The preparation and development of novel optical thin films are of great importance to functional optical and opto-electric components requiring a low refractive index. In this study, a typical metal-organic framework (MOF), MIL-101(Cr), is selected as the research model. The corresponding MOF nanoparticles are prepared by a hydrothermal method and the optical thin films are successfully prepared by spincoating. The optical properties of the corresponding MOF thin films are controlled by changing the type of functional groups on the benzene ring of the ligand (terephthalic acid) on MOFs. The functional groups are hydrogen atoms (H), electron donating groups (-NH 2, -OH) and electron withdrawing groups (-NO 2, -(NO 2 ) 2 or F 4 ), respectively. It is found that the effective refractive index (n eff ) of MOF thin films decreases along with the increasing voids among MOF nanoparticles. In addition, the extinction coefficient (k) increases with the addition of electron donating groups, and decreases with the addition of electron withdrawing groups. Among the MOFs used in this study, the n eff of NO 2 -MIL-101(Cr) containing electron withdrawing groups is as low as~1.2, and value of k is particularly low, which suggests its potential application in antireflective devices. In addition, the intrinsic refractive index (n dense ) of the dense MOF materials evaluated according to their porosity increases with the number of the functional groups, and the n dense of the two nitro-substituted MOFs is greater than that of the single nitro-substituted one, and the latter is bigger than that of hydroxyl-substituted one, which is close to that of amino-functionalized one. The diversity of ligands in MOFs makes them a promising new generation of optical materials.
Optical properties, which determine the application of optical devices in different fields, are the most significant properties of optical thin films. In recent years, Metal-organic framework (MOF)-based optical thin films have attracted increasing attention because of their novel optical properties and important potential applications in optical and photoelectric devices, especially optical thin films with tunable optical properties. This study reports the first example of tuning the optical properties of a MOF-based optical thin film via post-modification. The MOF-based optical thin film was composed of NH2-MIL-53(Al) nanorods (NRs) (MIL: Materials from Institute Lavoisier), and was constructed via a spin-coating method. Three aldehydes with different lengths of carbon chains were chosen to modify the MOF optical thin film to tune their optical properties. After post-modification, the structural color of the NH2-MIL-53(Al) thin film showed an obvious change from purple to bluish violet and cyan. The reflection spectrum and the reflectivity also altered in different degrees. The effective refractive index (neff) of MOFs thin film can also be tuned from 1.292 to 1.424 at a wavelength of 750 nm. The success of tuning of the optical properties of MOFs thin films through post-modification will make MOFs optical thin films meet different needs of optical properties in various optical and optoelectronic devices.
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