitons in hBN-encapsulated monolayer WSe2 in strong electric fields of up to 1.6 V/nm (16 MV/cm). We monitor free exciton photoluminescence peaks with increasing electric fields at a constant carrier density, carefully compensating for unintentional photodoping in our double-gated device at 4 K. We show that the Stark shift is smaller than 0.4 meV despite the large electric fields applied, yielding an upper limit of polarizability α z to be ∼10-11 Dm/V. Such a small polarizability, which is nearly two orders of magnitude smaller than the previously reported value for MoS2, indicates strong atomic confinement of electrons in this 2D system and highlights the unusual robustness of free excitons against surface potential fluctuations.

Exciton and charge carrier dynamics in few-layer WS2.

Semiconducting transition metal dichalcogenides (TMDs) have been applied as the active layer in photodetectors and solar cells, displaying substantial charge photogeneration yields. However, their large exciton binding energy, which increases with decreasing thickness (number of layers), as well as the strong resonance peaks in the absorption spectra suggest that excitons are the primary photoexcited states. Detailed time-domain studies of the photoexcitation dynamics in TMDs exist mostly for MoS2. Here, we use femtosecond optical spectroscopy to study the exciton and charge dynamics following impulsive photoexcitation in few-layer WS2. We confirm excitons as the primary photoexcitation species and find that they dissociate into charge pairs with a time constant of about 1.3 ps. The better separation of the spectral features compared to MoS2 allows us to resolve a previously undetected process: these charges diffuse through the samples and get trapped at defects, such as flake edges or grain boundaries, causing an appreciable change of their transient absorption spectra. This finding opens the way to further studies of traps in TMD samples with different defect contents.