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Structure and surface properties of size-tuneable CsPbBr3 nanocrystals

Hooper TJN, Fang Y, Brown AAM, Pu SH, White TJ

Nanoscale, 2021 Oct 01;13(37):15770-15780.
PMID: 34528047 DOI: 10.1039/d1nr04602k

This investigation has characterised the structure and surface chemistry of CsPbBr3 nanocrystals with controlled diameters between 6.4 to 12.8 nm. The nanocrystals were investigated via a thorough 133Cs solid state NMR and nuclear relaxation study, identifying and mapping radially-increasing nanoscale disorder. This work has formalised 133Cs NMR as a highly sensitive probe of nanocrystal size, which can conveniently analyse nanocrystals in solid forms, as they would be utilised in optoelectronic devices. A combined multinuclear solid state NMR and XPS approach, including 133Cs-1H heteronuclear correlation 2D (HETCOR) NMR, was utilised to study the nanocrystal surface and ligands, demonstrating that the surface is Cs-Br rich with vacancies passivated by didodecyldimethylammonium bromide (DDAB) ligands. Furthermore, it is shown that a negligible amount of phosphonate ligands remain on the powder nanocrystal surface, despite the key role of octylphosphonic acid (OPA) in controlling the colloidal nanocrystal growth. The CsPbBr3 NCs were shown to be structurally stable under ambient conditions for up to 6 months, albeit with some particle agglomeration.
Fulltext The Effects of Different Outdoor Environments, Sunglasses and Hats on Light Levels: Implications for Myopia Prevention

Lanca C, Teo A, Vivagandan A, Htoon HM, Najjar RP, Spiegel DP, et al.

Transl Vis Sci Technol, 2019 Jul;8(4):7.
PMID: 31360613 DOI: 10.1167/tvst.8.4.7

Purpose: Lack of outdoor time is a known risk factor for myopia. Knowledge of the light levels reaching the eye and exposure settings, including sun-protective measures, is essential for outdoor programs and myopia. We evaluated the impact of sun-protective strategies (hat and sunglasses) on maintaining high illuminance levels to prevent myopia.
Methods: A child-sized mannequin head was developed to measure light illuminance levels with and without sun-protective equipment, across a wide range of environments in Singapore, outdoors (open park, under a tree, street) and indoors (under a fluorescent illumination with window, under white LED-based lighting without window). A comparison was made between indoor and outdoor light levels that are experienced while children are involved in day-to-day activities.
Results: Outdoor light levels were much higher (11,080-18,176 lux) than indoors (112-156 lux). The higher lux levels protective of myopia (>1000 lux) were measured at the tree shade (5556-7876 lux) and with hat (4112-8156 lux). Sunglasses showed lux levels between 1792 and 6800 lux. Although with sunglasses readings were lower than tree shade and hat, light levels were still 11 to 43 times higher than indoors.
Conclusions: Recommendations on spending time outdoors for myopia prevention with adequate sun protection should be provided while partaking in outdoor activities, including protection under shaded areas, wearing a hat or sunglasses, sunscreen, and adequate hydration.
Translational Relevance: Light levels outdoors were higher than indoors and above the threshold illuminance for myopia prevention even with adequate sun-protective measures.
Fulltext Development of the FitSight Fitness Tracker to Increase Time Outdoors to Prevent Myopia

Verkicharla PK, Ramamurthy D, Nguyen QD, Zhang X, Pu SH, Malhotra R, et al.

Transl Vis Sci Technol, 2017 Jun;6(3):20.
PMID: 28660095 DOI: 10.1167/tvst.6.3.20

PURPOSE: To develop a fitness tracker (FitSight) to encourage children to increase time spent outdoors. To evaluate the wear pattern for this tracker and outdoor time pattern by estimating light illumination levels among children.
METHODS: The development of the FitSight fitness tracker involved the designing of two components: (1) the smartwatch with custom-made FitSight watch application (app) to log the instant light illuminance levels the wearer is exposed to, and (2) a companion smartphone app that synchronizes the time outdoors recorded by the smartwatch to smartphone via Bluetooth communication. Smartwatch wear patterns and tracker-recorded daily light illuminance levels data were gathered over 7 days from 23 Singapore children (mean ± standard deviation age: 9.2 ± 1.4 years). Feedback about the tracker was obtained from 14 parents using a three-level rating scale: very poor/poor/good.
RESULTS: Of the 14 parents, 93% rated the complete "FitSight fitness tracker" as good and 64% rated its wearability as good. While 61% of 23 children wore the watch on all study days (i.e., 0 nonwear days), 26% had 1 nonwear day, and 4.5% children each had 3, 4, and 5 nonwear days, respectively. On average, children spent approximately 1 hour in light levels greater than 1000 lux on weekdays and 1.3 hours on weekends (60 ± 46 vs. 79 ± 53 minutes, P = 0.19). Mean number of outdoor "spurts" (light illuminance levels >1000 lux) per day was 8 ± 3 spurts with spurt duration of 34 ± 32 minutes.
CONCLUSION: The FitSight tracker with its novel features may motivate children to increase time outdoors and play an important role in supplementing community outdoor programs to prevent myopia.
TRANSLATIONAL RELEVANCE: If the developed noninvasive, wearable, smartwatch-based fitness tracker, FitSight, promotes daytime outdoor activity among children, it will be beneficial in addressing the epidemic of myopia.
Self-assembly of a robust hydrogen-bonded octylphosphonate network on cesium lead bromide perovskite nanocrystals for light-emitting diodes

Brown AAM, Hooper TJN, Veldhuis SA, Chin XY, Bruno A, Vashishtha P, et al.

Nanoscale, 2019 Jul 07;11(25):12370-12380.
PMID: 31215940 DOI: 10.1039/c9nr02566a

We report the self-assembly of an extensive inter-ligand hydrogen-bonding network of octylphosphonates on the surface of cesium lead bromide nanocrystals (CsPbBr3 NCs). The post-synthetic addition of octylphosphonic acid to oleic acid/oleylamine-capped CsPbBr3 NCs promoted the attachment of octylphosphonate to the NC surface, while the remaining oleylammonium ligands maintained the high dispersability of the NCs in non-polar solvent. Through powerful 2D solid-state 31P-1H NMR, we demonstrated that an ethyl acetate/acetonitrile purification regime was crucial for initiating the self-assembly of extensive octylphosphonate chains. Octylphosphonate ligands were found to preferentially bind in a monodentate mode through P-O-, leaving polar P[double bond, length as m-dash]O and P-OH groups free to form inter-ligand hydrogen bonds. The octylphosphonate ligand network strongly passivated the nanocrystal surface, yielding a fully-purified CsPbBr3 NC ink with PLQY of 62%, over 3 times higher than untreated NCs. We translated this to LED devices, achieving maximum external quantum efficiency and luminance of 7.74% and 1022 cd m-2 with OPA treatment, as opposed to 3.59% and 229 cd m-2 for untreated CsPbBr3 NCs. This represents one of the highest efficiency LEDs obtained for all-inorganic CsPbBr3 NCs, accomplished through simple, effective passivation and purification processes. The robust binding of octylphosphonates to the perovskite lattice, and specifically their ability to interlink through hydrogen bonding, offers a promising passivation approach which could potentially be beneficial across a breadth of halide perovskite optoelectronic applications.