Glass containing optically active nanoparticles have been manufactured for centuries. However, only in the early 1900s, the invention of ultramicroscope and development of Mie theory paved the way to ...discovering the occurrence of nanoparticles in glass and their special role in imparting unique optical properties to glass. This groundbreaking insight inspired scientists to extensively research such nanoparticles‐in‐glass hybrid optical materials, which led to a series of fundamental breakthroughs (e.g., invention of glass ceramics, discovery of quantum dots) and commercial successes (e.g., photosensitive glass, photochromic glass, dichromic polarizer). Over the past decades, a new wave of research in this area has been initiated by opportunities of incorporating a large variety of synthetic nanoparticles in glass, which promises the development of advanced functional devices for lighting, display, smart window, data storage, and sensing applications. Recent development of various approaches of fabricating nanoparticles‐in‐glass hybrid optical materials and postmodifying nanoparticles that are embedded in glass is reviewed. The state‐of‐the‐art techniques relevant to controlling the dispersion, distribution, orientation, and nanostructure of nanoparticles in glass, as well as manipulating the macroscopic performance of the hybrid materials are discussed. Examples of applications with promising pathway to commercially viable devices based on hybrid optical materials are outlined.
The integration of optically active nanoparticles within a glass matrix is reviewed to provide a comprehensive discussion on the various techniques that are widely used to embed and postmodify nanoparticles in glass, and state‐of‐the‐art applications of their prototype devices that have been developed.
•Transparent NaLuF4:Tb3+–Yb3+ glass–ceramics were fabricated for the first time.•Samples exhibit intense characteristic emissions of Tb3+ and Yb3+ ionic pairs.•Greatly enhanced emission indicates the ...incorporation of Tb3+, Yb3+ into NaLuF4.
Novel Tb3+–Yb3+ co-doped transparent glass–ceramics containing NaLuF4 nanocrystals were successfully fabricated by melt-quenching technique for the first time. The structural and luminescent properties were investigated by XRD, TEM, absorption and upconversion spectra systemically. All samples exhibit intense characteristic emissions of Tb3+ (5D4→7FJ (J=3–5) and 5D3→7FJ (J=4–6)) and cooperative luminescence of Yb3+ ion pairs (476nm) excited by 980nm laser. The dramatically enhanced upconversion in glass–ceramics suggests that most rare earth ions have preferentially entered into NaLuF4 nanocrystals with lower phonon energy after crystallization. Our results indicate NaLuF4 based transparent glass–ceramics may be excellent hosts for rare earth ions doping.
Silicate glasses with metallic nanoparticles (NPs) have been of intense interest in art, science and technology as the plasmonic properties of these NPs equip glass with light modulation capability. ...The so-called striking technique has enabled precise control of the in situ formation of metallic NPs in silicate glasses for applications from coloured glasses to photonic devices. Since tellurite glasses exhibit the unique combination of comparably easy fabrication, low phonon energy, wide transmission window and high solubility of luminescent rare earth ions, there has been a significant amount of work over the past two decades to adapt the striking technique to form gold or silver NPs in tellurite glasses. Despite this effort, the striking technique has remained insufficient for tellurite glasses to form metal NPs suitable for photonic applications. Here, we first uncover the challenges of the traditional striking technique to create gold NPs in tellurite glass. Then, we demonstrate precise control of the size and concentration of gold NPs in tellurite glass by developing new approaches to both steps of the striking technique: a controlled gold crucible corrosion technique to incorporate gold ions in tellurite glass and a glass powder reheating technique to subsequently transform the gold ions to gold NPs. Using the Mie theory, the size, size distribution and concentration of the gold NPs formed in tellurite glass are determined from the plasmonic properties of the NPs. This fundamental research provides guidance for designing and manipulating the plasmonic properties in tellurite glass for photonics research and applications.
Tb3+–Yb3+ co-doped transparent oxyfluoride glass ceramics containing LaF3 nanocrystals were successfully fabricated by the melt-quenching technique in air atmosphere. The structural and luminescent ...properties were systemically investigated by X-ray diffraction, transmission electron microscopy and upconversion spectra. All samples exhibited intense characteristic emissions of Tb3+ (5D4→7FJ (J=3−6) and 5D3→7FJ (J=4−6)) under 980nm laser excitation. Besides, the upconversion intensity in glass ceramics was stronger than that in precursor glass and increased with crystallinity degree, which could be ascribed to the incorporation of Tb3+ and Yb3+ ions into LaF3 nanocrystals with low phonon energy. Laser power dependence of upconversion proved two-photon process was responsible for green emission.
