Abstract: The subject of the present invention is an electrolyte composition for depositing copper on semiconductor substrates covered with a barrier layer. This electrolyte contains the combination of imidazole and 2,2?-bipyridine, used as suppressor, and of thiodiglycolic acid, used as accelerator. The combination of these additives makes it possible to obtain a bottom-up filling on trenches of very small width, typically of less than 100 nm.

Abstract: The invention relates to a machine (1) adapted to metallize a cavity of a semi-conductive or conductive substrate such as a structure of the through silicon via type, according to a metallization process comprising the steps consisting of: a) depositing an insulating dielectric layer in the cavity, b) depositing a barrier layer to diffusion of the filling metal, c) filling the cavity by electrodeposition of metal, preferably copper, and d) carrying out annealing of the substrate, characterized in that it comprises a series of wet-processing modules (10-60) configured to conduct steps a), b) and c) by wet-processing in a chemical bath (B) and at least one additional module (70) adapted to conduct annealing step d) of the substrate (S) such that the machine (1) is capable of executing the entire metallization process of the cavity.

Abstract: The present invention relates to an electrolyte composition for depositing copper on metal substrates. The composition contains a combination of two aromatic amines and an electrochemically inert cation. This electrolyte makes it possible to increase the copper nucleation density. It also allows bottom-up filling in trenches that have a very small opening dimension, typically lower than 40 nm.

Abstract: A subject matter of the invention is a process for the formation of nickel silicide or of cobalt silicide, comprising the stages consisting in: exposing the surface of the silicon-comprising substrate with an aqueous solution comprising from 0.1 mM to 10 mM of gold ions and from 0.6 M to 3.0 M of fluorine ions for a duration of between 5 seconds and 5 minutes, depositing by an electroless route, on the activated substrate, a layer essentially composed of nickel or of cobalt, applying a rapid thermal annealing at a temperature of between 300° C. and 750° C., so as to form the nickel silicide or the cobalt silicide. The aqueous solution comprises a surface-active agent chosen from the compounds comprising at least one anionic or nonionic polar group and an alkyl chain comprising from 10 to 16 carbon atoms. This process essentially has applications in the manufacture of NAND memories and photovoltaic cells.

Abstract: The invention proposes a method for forming a vertical electrical connection (50) in a layered semiconductor structure (1), comprising the following steps: —providing (100) a layered semiconductor structure (1), said layered semiconductor structure (1) comprising: —a support substrate (20) including an first surface (22) and a second surface (24), —an insulating layer (30) overlying the first surface (22) of the support substrate (20), and —at least one device structure (40) formed in the insulating layer (30); and —drilling (300) a via (50) from the second surface of the support substrate (20) up to the device structure (40), in order to expose the device structure (40); characterized in that drilling (300) of the insulating layer is at least performed by wet etching (320).

Abstract: A subject matter of the invention is a process for the formation of nickel silicide or of cobalt silicide, comprising the stages consisting in: exposing the surface of the silicon-comprising substrate with an aqueous solution comprising from 0.1 mM to 10 mM of gold ions and from 0.6 M to 3.0 M of fluorine ions for a duration of between 5 seconds and 5 minutes, depositing by an electroless route, on the activated substrate, a layer essentially composed of nickel or of cobalt, applying a rapid thermal annealing at a temperature of between 300° C. and 750° C., so as to form the nickel silicide or the cobalt silicide. The aqueous solution comprises a surface-active agent chosen from the compounds comprising at least one anionic or nonionic polar group and an alkyl chain comprising from 10 to 16 carbon atoms. This process essentially has applications in the manufacture of NAND memories and photovoltaic cells.

Abstract: The present invention relates to a kit intended for the deposition of nickel or cobalt in the cavities of a semiconductor substrate intended to form through-silicon vias (TSV) for making interconnections in integrated circuits in three dimensions. The invention also relates to a method of metallization of the insulating surface of such a substrate which comprises contacting the surface with a liquid aqueous solution containing: at least one metal salt of nickel or cobalt; at least one reducing agent; at least one polymer bearing amine functions, and at least one agent stabilizing the metal ions. The step coverage of the layer of nickel or cobalt obtained can be greater than 80%, which facilitates subsequent filling of the vias with copper by electrodeposition.

