Several fields of applications require a reliable characterization of the photothermal response and heat dissipation of nanoscopic systems, which remains a challenging task for both modeling and experimental measurements. Here, we present an implementation of anti-Stokes thermometry that enables the in situ photothermal characterization of individual nanoparticles (NPs) from a single hyperspectral photoluminescence confocal image. The method is label-free, potentially applicable to any NP with detectable anti-Stokes emission, and does not require any prior information about the NP itself or the surrounding media. With it, we first studied the photothermal response of spherical gold NPs of different sizes on glass substrates, immersed in water, and found that heat dissipation is mainly dominated by the water for NPs larger than 50 nm. Then, the role of the substrate was studied by comparing the photothermal response of 80 nm gold NPs on glass with sapphire and graphene, two materials with high thermal conductivity. For a given irradiance level, the NPs reach temperatures 18% lower on sapphire and 24% higher on graphene than on bare glass. The fact that the presence of a highly conductive material such as graphene leads to a poorer thermal dissipation demonstrates that interfacial thermal resistances play a very significant role in nanoscopic systems and emphasize the need for in situ experimental thermometry techniques. The developed method will allow addressing several open questions about the role of temperature in plasmon-assisted applications, especially ones where NPs of arbitrary shapes are present in complex matrixes and environments.
Atomic layer deposition (ALD) is a standard technique employed to grow thin-film oxides for a variety of applications. We describe the technique and demonstrate its use for obtaining memristive devices. The metal/insulator/metal stack is fabricated by means of ALD-grown HfO 2 , deposited on top of a highly doped Si substrate with an SiO 2 film and a Ti electrode. Enhanced device capabilities (forming free, self-limiting current, non-crossing hysteretic current-voltage features) are presented and discussed. Careful analysis of the stack structure by means of X-ray reflectometry, atomic force microscopy, and secondary ion mass spectroscopy revealed a modification of the device stack from the intended sequence, HfO 2 /Ti/SiO 2 /Si. Analytical studies unravel an oxidation of the Ti layer which is addressed for the use of the ozone precursor in the HfO 2 ALD process. A new deposition process and the model deduced from impedance measurements support our hypothesis: the role played by ozone on the previously deposited Ti layer is found to determine the overall features of the device. Besides, these ALD-tailored multifunctional devices exhibit rectification capability and long enough retention time to deserve their use as memory cells in a crossbar architecture and multibit approach, envisaging other potential applications.
Micropatterning crystalline materials with oriented pores is necessary for the fabrication of devices with anisotropic properties. Crystalline and porous metal-organic frameworks (MOFs) are ideal materials as their chemical and structural mutability enables precise tuning of functional properties for applications ranging from microelectronics to photonics. Herein, a patternable oriented MOF film is designed: by using a photomask under X-ray exposure, the MOF film decomposes in the irradiated areas, remaining intact in the unexposed regions. The MOF film acts simultaneously as a resist and as functional porous material. While the heteroepitaxial growth from aligned Cu(OH) 2 nanobelts is used to deposit oriented MOF films, the sensitivity to radiation is achieved by integrating a brominated dicarboxylate ligand (Br 2 BDC) into a copper-based MOF Cu 2 L 2 DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane; L = BDC/Br 2 BDC). The lithographed samples act as diffraction gratings upon irradiation with a laser, thus confirming the quality of the extended MOF micropattern. Furthermore, the oriented MOF patterns are functionalized with fluorescent dyes. As a result, by rotating the polarization angle of the laser excitation, the alignment of the dye in the MOF is demonstrated. By controlling the functional response to light, this MOF patterning protocol can be used for the microfabrication of optical components for photonic devices.
While colloidal chemistry provides ways to obtain a great variety of nanoparticles, with different shapes, sizes, material composition, and surface functions, their controlled deposition and combination on arbitrary positions of substrates remains a considerable challenge. Over the last ten years, optical printing arose as a versatile method to achieve this purpose for different kinds of nanoparticles. In this article we review the state of the art of optical printing of single nanoparticles, and discuss its strengths, limitations, and future perspectives, by focusing on four main challenges: printing accuracy, resolution, selectivity, and nanoparticles photostability.
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