Nanolayered metal-ceramic composite systems provide the possibility to produce new materials with exceptional strength, toughness, and radiation resistance not exhibited by their individual constituents. The unusual behaviors are frequently attributed to the high density of internal interfaces. Most layered structures studied to date contain sharp interfaces and the synthesis of more diffuse interfacial structures, where the interface is 2 graded out of the interface plane, has not been deeply explored. Here we show how neutron reflectometry was used to study the structure of magnetron sputter deposited titanium and titanium nitride (Ti/TiN) layers as a function of deposition parameters: temperature, rate of N 2 flow or pressure, electrical bias applied to the sample, and orientation of the ion source relative to the sample. These different deposition and postprocessing strategies resulted in profound changes in the structure of the interfacial region between the two components in Ti/TiN x bilayers. The results show that temperature and low step-wise N 2 flow rates, but not electrical bias, can form graded interfaces in a controlled manner.
INTRODUCTIONIt has long been realized that interfaces play a critical role in the structural properties of nanolayered composites [1][2][3][4]. Over the years, the aim in engineering interfaces has been to radically improve several structural properties simultaneously, such as strength, ductility, and fracture toughness [5,6]. In this pursuit, intense research has been dedicated toward better understanding of how interfaces govern the interactions and reactions of discrete defects generated during deformation. For dissimilar metal-metal interfaces, it has been shown that the structure of the interface, including its atomic structure, misfit dislocation network, and crystallographic character, can greatly affect many properties, 3 such as dislocation annihilation and nucleation, twinnability, recovery from radiation induced defects, thermal stability, and strength [7][8][9][10][11].Compared to bimetal interfaces, engineering metal-ceramic interfaces in nano-layered composites have received far less attention and yet they represent a promising and relevant frontier for advanced nanomaterials design. As a representative example, here we focus on the Ti/TiN system. With an unprecedented combination of high hardness, chemical resistance to corrosion, bio-compatibility, diffusion barrier properties, and high electrical conductivity, titanium nitride (TiN) has been widely used in many industrial applications [12][13][14][15][16]. It has been found, for instance, that when TiN is coupled to a layer of metal to form a nano-laminate composite, correlated fracture toughness can be significantly enhanced [17,18]. Further, enhanced wear resistance [19,20], fracture toughness [21], corrosion protection [22,23], and improved performance as a diffusion barrier [24,25] have been frequently reported in Ti/TiN nano-layered composites. For similar metal-ceramic systems, prior in situ nano-indenta...