A wearable microfluidic system for efficient sweat collection and real-time detection.

Sweat is an important biofluid with rich physiological information that can evaluate human health condition. Wearable sweat sensors have received widespread attention in recent years due to the benefits of non-invasive, continuous, and real-time monitoring. Currently, an efficient device integrating sweat collection and detection is still needed. Here, a wearable sweat microfluidic system was fabricated for real-time collection and analysis of sweat. The fabricated microfluidic system consisted of four layers, including a skin adhesive layer, a microfluidic layer, an electrode layer, and a capping layer. The sweat collection rate was around 0.79 µL/min, which demonstrated efficient sweat sampling, storage, and refreshing capabilities. Simultaneous detection of multiple sweat biomarkers was achieved with a screen-printed sweat sensing array, which could realize high-precision detection of Na+, K+, and glucose. Moreover, the sensing array also showed good repeatability and stability, with a relative standard deviation of sensitivity of less than 5%. Additionally, human testing was conducted to demonstrate that this microfluidic system can continuously monitor Na+, K+, and glucose in subjects' sweat during exercise, which showed high potential for non-invasive human health monitoring.

Editorial for the Special Issue on Physics in Micro/Nano Devices: From Fundamental to Application.

With the continuous miniaturization of micro/nano devices, it is of great importance to study the physics of these devices, both for fundamental and practical research [...].

Determination of a Raman shift laser power coefficient based on cross correlation.

This work presents a novel, to the best of our knowledge, cross correlation technique for determining the laser heating-induced Raman shift laser power coefficient ψ required for energy transport state-resolved Raman (ET-Raman) methods. The cross correlation method determines the measure of similarity between the experimental intensity data and a varying test Gaussian signal. By circumventing the errors inherent in any curve fittings, the cross correlation method quickly and accurately determines the location where the test Gaussian signal peak is most like the Raman peak, thereby revealing the peak location and ultimately the value of ψ. This method improves the reliability of optothermal Raman-based methods for micro/nanoscale thermal measurements and offers a robust approach to data processing through a global treatment of Raman spectra.

Critical problems faced in Raman-based energy transport characterization of nanomaterials.

In the last two decades, tremendous research has been conducted on the discovery, design and synthesis, characterization, and applications of two-dimensional (2D) materials. Thermal conductivity and interface thermal conductance/resistance of 2D materials are two critical properties in their applications. Raman spectroscopy, which measures the inelastic scattering of photons by optical phonons, can distinct a 2D material's temperature from its surrounding materials', featuring unprecedented spatial resolution (down to the atomic level). Raman-based thermometry has been used tremendously for characterizing the thermal conductivity of 2D materials (suspended or supported) and interface thermal conductance/resistance. Very large data deviations have been observed in literature, partly due to physical phenomena and factors not considered in measurements. Here, we provide a critical review, analysis, and perspectives about a broad spectrum of physical problems faced in Raman-based thermal characterization of 2D materials, namely interface separation, localized stress due to thermal expansion mismatch, optical interference, conjugated phonon, and hot carrier transport, optical-acoustic phonon thermal nonequilibrium, and radiative electron-hole recombination in monolayer 2D materials. Neglect of these problems will lead to a physically unreasonable understanding of phonon transport and interface energy coupling. In-depth discussions are also provided on the energy transport state-resolved Raman (ET-Raman) technique to overcome these problems and on future research challenges and needs.

A Fiber-Based SPR Aptasensor for the In Vitro Detection of Inflammation Biomarkers.

It is widely accepted that the abnormal concentrations of different inflammation biomarkers can be used for the early diagnosis of cardiovascular disease (CVD). Currently, many reported strategies, which require extra report tags or bulky detection equipment, are not portable enough for onsite inflammation biomarker detection. In this work, a fiber-based surface plasmon resonance (SPR) biosensor decorated with DNA aptamers, which were specific to two typical inflammation biomarkers, C-reactive protein (CRP) and cardiac troponin I (cTn-I), was developed. By optimizing the surface concentration of the DNA aptamer, the proposed sensor could achieve a limit of detection (LOD) of 1.7 nM (0.204 µg/mL) and 2.5 nM (57.5 ng/mL) to CRP and cTn-I, respectively. Additionally, this biosensor could also be used to detect other biomarkers by immobilizing corresponding specific DNA aptamers. Integrated with a miniaturized spectral analysis device, the proposed sensor could be applied for constructing a portable instrument to provide the point of care testing (POCT) for CVD patients.

DNA-Based Biosensors for the Biochemical Analysis: A Review.

