Methods of forming patterns using photoresist polymers

Patent metadata

Field	Value
Publication number	US-9625816-B2
Application number	US-201514886155-A
Country	US
Kind code	B2
Filing date	Oct 19, 2015
Priority date	Nov 27, 2014
Publication date	Apr 18, 2017
Grant date	Apr 18, 2017

Abstract

A photoresist polymer comprising a first repeating unit including a halogen donor group and a second repeating unit including a protecting group connected by a sulfide bond.

First claim

What is claimed is:

1. A method of forming a pattern, comprising:
forming a photoresist layer on an object layer, the photoresist layer including a polymer that comprises a first repeating unit including a halogen donor group, and a second repeating unit including a leaving group capable of being removed from the polymer by a photochemical reaction, the leaving group being connected to the second repeating unit by a sulfide bond;
performing an exposure process on the photoresist layer such that the photoresist layer is divided into an exposed portion and a non-exposed portion, wherein the exposure process is performed by at least one light source; and
removing the exposed portion of the photoresist layer to form a photoresist pattern.

2. The method of claim 1 , wherein a halonium ion or a halogen radical is generated from the halogen donor group by the exposure process.

3. The method of claim 2 , wherein the leaving group is separated from the second repeating unit by the halonium ion or the halogen radical.

4. The method of claim 1 , wherein the at least one light source is selected from ArF, KrF, an electron beam, I-line or extreme ultraviolet (EUV).

5. The method of claim 1 , wherein forming the photoresist layer includes coating a photoresist composition on the object layer, the photoresist composition including the polymer, a solvent and a photoacid generator.

6. The method of claim 5 , wherein a proton (H + ) generated from the photoacid generator is trapped by the halogen donor group.

7. The method of claim 6 , wherein the halogen donor group includes a nitrogen-halogen bond and a carbonyl bond, and
the proton is trapped by the carbonyl bond so that a halonium ion is generated from the nitrogen-halogen bond.

8. The method of claim 1 , wherein the exposed portion is more hydrophilic than the non-exposed portion.

9. The method of claim 8 , wherein the exposed portion includes an acetal structure to which a hydroxyl group is combined.

10. The method of claim 8 , wherein removing the exposed portion includes selectively removing the exposed portion using a developing solution.

11. The method of claim 1 , wherein the polymer includes a structure that is represented by Chemical Formula 1 or Chemical Formula 2:

wherein, in Chemical Formulae 1 and 2, R 1 and R 4 are each independently a divalent group selected from styrene, hydroxystyrene, acrylate, C 1 -C 6 alkylene, arylene, carbonyl, oxy, C 6 -C 30 aliphatic ester, C 6 -C 30 unsaturated aliphatic group or a combination thereof,
R 2 is hydrogen or a C 1 -C 20 alkyl group,
R 3 is a C 6 -C 30 aromatic group or a C 1 -C 20 alkyl group,
X represents chlorine (Cl), bromine (Br) or iodine (I), and
each a and b represents a mole ratio in a range of about 0.4 to about 0.6, and a sum of a and b is 1.

12. The method of claim 1 , further comprising patterning the object layer using the photoresist pattern as an etching mask.

13. A method of forming a pattern, comprising:
forming a photoresist layer on an object layer, the photoresist layer including a polymer in which a first unit including a nitrogen-halogen bond, and a second unit including a sulfide bond are alternately polymerized;
performing a selective exposure process on the photoresist layer so that an active halogen is generated from the nitrogen-halogen bond, and the active halogen is transferred to the sulfide bond, wherein the selective exposure process performed by at least one light source; and
removing an exposed portion of the photoresist layer to form a photoresist pattern.

14. The method of claim 13 , wherein the first unit includes at least one moiety selected from N-iodosuccinimide N-bromosuccinimide (NBS), N-chlorosuccinimide (NCS), N-iodophthalimide (NIPI), N-bromophthalimide (NBPI) or N-chlorophthalimide (NCPI).

15. The method of claim 13 , wherein the second unit is represented by Chemical Formula 5:

wherein, in Chemical Formula 5, R 1 is a divalent group selected from styrene, hydroxystyrene, acrylate, C 1 -C 6 alkylene, arylene, carbonyl, oxy, C 6 -C 30 aliphatic ester, C 6 -C 30 unsaturated aliphatic group or a combination thereof,
R 2 is hydrogen or a C 1 -C 20 alkyl group, and
R 3 is a C 6 -C 30 aromatic group or a C 1 -C 20 alkyl group.

16. The method of claim 15 , wherein —SR 3 in the second unit is separated from the second unit by the active halogen.

17. The method of claim 16 , wherein the exposed portion is converted to a hydrophilic pattern.

18. A method of forming a pattern, comprising:
forming a photoresist layer on an object layer, the photoresist layer including a polymer that comprises a first repeating unit including a halogen donor group, and a second repeating unit including a leaving group capable of being removed from the polymer by a photochemical reaction, the leaving group being connected to the second repeating unit by a sulfide bond;
generating a halonium ion or a halogen radical from the first repeating unit of the polymer by performing an exposure process on the photoresist layer such that the photoresist layer is divided into an exposed portion and a non-exposed portion, wherein the exposure process is performed by at least one light source;
removing the leaving group from the second repeating unit of the polymer; and
removing the exposed portion of the photoresist layer to form a photoresist pattern.

19. The method of claim 18 , wherein the halonium on or the halogen radical reacts with a sulfur atom in the sulfide bond to remove the leaving group from the second repeating unit of the polymer.

20. The method of claim 18 , wherein the leaving group from the second repeating unit of the polymer is replaced with a hydroxyl group.

Assignees

• Park Jin
• Kim Hyun-Woo
• Han Jin-Kyu
• Samsung Electronics Co Ltd

Inventors

• Park Jin
• Kim Hyun-Woo
• Han Jin-Kyu

Classifications

• H10P76/2041

  Photolithographic processes · CPC title

• G03F7/0045 Primary

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• G03F7/0392 Primary

  the macromolecular compound being present in a chemically amplified positive photoresist composition · CPC title

• G03F7/30

  Imagewise removal using liquid means · CPC title

• G03F7/26

  Processing photosensitive materials; Apparatus therefor (G03F7/12 - G03F7/24 take precedence) · CPC title