► High transparent LaF3:Tb3+–Yb3+ glass ceramics were successfully fabricated. ► Glass ceramics exhibit intense green emissions of Tb3+ excited by 980nm laser. ► Two-photon process is responsible for green upconversion of Tb3+.
Highly transparent Er3+ doped oxyfluoride glass-ceramics containing cubic NaYbF4 nanocrystals were fabricated in an aluminosilicate matrix by melt-quenching technique. Their structural properties, ...optical properties and enhanced up-conversion behaviors were systemically investigated by XRD, TEM, HRTEM techniques and absorption, up-conversion spectra. Excited by 980nm laser, samples present characteristic emissions of Er3+. Compared with precursor glasses, the intensity of red emission increases by 15 times for GC650 after crystallization. Our work indicates that transparent NaYbF4 glass-ceramics may be used as potential host for up-conversion.
•NaYbF4:Er3+ nanocrystals (10nm) based glass-ceramics with 90% transmittance were successfully fabricated.•Glass ceramics exhibit intense characteristic red up-conversion of Er3+ under 980nm laser excitation.•Transparent NaYbF4 glass-ceramics may be used as potential host for up-conversion.
Self-crystallized fluoride K3YF6 glass ceramics (GC) doped with lanthanide ions were successfully manufactured via traditional melt-quenching route with further heat-treatment. Different from common ...cases previously reported, nano-crystals have already formed after melt-quenching, which is beneficial to the realization of controllable glass crystallization to some degree for affording desirable nano-crystal size and activator partition. Optical spectroscopy analysis demonstrates the partition of the active centers into the K3YF6 crystalline lattice with low phonon energy. Hence, luminescence of GC doped with lanthanide ions is highly enhanced after further heat-treatment. Moreover, the temperature-dependent green up-conversion emissions of Er3+ doped GC were investigated by the fluorescence intensity ratio (FIR) of the thermally coupled emitting states (2H11/2 and 4S3/2). The sensitivity is 1.27%K−1 at 300K and the obtained high energy difference (ΔE) is 793cm−1. Such Er3+ doped K3YF6 GC may present potential application in optical temperature sensors.
The luminescent properties of novel Cu⁺, Sm³⁺ single- and co-doped borosilicate glasses were systematically investigated by absorption, excitation, emission spectra and decay curves. Cu⁺ single-doped ...glasses emit broad luminescence band covering all the visible range. And their peaks shift to blue with decreasing excitation wavelength from 330 to 280 nm. Cu⁺, Sm³⁺ co-doped samples generate the varied hues from blue white to pure white and eventually to yellow white due to an efficient energy transfer from Cu⁺ to Sm³⁺. Our research indicates the potential application of Cu⁺, Sm³⁺ co-doped borosilicate glasses as converting phosphors for white LEDs pumped by UV LED chips.
Transparent novel glass‐ceramics containing Sr2YbF7:Er3+ nanocrystals were successfully fabricated by melt‐quenching technique. Their structural and up‐conversion luminescent properties were ...systemically investigated by XRD, HRTEM, and a series of spectroscopy methods. The temperature‐dependent up‐conversion spectra prove that 2H11/2 and 4S3/2 levels of Er3+ are thermally coupled energy levels (TCEL). Consequently, the 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 emissions of Er3+ in Sr2YbF7:Er3+ glass‐ceramics can be used as optical thermometry based on fluorescence intensity ratio (FIR) technique. Combined with low phonon energy and high thermal stability, Er3+ ions in Sr2YbF7 glass‐ceramics present broad operating temperature range (300–500 K), large energy gap of TCEL (786 cm−1) and high theoretical maximum value of relative sensitivity (62.14 × 10−4 K−1 at 560 K), which suggests that Sr2YbF7:Er3+ glass‐ceramics may be excellent candidates for optical temperature sensors.
KLu2F7: Tb3+ oxyfluoride glass ceramics (GC) were successfully manufactured via traditional melt-quenching route with further heat-treatment. Their micro-structural and optical properties were ...systemically investigated by XRD, TEM, HRTEM techniques, transmittance spectra, excitation spectra, emission spectra, luminescence lifetime measurements and X-ray excited luminescence (XEL). Both photoluminescence and XEL of KLu2F7 GC doped with Tb3+ are highly enhanced after further heat-treatment resulting from the partition of Tb3+ ions into the KLu2F7 crystalline lattice with low phonon energy. Our investigation suggests that such Tb3+-doped transparent KLu2F7 glass ceramics may present potential application in X-ray scintillator for slow event detection.
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