In recent years, DNA-based biosensors have shown great potential as the candidate of the next generation biomedical detection device due to their robust chemical properties and customizable biosensing functions. Compared with the conventional biosensors, the DNA-based biosensors have advantages such as wider detection targets, more durable lifetime, and lower production cost. Additionally, the ingenious DNA structures can control the signal conduction near the biosensor surface, which could significantly improve the performance of biosensors. In order to show a big picture of the DNA biosensor's advantages, this article reviews the background knowledge and recent advances of DNA-based biosensors, including the functional DNA strands-based biosensors, DNA hybridization-based biosensors, and DNA templated biosensors. Then, the challenges and future directions of DNA-based biosensors are discussed and proposed.

Methods for Measuring Thermal Conductivity of Two-Dimensional Materials: A Review.

Two-dimensional (2D) materials are widely used in microelectronic devices due to their excellent optical, electrical, and mechanical properties. The performance and reliability of microelectronic devices based 2D materials are affected by heat dissipation performance, which can be evaluated by studying the thermal conductivity of 2D materials. Currently, many theoretical and experimental methods have been developed to characterize the thermal conductivity of 2D materials. In this paper, firstly, typical theoretical methods, such as molecular dynamics, phonon Boltzmann transport equation, and atomic Green's function method, are introduced and compared. Then, experimental methods, such as suspended micro-bridge, 3ω, time-domain thermal reflectance and Raman methods, are systematically and critically reviewed. In addition, the physical factors affecting the thermal conductivity of 2D materials are discussed. At last, future prospects for both theoretical and experimental thermal conductivity characterization of 2D materials is given. This paper provides an in-depth understanding of the existing thermal conductivity measurement methods of 2D materials, which has guiding significance for the application of 2D materials in micro/nanodevices.

Direct Characterization of Thermal Nonequilibrium between Optical and Acoustic Phonons in Graphene Paper under Photon Excitation.

Raman spectroscopy has been widely used to measure thermophysical properties of 2D materials. The local intense photon heating induces strong thermal nonequilibrium between optical and acoustic phonons. Both first principle calculations and recent indirect Raman measurements prove this phenomenon. To date, no direct measurement of the thermal nonequilibrium between optical and acoustic phonons has been reported. Here, this physical phenomenon is directly characterized for the first time through a novel approach combining both electrothermal and optothermal techniques. While the optical phonon temperature is determined from Raman wavenumber, the acoustic phonon temperature is precisely determined using high-precision thermal conductivity and laser power absorption that are measured with negligible nonequilibrium among energy carriers. For graphene paper, the energy coupling factor between in-plane optical and overall acoustic phonons is found at (1.59-3.10) × 1015 W m-3 K-1, agreeing well with the quantum mechanical modeling result of 4.1 × 1015 W m-3 K-1. Under ≈1 µm diameter laser heating, the optical phonon temperature rise is over 80% higher than that of the acoustic phonons. This observation points out the importance of subtracting optical-acoustic phonon thermal nonequilibrium in Raman-based thermal characterization.

The in-plane structure domain size of nm-thick MoSe2 uncovered by low-momentum phonon scattering.

Although 2D materials have been widely studied for more than a decade, very few studies have been reported on the in-plane structure domain (STD) size even though such a physical property is critical in determining the charge carrier and energy carrier transport. Grazing incidence X-ray diffraction (XRD) can be used for studying the in-plane structure of very thin samples, but it becomes more challenging to study few-layer 2D materials. In this work the nanosecond energy transport state-resolved Raman (nET-Raman) technique is applied to resolve this key problem by directly measuring the thermal reffusivity of 2D materials and determining the residual value at the 0 K-limit. Such a residual value is determined by low-momentum phonon scattering and can be directly used to characterize the in-plane STD size of 2D materials. Three suspended MoSe2 (15, 50 and 62 nm thick) samples are measured using nET-Raman from room temperature down to 77 K. Based on low-momentum phonon scattering, the STD size is determined to be 58.7 nm and 84.5 nm for 50 nm and 62 nm thick samples, respectively. For comparison, the in-plane structure of bulk MoSe2 that is used to prepare the measured nm-thick samples is characterized using XRD. It uncovers crystallite sizes of 64.8 nm in the (100) direction and 121 nm in the (010) direction. The STD size determined by our low momentum phonon scattering is close to the crystallite size determined by XRD, but still shows differences. The STD size by low-momentum phonon scattering is more affected by the crystallite sizes in all in-plane directions rather than that by XRD that is for a specific crystallographic orientation. Their close values demonstrate that during nanosheet preparation (peeling and transfer), the in-plane structure experiences very little damage.

A thermal activated and differential self-calibrated flexible epidermal biomicrofluidic device for wearable accurate blood glucose monitoring.

