The feasibility of the inversion of metal images obtained by the chemical deposition of nickel onto Pd 2+ -loaded films of nanostructural TiO 2 exposed to high irradiation doses has been demonstrated. This permits the generation of both negative and positive metallic pictures by varying the irradiation dose, which expands the scope for obtaining planar metallic elements with complex structural organization.The feasibility of the photoselective deposition of catalytic metals such as palladium and silver onto the surface of broad-band oxide semiconductors such as TiO 2 , SnO 2 , and ZnO provides conditions for the subsequent chemical precipitation of another metal onto the exposed segments, which, in turn, permits the formation of various metallic elements such as current-conducting pathways, microelectrode assemblies, and catalytic surfaces for growing carbon nanotubes [1][2][3][4][5]. An important advantage of such photocatalytic lithography is the possibility of obtaining metallic pictures with micron resolution on large-format bases without using photoresists and vacuum spraying.The use of nanostructural TiO 2 as the photosensitivity carrier of thin films containing Pd 2+ ions and hole acceptors (organic acids) permits the formation of a palladium latent image in one step [6,7]. The rapid and irreversible capture of basic and nonbasic charge carriers generated in TiO 2 , which occurs in the case of these photolayers, prevents their spreading and permits us to obtain negative metallic figures (relative to the photopattern used) on both dielectric and conducting bases. In the present work, we examine the inversion of the final metallic image on TiO 2 : Pd 2+ films observed upon high-dose exposure.Model TiO 2 : Pd 2+ photosensitive layers were obtained by pouring a 2-propanol solution of 0.25% polybutyl titanate also containing 0.05% H 2 PdCl 4 and 0.25% oxalic acid onto a rotating base. The titanium dioxide films formed as the result of hydrolysis are X-ray-amorphous and contain a large amount of bound water; thermogravimetric analysis indicates that their composition corresponds to the chemical formula TiO 2 ·1.5H 2 O. Rutherford backscattering ( 4 He + ions) indicates that the thickness of the TiO 2 : Pd 2+ films is~100 nm. The procedure for obtaining metallic figures involves exposure through a contact quartz photopattern, washing in 10 vol.% aqueous 2-isopropanol, and palladium-catalyzed chemical deposition of nickel from a standard hypophosphite deposition solution [8]. When necessary, copper, silver, or platinum may be additionally deposited onto the surface of nickel images by galvanic or chemical deposition in order to provide high electrical conductance of the metallic elements formed.In previous work [6,7], we showed that the possibility of accumulating photoinduced charge in the form of Pd(I) intermediates stabilized in the TiO 2 matrix lies at the basis of the photoactivation of TiO 2 : Pd 2+ films. During further treatment of the photolayer in aqueous 2-propanol, photogenerated Pd(I) sites disproport...