The research work reported here was undertaken in order to develop a manufacturing technology for the synthesis of composite diamond-based layers composed of aggregates, clusters, or nanodispersions of metallic and/or ceramic phases embedded in diamond matrices. The interest in depositing such composite films is motivated by the variety of demanding applications (abrasive and protective coatings, wear resistance, high-temperature electronics, electro-optical devices, solid-state semiconductors, etc.) that can be envisaged for a novel class of materials characterized by a remarkable combination of unique properties. However, whereas metal-and silicon-containing diamondlike or amorphous carbon films have been the subject of extensive research work [1±3] and today have a range of established applications, up to now only a limited number of papers have been reported the preparation of composite layers with the structure of crystalline diamond. [4,5] To address the issue of depositing composite diamondbased layers, we have recently developed a new CVDbased technique.[6] The diamond-based deposits are produced through the activation of hydrocarbon/hydrogen mixtures by a hot filament in a CVD reactor [7] equipped with a powder spraying system specifically designed and realized for the present investigation. The spraying system essentially consists of a powder reservoir, a nozzle, and a tubing system connecting them. An inert gas is used as a carrier to supply fine-grained tungsten powders (mean diameter £500 nm) to the growing diamond phase at controlled delivery rates. Specifically, the nozzle is a Mo cylinder with a series of conical holes arranged on the same generatrix. The conical shape of the holes and their distribution guarantee a relatively good homogeneity for powder distribution on the diamond growing area. The nozzle axis is kept parallel to the filament, and the powder-containing carrier flux reaches the deposition area such that it intersects the flux of the film-forming CH 4 /H 2 mixture at about 30. The experimental arrangement is sketched in Figure 1. The general CVD operating conditions were as follows: active gas phase composition: CH 4 /H 2 : 1 %; flow rate of the CH 4 /H 2 mixture: 200 cm 3 min ±1 ; filament temperature: 2200 C. The films were deposited on a-Ti substrates. Different series of deposits were obtained by changing the other deposition parameters, as summarized in Table 1. Table 1. Specific deposition parameters for the hybrid spraying±CVD processes by which the three different groups (A, B, and C) of W-containing diamond films were obtained.The microstructure and the crystallographic features of the composite layers were determined by the combined use of RHEED (reflection high energy electron diffraction) and XRPD (X-ray powder diffraction). For RHEED we used an AEI EM6G instrument equipped with a high resolution diffraction stage (60 kV). The measurements were performed in selected area (SA) conditions, with the possibility of varying the angle of incidence of the electron beam with r...