This paper reports a flexible electronics-based epidermal biomicrofluidics technique for clinical continuous blood glucose monitoring, overcoming the drawback of the present wearables, unreliable measurements. A thermal activation method is proposed to improve the efficiency of transdermal interstitial fluid (ISF) extraction, enabling extraction with a low current density to notably reduce skin irritation. An Na+ sensor and a correction model are proposed to eliminate the effect of individual differences, which leads to fluctuations in the amount of ISF extraction. An electrochemical sensor with a 3D nanostructured working electrode surface is designed to enable precise in situ glucose measurement. A differential structure is proposed to eliminate the effect of passive perspiration, which leads to inaccurate blood glucose prediction. Fabrications of the epidermal biomicrofluidic device including formation of flexible electrodes, nanomaterial modification, and enzyme immobilization are fully realized by inkjet printing to enable facile manufacturing with low cost, which benefits practical production.

Interfacial Thermal Conductance between Monolayer WSe2 and SiO2 under Consideration of Radiative Electron-Hole Recombination.

This work reports the interfacial thermal conductance (G) and radiative recombination efficiency (ß), also known as photoluminescence quantum yield (PL QY), of monolayer WSe2 flakes supported by fused silica substrates via energy-transport state-resolved Raman (ET-Raman). This is the first known work to consider the effect of radiative electron-hole recombination on the thermal transport characteristics of single-layer transition-metal dichalcogenides (TMDs). ET-Raman uses a continuous-wave laser for steady-state heating as well as nanosecond and picosecond lasers for transient energy transport to simultaneously heat the monolayer flakes and extract the Raman signal. The three lasers induce distinct heating phenomena that distinguish the interfacial thermal conductance and radiative recombination efficiency, which can then be determined in tandem with three-dimensional (3D) numerical modeling of the temperature rise from respective laser irradiation. For the five samples measured, G is found to range from 2.10 ± 0.14 to 15.9 ± 5.0 MW m-2 K-1 and ß ranges from 36 ± 6 to 65 ± 7%. These values support the claim that interfacial phenomena such as surface roughness and two-dimensional (2D) material-substrate bonding strength play critical roles in interfacial thermal transport and electron-hole recombination mechanisms in TMD monolayers. It is also determined that low-level defect density enhances the radiative recombination efficiency of single-layer WSe2.

Energy and Charge Transport in 2D Atomic Layer Materials: Raman-Based Characterization.

As they hold extraordinary mechanical and physical properties, two-dimensional (2D) atomic layer materials, including graphene, transition metal dichalcogenides, and MXenes, have attracted a great deal of attention. The characterization of energy and charge transport in these materials is particularly crucial for their applications. As noncontact methods, Raman-based techniques are widely used in exploring the energy and charge transport in 2D materials. In this review, we explain the principle of Raman-based thermometry in detail. We critically review different Raman-based techniques, which include steady state Raman, time-domain differential Raman, frequency-resolved Raman, and energy transport state-resolved Raman techniques constructed in the frequency domain, space domain, and time domain. Detailed outlooks are provided about Raman-based energy and charge transport in 2D materials and issues that need special attention.

Step emulsification in microfluidic droplet generation: mechanisms and structures.

The droplet-based microfluidic techniques have been applied widely in functional material synthesis and biomedical information measurements, wherein step emulsification as an integrated system combines the advantages of homogeneity and throughput in monodisperse droplet formation. This paper reviews the mechanisms and classical structures of step emulsification. In terms of droplet formation mechanisms, we describe the droplet size and detachment regimes related to the microchannel geometry. Distinguished by droplet formation, microfluidic step emulsification driven by interfacial tension and centrifugal step emulsification related to buoyancy are introduced respectively, including their improved structures for enhancing the droplet homogeneity and throughput. Finally, the perspectives about the developments of step emulsification in mechanisms, fabrications, and applications are discussed.

Distinguishing Optical and Acoustic Phonon Temperatures and Their Energy Coupling Factor under Photon Excitation in nm 2D Materials.