Abstract: A solution and a process are used for activating the surface of a substrate comprising at least one area formed from a polymer, for the purpose of subsequently covering it with a metallic layer deposited via an electroless process. The composition contains: A) an activator formed from one or more palladium complexes; B) a binder formed from one or more organic compounds chosen from compounds comprising at least two glycidyl functions and at least two isocyanate functions; and C) a solvent system formed from one or more solvents capable of dissolving said activator and said binder. The solution and process may be applied for the manufacture of electronic devices such as integrated circuits, especially in three dimensions.

Abstract: The object of the present invention is an electroplating composition intended in particular for coating a copper-diffusion barrier layer with a seed layer, This composition comprises a source of copper ions, in a concentration of between 0.4 and 40mM; at least one copper complexing agent chosen from the group of primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, aromatic amines, nitrogen heterocycles and oximes; the copper/complexing agent(s) molar ratio being between 0.1 and 2.5, preferably between 0.3 and 1.3; and the pH of the composition being less than 7, preferably between 3.5 and 6.5.

Abstract: The invention relates to a method for grafting an organic film onto an electrically conductive or semiconductive surface by electro-reduction of a solution, wherein the solution comprises one diazonium salt and one monomer bearing at least one chain polymerizable functional group. During the electrolyzing process, at least one protocols consisting of an electrical polarization of the surface by applying a variable potential over at least a range of values which are more cathodic that the reduction or peak potential of all diazonium salts in said solution is applied. The invention also relates to an electrically conducting or semiconducting surface obtained by implementing this method. The invention further relates to electrolytic compositions.

Abstract: The present invention relates to a solution and a method for activating the oxidized surface of a substrate, in particular of a semiconducting substrate, for its subsequent coating by a metal layer deposited by the electroless method. According to the invention, this composition contains: A) an activator consisting of one or more palladium complexes; B) a bifunctional organic binder consisting one or more organosilane complexes; C) a solvent system consisting one or more solvents for solubilizing the said activator and the said binder.

Abstract: The invention relates to a machine (1) adapted to metallise a cavity of a semi-conductive or conductive substrate such as a structure of the through silicon via type, according to a metallisation process comprising the steps consisting of: a) depositing an insulating dielectric layer in the cavity, b) depositing a barrier layer to diffusion of the filling metal, c) filling the cavity by electrodeposition of metal, preferably copper, and d) carrying out annealing of the substrate, characterised in that it comprises a series of wet-processing modules (10-60) configured to conduct steps a), b) and c) by wet-processing in a chemical bath (B) and at least one additional module (70) adapted to conduct annealing step d) of the substrate (S) such that the machine (1) is capable of executing the entire metallisation process of the cavity.

Abstract: The invention concerns a device to conduct an electrochemical reaction on the surface of a semiconductor substrate (S), characterized in that the device comprises: a container (10) intended to contain an electrolyte (E), a support (20) arranged in the container, said support being adapted for attachment of the semiconductor substrate (S) on said support (20), a counter-electrode (30) arranged in the container (10), illumination means (50) comprising a source (51) emitting light rays and means (52) to homogenize the light rays on all of said surface of the semiconductor substrate (S), so as to activate the surface of the semiconductor substrate (S), and an electric supply (40) comprising connection means for connection to the semiconductor substrate and to the counter-electrode in order to polarize said surface of said semiconductor substrate (S) at an electric potential permitting the electrochemical reaction.

Abstract: The invention relates to a method for grafting an organic film onto an electrically conductive or semiconductive surface by electro-reduction of a solution, wherein the solution comprises one diazonium salt and one monomer bearing at least one chain polymerizable functional group. During the electrolyzing process, at least one protocol consisting of an electrical polarization of the surface by applying a variable potential over at least a range of values which are more cathodic that the reduction or peak potential of all diazonium salts in said solution is applied. The invention also relates to an electrically conducting or semiconducting surface obtained by implementing this method. The invention further relates to electrolytic compositions.

