We present a multigram scale, one-step nonaqueous synthesis route to monodisperse, highly crystalline ZrO(2) nanoparticles. The nanoparticles can be stabilized in nonpolar solvents via a simple functionalization procedure using only minute amounts of organic stabilizers. Their great potential in materials applications is demonstrated by the fabrication of organic-inorganic nanocomposites that can be selectively photopolymerized to inscribe extremely effective and volume holographic gratings with the highest refractive index contrast (n(1) of up to 0.024) achieved so far.

The improved synthesis of large quantities of small (hydrodynamic diameter 6–8 nm) TiO2 and ZrO2 nanoparticles tailored as a high refractive index agent in holographic acrylate photopolymer composites has been developed. The surface of the particles was modified by p-dodecylbenzenesulfonic acid (organic shell weight fraction is about 50–70%) to render them highly compatible with organic monomer mixtures avoiding aggregation. The exposure to the interference pattern provides fast one-step formation of permanent highly efficient volume phase gratings with excellent transparency in the visible range. A high refractive index modulation amplitude n1 of about 0.0165 has been achieved in the composites containing 25 wt% of TiO2 nanoparticles. The level of light scattering in the gratings does not exceed 8–10% compared to the film without nanoparticles. The holographic grating based on acrylates doped with ZrO2 nanoparticles, first employed in this work, exhibited high photostability in contrast to holographic nanocomposites with TiO2 nanoparticles. Possible applications of such photocurable organic–inorganic nanocomposites are holographic diffractive elements for a number of optical and electro-optical applications or devices based on ordered arrays of functional nanoparticles within organic films.

Here, the facile synthesis of fluorescent ZrO2:Eu3+ nanoparticles with luminescence quantum yield of up to 8.7% that can be easily dispersed in organic solvents and utilized for the preparation of organic/inorganic volume holographic gratings is presented. The nanoparticles are prepared through a one‐step solvothermal process resulting in spherical particles with a mean size of 4 nm that were highly crystalline directly after the synthesis, without any need for calcination treatment. Detailed luminescence studies of the nanoparticles as a function of Eu3+ content demonstrate that the dopant concentration and its site symmetry play an important role in the emissive properties and lifetime of the luminescent centers. It is shown that the luminescence quantum yield of the colloidal ZrO2:Eu3+ nanoparticles increases with dopant concentration up to a critical concentration of 11 mol% while the luminescence lifetime is shortened from 1.8 to 1.4 ms. Holographic photopolymerization of suitable monomer mixtures containing the luminescent nanoparticles demonstrated the ability to inscribe volume Bragg gratings (refractive index contrast n1 up to 0.011) with light‐emissive properties, evidencing the high suitability of this approach for the fabrication of tailored nanomaterials for elaborate and demanding applications.

New nanocomposites containing functionalized acrylate monomers and Au nanoparticles (NPs, 1.5−3 nm core diameter, 1−2 wt %) have been developed for an all-optical fabrication of periodic bulk structures by holographic photopolymerization. The Au NPs were coated with ethyl 11-mercaptoundecanoate to ensure good solubility in low-polarity organic media. The materials with only 1.5 wt % Au NPs show unusually high amplitude of the refractive index modulation in the diffraction volume gratings (0.0073). Both volume and surface relief gratings are formed during the holographic exposure. The proposed mechanism of the refractive index contrast amplification (as compared to monomer mixture without NPs) includes interception of free radicals by Au nanoparticles. This slows down the free-radical photopolymerization, thus promoting the increase in lateral periodic redistribution of the components in the interference pattern. The redistribution of both NP and monomers provides high efficient grating formation with the spatial period of 0.5−4.5 μm. The formation of the surface relief coincident with the interference pattern is also observed. The introduction of 1.5 wt % Au NPs into the prepolymer mixture more than doubles the surface relief depth (from ca. 150 to 400 nm for the period 4.2 μm), thus proving the NP influence on the structure and, consequently, on the shrinkage of the polymer matrix.