Under photon excitation, 2D materials experience cascading energy transfer from electrons to optical phonons (OPs) and acoustic phonons (APs). Despite few modeling works, it remains a long-history open problem to distinguish the OP and AP temperatures, not to mention characterizing their energy coupling factor (G). Here, the temperatures of longitudinal/transverse optical (LO/TO) phonons, flexural optical (ZO) phonons, and APs are distinguished by constructing steady and nanosecond (ns) interphonon branch energy transport states and simultaneously probing them using nanosecond energy transport state-resolved Raman spectroscopy. ΔT OP -AP is measured to take more than 30% of the Raman-probed temperature rise. A breakthrough is made on measuring the intrinsic in-plane thermal conductivity of suspended nm MoS2 and MoSe2 by completely excluding the interphonon cascading energy transfer effect, rewriting the Raman-based thermal conductivity measurement of 2D materials. G OP↔AP for MoS2, MoSe2, and graphene paper (GP) are characterized. For MoS2 and MoSe2, G OP↔AP is in the order of 1015 and 1014 W m-3 K-1 and G ZO↔AP is much smaller than G LO/TO↔AP. Under ns laser excitation, G OP↔AP is significantly increased, probably due to the reduced phonon scattering time by the significantly increased hot carrier population. For GP, G LO/TO↔AP is 0.549 × 1016 W m-3 K-1, agreeing well with the value of 0.41 × 1016 W m-3 K-1 by first-principles modeling.

Thermal conductance between water and nm-thick WS2: extremely localized probing using nanosecond energy transport state-resolved Raman.

Liquid-solid interface energy transport has been a long-term research topic. Past research mostly focused on theoretical studies while there are only a handful of experimental reports because of the extreme challenges faced in measuring such interfaces. Here, by constructing nanosecond energy transport state-resolved Raman spectroscopy (nET-Raman), we characterize thermal conductance across a liquid-solid interface: water-WS2 nm film. In the studied system, one side of a nm-thick WS2 film is in contact with water and the other side is isolated. WS2 samples are irradiated with 532 nm wavelength lasers and their temperature evolution is monitored by tracking the Raman shift variation in the E2g mode at several laser powers. Steady and transient heating states are created using continuous wave and nanosecond pulsed lasers, respectively. We find that the thermal conductance between water and WS2 is in the range of 2.5-11.8 MW m-2 K-1 for three measured samples (22, 33, and 88 nm thick). This is in agreement with molecular dynamics simulation results and previous experimental work. The slight differences are attributed mostly to the solid-liquid interaction at the boundary and the surface energies of different solid materials. Our detailed analysis confirms that nET-Raman is very robust in characterizing such interface thermal conductance. It completely eliminates the need for laser power absorption and Raman temperature coefficients, and is insensitive to the large uncertainties in 2D material properties input.

Graphene Aerogel Based Bolometer for Ultrasensitive Sensing from Ultraviolet to Far-Infrared.

This work uncovers that free-standing partly reduced graphene aerogel (PRGA) films in vacuum exhibit extraordinarily bolometric responses. This high performance is mainly attributed to four structure characteristics: extremely low thermal conductivity (6.0-0.6 mW·m-1·K-1 from 295 to 10 K), high porosity, ultralow density (4 mg·cm-3), and abundant functional groups (resulting in tunable band gap). Under infrared radiation (peaked at 5.8-9.7 µm), the PRGA film can detect a temperature change of 0.2, 1.0, and 3.0 K of a target at 3, 25, and 54 cm distance. Even through a quartz window (transmissivity of ∼0.98 in the range of 2-4 µm), it can still successfully detect a temperature change of 0.6 and 5.8 K of a target at 3 and 28 cm distance. At room temperature, a laser power as low as 7.5 µW from a 405 nm laser and 5.9 µW from a 1550 nm laser can be detected. The detecting sensitivity to the 1550 nm laser is further increased by 3-fold when the sensor temperature was reduced from 295 K to 12 K. PRGA films are demonstrated to be a promising ultrasensitive bolometric detector, especially at low temperatures.

Measurement of the thermal conductivities of suspended MoS2 and MoSe2 by nanosecond ET-Raman without temperature calibration and laser absorption evaluation.

Steady state Raman spectroscopy is the most widely used opto-thermal technique for measuring a 2D atomic-layer material's thermal conductivity. It requires the calibration of temperature coefficients of Raman properties and measurement/calculation of the absolution laser absorption in 2D materials. Such a requirement is very laborious and introduces very large measurement errors (of the order of 100%) and hinders gaining a precise and deep understanding of phonon-structure interactions in 2D materials. In this work, a novel nanosecond energy transport state resolved Raman (ns ET-Raman) technique is developed to resolve these critical issues and achieve unprecedented measurement precision, accuracy and ease of implementation. In ns ET-Raman, two energy transport states are constructed: steady state and nanosecond thermal transport and Raman probing. The ratio of the temperature rise under the two states eliminates the need for Raman temperature calibration and laser absorption evaluation. Four suspended MoS2 (45-115 nm thick) and four suspended MoSe2 (45-140 nm thick) samples are measured and compared using ns ET-Raman. With the increase of the sample thickness, the measured thermal conductivity increases from 40.0 ± 2.2 to 74.3 ± 3.2 W m-1 K-1 for MoS2, and from 11.1 ± 0.4 to 20.3 ± 0.9 W m-1 K-1 for MoSe2. This is attributed to the decreased significance of surface phonon scattering in thicker samples. The ns ET-Raman features the most advanced capability to measure the thermal conductivity of 2D materials and will find broad applications in studying low-dimensional materials.