Abstract: The present invention relates to a kit intended for the deposition of nickel or cobalt in the cavities of a semiconductor substrate intended to form through-silicon vias (TSV) for making interconnections in integrated circuits in three dimensions. The invention also relates to a method of metallization of the insulating surface of such a substrate which comprises contacting the surface with a liquid aqueous solution containing: at least one metal salt of nickel or cobalt; at least one reducing agent; at least one polymer bearing amine functions, and at least one agent stabilizing the metal ions. The step coverage of the layer of nickel or cobalt obtained can be greater than 80%, which facilitates subsequent filling of the vias with copper by electrodeposition.

Abstract: The present invention relates to an electrodeposition composition intended particularly for coating a semiconductor substrate in order to fabricate structures of the “through via” type for the production of interconnects in integrated circuits. According to the invention, the said solution comprises copper ions in a concentration of between 14 and 120 mM and ethylenediamine, the molar ratio between ethylenediamine and copper being between 1.80 and 2.03 and the pH of the electrodeposition solution being between 6.6 and 7.5. The present invention also relates to the use of the said electrodeposition solution for the deposition of a copper seed layer, and to the method for depositing a copper a seed layer with the aid of the electrodeposition solution according to the invention.

Abstract: The object of the present invention is a method of coating a surface of a substrate with copper by electroplating. According to the invention, this method comprises: a step during which the surface to be coated is brought into contact with an electroplating bath while the surface is not under electrical bias; a step of forming the coating during which the surface is biased; a step during which the surface is separated from the electroplating bath while it is under electrical bias; the aforementioned electroplating bath comprising, in solution in a solvent: a source of copper ions, with a concentration of between 0.4 and 40mM; and at least one copper complexing agent.

Abstract: Method for repairing copper diffusion barrier layers on a semiconductor solid substrate and repair kit for implementing this method. One subject of the present invention is a method for repairing a surface of a substrate coated with a discontinuous copper diffusion barrier layer of a titanium-based material. According to the invention, this method comprises: a) the contacting of the surface with a suspension containing copper or copper alloy nanoparticles for a time of between 1 s and 15 min; and b) the contacting of the thus treated surface with a liquid solution having a pH of between 8.5 and 12 and containing: at least one metal salt, at least one reducing agent, at least one stabilizer at a temperature of between 50° C. and 90° C., preferably between 60° C. and 80° C., for a time of between 30 s and 10 min, preferably between 1 min and 5 min, in order to thus form a metallic film having a thickness of at least 50 nanometers re-establishing the continuity of the copper diffusion barrier layer.

Abstract: The subject-matter of the present invention is a composition especially intended for filling, by the electroplating of copper, a cavity in a semiconductor substrate such as a “through-via” structure for the production of interconnects in three-dimensional integrated circuits. According to the invention, this composition comprises in solution in a solvent: copper ions in a concentration lying between 45 and 1500 mM; a complexing agent for the copper consisting of at least one compound chosen from aliphatic polyamines having 2 to 4 amino groups, preferably ethylenediamine, in a concentration lying between 45 and 3000 mM; the molar ratio between the copper and said complexing agent lying between 0.1 and 5; thiodiglycolic acid in a concentration lying between 1 and 500 mg/l; and optionally a buffer system, in particular ammonium sulfate, in a concentration lying between 0.1 and 3M.

Abstract: The present invention concerns a methods and compositions for preparing a multi layer composite device, such as a semiconductor device. Said method comprises (A) forming a dielectric layer on the surface of a composite material by bringing said surface into contact: a) either with a solution, comprising the diazonium salt of aniline, a diazonium salt bearing at least one functional group or an amine compound of formula H2N-A-X—Z as defined in claim 1: b) or with a first solution containing an aryl diazonium salt and successively a second solution containing a compound bearing at least one functional group and bearing at least one functional group capable of reacting with the aryl radical grafted on the surface of the composite material thanks to the aryl diazonium salt; (B) forming an overlayer on said surface of said composite material obtained in step (A), said overlayer consisting of a Si-containing dielectric Cu-Etch Stop Layer and/or copper diffusion barrier.