Stress state of silver nanoparticles embedded in a silicate glass matrix investigated by HREM and EXAFS spectroscopy

Ag particles of 3.9 and 5.1 nm mean size in silicate glasses were produced by ion exchange and subsequent annealing at 480 and 600 °C. These thermal treatments may induce stresses in matrix and particles in addition to the well known effect of surface atoms because of the thermal expansion mismatch of both materials. Structural characterisation of the particles by high-resolution electron microscopy revealed a size-dependent lattice dilatation quite opposite to the so far observed lattice contraction of similar metal/glass composites. This result, confirmed by X-ray absorption spectroscopy at the Ag K-edge, is discussed in terms of an Ag-Ag bond length increase near the particle surface. The temperature-dependent EXAFS spectra (10-300 K) indicate an increased thermal expansion coefficient of the particles with an increased mean particle size calculated on the basis of an anharmonic Einstein model. With that the bond length increase can be explained. The results can be interpreted by a combination of both the particle size effects and the influence of the surrounding matrix.