Method of forming semiconductor device using metal-containing hardmask to pattern photoresist having protected polymer

A method of forming a semiconductor device, the method comprising:

• forming an etching layer on a substrate;
• forming a photoresist layer on the etching layer;
• selectively exposing the photoresist layer to light to define an exposed area and an unexposed area in the photoresist layer;
• forming a hardmask layer including a metal oxide or metal nitride on the photoresist layer, the photoresist layer being in a state of including the exposed area and the unexposed area, using a selective deposition process that forms the hardmask layer on the unexposed area and does not form the hardmask layer on the exposed area;
• forming a photoresist pattern by removing the exposed area of the photoresist layer using the hardmask layer as an etch mask the photoresist pattern having at least a portion of the unexposed area;
• and
• etching the etching layer using the photoresist pattern as an etch mask and forming a fine pattern,
• wherein forming the hardmask layer is performed prior to forming the photoresist pattern.

A method of forming a pattern, the method comprising:

• forming an etching layer on a substrate;
• forming a photoresist layer on the etching layer;
• wherein the photoresist layer includes one of a material that generates a hydroxyl group, a carboxylic acid group, or an amine group upon selective exposure to light and post-exposure baking and a material that includes a hydroxyl group, a carboxylic acid group, or an amine group and that loses the hydroxyl group, carboxylic acid group, or amine group by crosslinking upon selective exposure to light and post-exposure baking;
• selectively exposing the photoresist layer to light to define an exposed area and an unexposed area in the photoresist layer;
• forming a hardmask layer including a metal oxide or metal nitride on the photoresist layer using a selective deposition process such that:
• when the photoresist layer includes the material that generates a hydroxyl group, a carboxylic acid group, or an amine group upon selective exposure to light and post-exposure baking, the hardmask layer including the metal oxide or metal nitride is formed on the exposed area and is not formed on the unexposed area, and
• when photoresist layer includes the material that includes a hydroxyl group, a carboxylic acid group, or an amine group and that loses the hydroxyl group, carboxylic acid group, or amine group by crosslinking upon selective exposure to light and post-exposure baking, the hardmask layer including the metal oxide or metal nitride is formed on the unexposed area, and is not formed on the exposed area;
• partially removing the photoresist layer using the hardmask layer as an etch mask and forming a photoresist pattern;
• and
• etching the etching layer using the photoresist pattern as an etch mask and forming a fine pattern,
• wherein the selective deposition process includes providing a metal compound to the photoresist layer, the metal compound reacting with a hydroxyl group, a carboxylic acid group, or an amine group of the exposed area or unexposed area to selectively deposit metal.