Towards rewritable multilevel optical data storage in single nanocrystals.

Novel approaches for digital data storage are imperative, as storage capacities are drastically being outpaced by the exponential growth in data generation. Optical data storage represents the most promising alternative to traditional magnetic and solid-state data storage. In this paper, a novel and energy efficient approach to optical data storage using rare-earth ion doped inorganic insulators is demonstrated. In particular, the nanocrystalline alkaline earth halide BaFCl:Sm is shown to provide great potential for multilevel optical data storage. Proof-of-concept demonstrations reveal for the first time that these phosphors could be used for rewritable, multilevel optical data storage on the physical dimensions of a single nanocrystal. Multilevel information storage is based on the very efficient and reversible conversion of Sm3+ to Sm2+ ions upon exposure to UV-C light. The stored information is then read-out using confocal optics by employing the photoluminescence of the Sm2+ ions in the nanocrystals, with the signal strength depending on the UV-C fluence used during the write step. The latter serves as the mechanism for multilevel data storage in the individual nanocrystals, as demonstrated in this paper. This data storage platform has the potential to be extended to 2D and 3D memory for storage densities that could potentially approach petabyte/cm3 levels.

Photoreduction of Sm(3+) in Nanocrystalline BaFCl.

We demonstrate that exposure of nanocrystalline BaFCl:Sm(3+) X-ray storage phosphor to blue laser pulses with peak power densities on the order of 10 GW/cm(2) results in conversion of Sm(3+) to Sm(2+). This photoreduction is found to be strongly power-dependent with an initial fast rate, followed by a slower rate. The photoreduction appears to be orders of magnitude more efficient than that for previously reported systems, and it is estimated that up to 50% of the samarium ions can be photoreduced to the divalent state. The main mechanism is most likely based on multiphoton electron-hole creation, followed by subsequent trapping of the electrons in the conduction band at the Sm(3+) centers. Nanocrystalline BaFCl:Sm(3+) is an efficient photoluminescent X-ray storage phosphor with possible applications as dosimetry probes, and the present study shows for the first time that the power levels of the blue light have to be kept relatively low to avoid the generation of Sm(2+) in the readout process. A system comprising the BaFCl:Sm(3+) nanocrystallites embedded into a glass is also envisioned for 3D memory applications.

Ultra-high-resolution greyscale fluorescence images via UV-exposure of thin flexible phosphor films.

Thin films of BaFCl:Sm nanocrystals prepared using a polymer binder were used to create fluorescence images. The phosphor films were exposed to a UV-C mercury lamp light source via chromium-coated quartz greyscale masks to create 4 µm resolution greyscale fluorescence images. The mechanism relies on the highly efficient conversion of Sm3+ to Sm2+ ions upon exposure to UV-C light which displays a large linear dynamic range. The red fluorescence around 688 nm of the Sm2+ is then read-out using blue-violet illumination under a laser scanning confocal microscope. The greyscale images with 16 greyscale levels had a resolution equivalent to ∼125 line pairs per mm or ∼6400 dpi. Improvements in the resolution would be possible using collimated UV-C laser exposure of the film or the use of higher resolution photomasks. Ultra-high resolution binary fluorescence images were also created with resolutions down to 2 µm (∼250 line pairs per mm, ∼12 700 dpi). Downstream applications of the technology could include tailored covert or overt anti-counterfeiting labelling.

On the origins of the green luminescence in the "zero-dimensional perovskite" Cs4PbBr6: conclusive results from cathodoluminescence imaging.

There is great interest in the use of highly-efficient all-inorganic halide perovskites CsnPbBr2+n for optoelectronic applications. There however remains considerable debate as to the origins of the green luminescence in the zero-dimensional phase of the perovskite Cs4PbBr6, with theories suggesting it originates either from defects in the Cs4PbBr6 lattice or CsPbBr3 impurities/inclusions. The confusion has arisen due to the two phases being miscible and typically co-existing. Moreover, low impurity levels of CsPbBr3 in Cs4PbBr6 are difficult to detect by XRD measurements, yet have much stronger photoluminescence than bulk CsPbBr3 that exhibits quenching, further contributing to the confusion as to the origins of the green photoluminescence. With the rise of significant debate and misconceptions, we provide conclusive evidence that the green emission from Cs4PbBr6 is indeed due to nanocrystalline CsPbBr3 impurities. This is demonstrated by undertaking cathodoluminescence and EDX measurements on samples prepared mechanochemically by ball-milling. Cathodoluminescence imaging clearly shows the presence of small crystals embedded in/or between larger crystallites of Cs4PbBr6 and they emit around 520 nm. EDX shows that the smaller crystal inclusions have a Pb : Br ratio that is approximately 2 times higher, confirming the CsPbBr3 phase, which has the expected size-dependent shift to shorter wavelengths (about 528 to 515 nm). These studies make significant inroads into understanding these lead halide perovskites for their use in a variety of optoelectronic and photovoltaic applications.