Nonmonotonic thickness-dependence of in-plane thermal conductivity of few-layered MoS2: 2.4 to 37.8 nm.

Recent first-principles modeling reported a decrease of in-plane thermal conductivity (k) with increased thickness for few layered MoS2, which results from the change in phonon dispersion and missing symmetry in the anharmonic atomic force constant. For other 2D materials, it has been well documented that a higher thickness could cause a higher in-plane k due to a lower density of surface disorder. However, the effect of thickness on the k of MoS2 has not been systematically uncovered by experiments. In addition, from either experimental or theoretical approaches, the in-plane k value of tens-of-nm-thick MoS2 is still missing, which makes the physics on the thickness-dependent k remain ambiguous. In this work, we measure the k of few-layered (FL) MoS2 with thickness spanning a large range: 2.4 nm to 37.8 nm. A novel five energy transport state-resolved Raman (ET-Raman) method is developed for the measurement. For the first time, the critical effects of hot carrier diffusion, electron-hole recombination, and energy coupling with phonons are taken into consideration when determining the k of FL MoS2. By eliminating the use of laser energy absorption data and Raman temperature calibration, unprecedented data confidence is achieved. A nonmonotonic thickness-dependent k trend is discovered. k decreases from 60.3 W m-1 K-1 (2.4 nm thick) to 31.0 W m-1 K-1 (9.2 nm thick), and then increases to 76.2 W m-1 K-1 (37.8 nm thick), which is close to the reported k of bulk MoS2. This nonmonotonic behavior is analyzed in detail and attributed to the change of phonon dispersion for very thin MoS2 and a reduced surface scattering effect for thicker samples.

Very fast hot carrier diffusion in unconstrained MoS2 on a glass substrate: discovered by picosecond ET-Raman.

The currently reported optical-phonon-scattering-limited carrier mobility of MoS2 is up to 417 cm2 V-1 s-1 with two-side dielectric screening: one normal-κ side and one high-κ side. Herein, using picosecond energy transport state-resolved Raman (ET-Raman), we demonstrated very fast hot carrier diffusion in µm-scale (lateral) unconstrained MoS2 (1.8-18 nm thick) on a glass substrate; this method enables only one-side normal-κ dielectric screening. The ET-Raman method directly probes the diffusion of the hot carrier and its contribution to phonon transfer without contact and additional sample preparation and provides unprecedented insight into the intrinsic D of MoS2. The measured D values span from 0.76 to 9.7 cm2 s-1. A nonmonotonic thickness-dependent D trend is discovered, and it peaks at 3.0 nm thickness. This is explained by the competition between two physical phenomena: with an increase in sample thickness, the increased screening of the substrate results in higher mobility; moreover, thicker samples are subject to more surface contamination, loose substrate contact and weaker substrate dielectric screening. The corresponding carrier mobility varies from 31.0 to 388.5 cm2 V-1 s-1. This mobility is surprisingly high considering the normal-κ and single side dielectric screening by the glass substrate. This is a direct result of the less-damaged structure of MoS2 that is superior to those of MoS2 samples reported in literature studies that are subjected to various post-processing techniques to facilitate measurement. The very high hot carrier mobility reduces the local carrier concentration and enhances the Raman signal, which is further confirmed by our Raman signal studies and comparison with theoretical studies.

Identifying the Crystalline Orientation of Black Phosphorus by Using Optothermal Raman Spectroscopy.

Current polarized Raman-based techniques for identifying the crystalline orientation of black phosphorus suffer significant uncertainty and unreliability because of the complex interference involving excitation laser wavelength, scattering light wavelength, and sample thickness. Herein, for the first time, we present a new method, optothermal Raman spectroscopy (OT-Raman), for identifying crystalline orientation. With a physical mechanism based on the anisotropic optical absorption of the polarized laser and the resulting heating, the OT-Raman can identify the crystalline orientation explicitly, regardless of excitation wavelength and sample thickness, by Raman frequency-power differential Φ (=∂ω/∂P). The parameter Φ has the largest (smallest) value when the laser polarization is along the armchair (zigzag) direction. The OT-Raman technique is robust and is able to identify the crystalline orientation of BP samples with thicknesses up to 300 nm at a minimum and potentially as high as 1200 nm.