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

1. 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 a 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 exposed area and does not form the hardmask layer on the unexposed area;

forming a photoresist pattern by removing at least a portion of the unexposed area of the photoresist layer using the hardmask layer as an etch mask, the photoresist pattern having the exposed area; and

etching the etching layer using the photoresist pattern as an etch mask and forming a fine pattern.

2. The method as claimed in claim 1 , wherein the photoresist layer includes a material capable of generating a hydroxyl group (—OH), a carboxylic acid, or an amine group (—NH 2 ) upon selective exposure to light.

3. The method as claimed in claim 1 , wherein:

the photoresist layer includes a polymer represented by Chemical Formula 1 or a polymer represented by Chemical Formula 2, and a protecting group R in Chemical Formula 1 and Chemical Formula 2 contains 1 to 100 carbon atoms and includes an aliphatic unit, an alicyclic unit, or an aromatic unit:

4. The method as claimed in claim 3 , wherein the protecting group R includes an acetal, a ketal, an ether, a tert-butoxycarbonyl (t-BOC) group, a tetrahydropyranyl group, a trimethylsilyl group, a phenoxyethyl group, a cyclohexenyl group, a tert-butoxycarbonyl methyl group, a tert-butyl group, an adamantyl group, or a norbornyl group.

5. The method as claimed in claim 3 , wherein the photoresist layer further includes a photoacid generator (PAG).

6. The method as claimed in claim 1 , wherein:

the hardmask layer includes the metal oxide, and

the metal oxide is TiO or HfO.

7. The method as claimed in claim 1 , wherein forming the photoresist pattern includes a dry development process.

8. The method as claimed in claim 1 , wherein:

the hardmask layer includes the metal oxide, the metal oxide being TiO, and

forming the hardmask layer includes:

providing tetrakis-dimethyl-amino-titanium, to the photoresist layer having the exposed area, and

providing ozone (O 3 ) on the photoresist layer having the exposed area.

9. The method as claimed in claim 1 , wherein:

the hardmask layer includes the metal oxide, the metal oxide being HfO, and

forming the hardmask layer includes:

providing Hf[C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 or Hf[C 5 H 4 (CH 3 )] 2 (OCH 3 )CH 3 to the photoresist layer having the exposed area, and

providing ozone (O 3 ) to the photoresist layer having the exposed area.

10. The method as claimed in claim 1 , further comprising performing a post exposure bake process on the photoresist layer having the exposed area and the unexposed area before the hardmask layer is formed.

11. 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.

12. The method as claimed in claim 11 , wherein the photoresist layer includes a material having a hydroxyl group (—OH), a carboxylic acid, or an amine group (—NH 2 ).

13. The method as claimed in claim 11 , wherein the photoresist layer includes a polymer having a protected polyhydroxy styrene (PHS), a photoacid generator (PAG), and a crosslinker.

14. The method as claimed in claim 13 , wherein the crosslinker includes an epoxy compound, a melamine compound, a guanamine compound, a glycoluril compound substituted with at least one selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a urea compound, an epoxy compound, an isocyanate compound, an azide compound, or an compound having an alkenyl ether group.

15. The method as claimed in claim 11 , wherein the forming of the photoresist pattern includes a dry development process.

16. 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.

17. The method as claimed in claim 16 , wherein the selective deposition process includes providing a titanium compound to the photoresist layer, the titanium compound being a compound that reacts with a hydroxyl group, a carboxylic acid group, or an amine group of the exposed area or unexposed area to selectively deposit titanium on the surface of the photoresist layer.

18. The method as claimed in claim 17 , wherein:

titanium compound is tetrakis-dimethyl-amino-titanium, and

the method further includes providing O 3 to the photoresist layer.

19. The method as claimed in claim 16 , wherein the selective deposition process includes providing a hafnium compound to the photoresist layer, the hafnium compound being a compound that reacts with a hydroxyl group, a carboxylic acid group, or an amine group of the exposed area or unexposed area to selectively deposit hafnium on the surface of the photoresist layer.

20. The method as claimed in claim 19 , wherein:

the hafnium compound is Hf[C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 or Hf[C 5 H 4 (CH 3 )] 2 (OCH 3 )CH 3 , and the method further includes providing O 3 to the photoresist layer.