There is provided a technique that includes (a) forming a first film having a first thickness on an underlayer by supplying a first process gas not including oxidizing gas to a substrate, wherein the first film contains silicon, carbon, and nitrogen and does not contain oxygen, and the underlayer is exposed on a surface of the substrate and is at least one selected from the group of a conductive metal-element-containing film and a nitride film; and (b) forming a second film having a second thickness larger than the first thickness on the first film by supplying a second process gas including oxidizing gas to the substrate, wherein the second film contains silicon, oxygen, and nitrogen, and wherein in (b), oxygen atoms derived from the oxidizing gas and diffuse from a surface of the first film toward the underlayer are absorbed by the first film and the first film is modified.

Provided is a plasma enhanced atomic layer deposition (PEALD) process for depositing etch-resistant SiOCN films. These films provide improved growth rate, improved step coverage and excellent etch resistance to wet etchants and post-deposition plasma treatments containing O.sub.2 and NH.sub.3 co-reactants. This PEALD process relies on one or more precursors reacting in tandem with the plasma exposure to deposit the etch-resistant thin-films of SiOCN. The films display excellent resistance to wet etching with dilute aqueous HF solutions, both after deposition and after post-deposition plasma treatment(s). Accordingly, these films are expected to display excellent stability towards post-deposition fabrication steps utilized during device manufacturing and build.

Provided is a plasma enhanced atomic layer deposition (PEALD) process for depositing etch-resistant SiOCN films. These films provide improved growth rate, improved step coverage and excellent etch resistance to wet etchants and post-deposition plasma treatments containing O.sub.2 and NH.sub.3 co-reactants. This PEALD process relies on one or more precursors reacting in tandem with the plasma exposure to deposit the etch-resistant thin-films of SiOCN. The films display excellent resistance to wet etching with dilute aqueous HF solutions, both after deposition and after post-deposition plasma treatment(s). Accordingly, these films are expected to display excellent stability towards post-deposition fabrication steps utilized during device manufacturing and build.

A semiconductor may include a first inter metal dielectric (IMD) layer, a first blocking layer on the first IMD layer, a metal wiring and a second blocking layer. The first inter metal dielectric (IMD) layer may be formed on a substrate, the first IMD layer may include a low-k material having a dielectric constant lower than a dielectric constant of silicon oxide. The first blocking layer may be formed on the first IMD layer. The first blocking layer may include an oxide having a dielectric constant higher than the dielectric constant of the first IMD layer. The metal wiring may be through the first IMD layer and the first blocking layer. The second blocking layer may be formed on the metal wiring and the first blocking layer. The second blocking layer may include a nitride. The first and second blocking layers may reduce or prevent from the out gassing, so that a semiconductor device may have good characteristics.

An object of the invention is to provide a coated cutting tool whose tool life can be extended by having excellent wear resistance and fracture resistance. The coated cutting tool includes: a substrate; and a coating layer formed on a surface of the substrate, in which the coating layer includes a lower layer, an intermediate layer, and an upper layer in this order from a substrate side to a surface side of the coating layer, the lower layer includes one or more Ti compound layers formed of a specific Ti compound, the intermediate layer contains TiCNO, TiCO, or TiAlCNO, the upper layer contains α-type Al.sub.2O.sub.3, an average thickness of the lower layer is 2.0 μm or more and 8.0 μm or less, an average thickness of the intermediate layer is 0.5 μm or more and 2.0 μm or less and is 10% or more and 20% or less of a thickness of the entire coating layer, an average thickness of the upper layer is 0.8 μm or more and 6.0 μm or less, and in the intermediate layer, a ratio of a length of CSL grain boundaries to a total length 100% of a total grain boundary is 20% or more and 60% or less.

An object of the invention is to provide a coated cutting tool whose tool life can be extended by having excellent wear resistance and fracture resistance. The coated cutting tool includes: a substrate; and a coating layer formed on a surface of the substrate, in which the coating layer includes a lower layer, an intermediate layer, and an upper layer in this order from a substrate side to a surface side of the coating layer, the lower layer includes one or more Ti compound layers formed of a specific Ti compound, the intermediate layer contains TiCNO, TiCO, or TiAlCNO, the upper layer contains α-type Al.sub.2O.sub.3, an average thickness of the lower layer is 2.0 μm or more and 8.0 μm or less, an average thickness of the intermediate layer is 0.5 μm or more and 2.0 μm or less and is 10% or more and 20% or less of a thickness of the entire coating layer, an average thickness of the upper layer is 0.8 μm or more and 6.0 μm or less, and in the intermediate layer, a ratio of a length of CSL grain boundaries to a total length 100% of a total grain boundary is 20% or more and 60% or less.

The disclosure provides a metal surface layer treating method, a metal assembly and an electronic device. The metal surface layer treating method includes: putting metal into a vacuum chamber, and vacuumizing the vacuum chamber to a first vacuum degree; adding a mixed gas of acetylene, nitrogen and hydrogen into the vacuum chamber; and heating the vacuum chamber to a temperature above an ambient temperature. In response to the temperature in the vacuum chamber reaching a first temperature value above the ambient temperature and a gas pressure of the vacuum chamber reaching a first pressure value, performing glow discharge so that a carbon-nitrogen gradient hardening layer is formed on a surface layer of the metal. The method includes removing part of a carbon layer of the surface layer of the carbon-nitrogen gradient hardening layer.

The disclosure provides a metal surface layer treating method, a metal assembly and an electronic device. The metal surface layer treating method includes: putting metal into a vacuum chamber, and vacuumizing the vacuum chamber to a first vacuum degree; adding a mixed gas of acetylene, nitrogen and hydrogen into the vacuum chamber; and heating the vacuum chamber to a temperature above an ambient temperature. In response to the temperature in the vacuum chamber reaching a first temperature value above the ambient temperature and a gas pressure of the vacuum chamber reaching a first pressure value, performing glow discharge so that a carbon-nitrogen gradient hardening layer is formed on a surface layer of the metal. The method includes removing part of a carbon layer of the surface layer of the carbon-nitrogen gradient hardening layer.

There is provided a technique that includes: forming a film containing silicon, a predetermined element, and nitrogen on a substrate by performing a cycle a predetermined number of times, the cycle including: (a) forming a first layer by supplying a first gas containing silicon to the substrate; (b) forming a second layer by supplying a second gas containing silicon and differing in molecular structure from the first gas, to the substrate; (c) supplying a third gas containing the predetermined element to the substrate; and (d) modifying the first layer and the second layer by supplying a fourth gas containing nitrogen to the substrate, wherein an element capable of forming defects in the film is used as the predetermined element, and wherein in the cycle, (a) to (d) are performed in an order of: (a), (c), (b), and (d); (c), (a), (b), and (d); or (c), (a), (c), (b), and (d).

There is provided a technique that includes: forming a film containing silicon, a predetermined element, and nitrogen on a substrate by performing a cycle a predetermined number of times, the cycle including: (a) forming a first layer by supplying a first gas containing silicon to the substrate; (b) forming a second layer by supplying a second gas containing silicon and differing in molecular structure from the first gas, to the substrate; (c) supplying a third gas containing the predetermined element to the substrate; and (d) modifying the first layer and the second layer by supplying a fourth gas containing nitrogen to the substrate, wherein an element capable of forming defects in the film is used as the predetermined element, and wherein in the cycle, (a) to (d) are performed in an order of: (a), (c), (b), and (d); (c), (a), (b), and (d); or (c), (a), (c), (b), and (d).