Use of compositions comprising a surfactant and a hydrophobizer for avoiding anti pattern collapse when treating patterned materials with line-space dimensions of 50 nm or below

Patent metadata

Field	Value
Publication number	US-9557652-B2
Application number	US-201314652120-A
Country	US
Kind code	B2
Filing date	Dec 4, 2013
Priority date	Dec 14, 2012
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

In a method of treating a substrate including patterns having line-space dimensions of 50 nm or below, the substrate is rinsed by an aqueous composition including at least one non-ionic surfactant A and at least one hydrophobizer B. The at least one surfactant A has an equilibrium surface tension of 10 mN/m to 35 mN/m, determined from a solution of the at least one surfactant A in water at the critical micelle concentration. The hydrophobizer B is selected so that the contact angle of water to the substrate is increased by contacting the substrate with a solution of the hydrophobizer B in water by 5-95° compared to the contact angle of water to the substrate before such contacting.

First claim

The invention claimed is:

1. A method for treating a substrate including patterns having line-space dimensions of 50 nm or below, the method comprising rinsing the substrate with an aqueous composition comprising at least one non-ionic surfactant A and at least one hydrophobizer B, wherein
(a) the at least one surfactant A has an equilibrium surface tension of 10 mN/m to 35 mN/m, determined from a solution of the at least one surfactant A in water at the critical micelle concentration, and
(b) the at least one hydrophobizer B is selected so that the contact angle of water to the substrate is increased by contacting the substrate with a solution of the hydrophobizer B in water by 5-95° compared to the contact angle of water to the substrate before such contacting.

2. The method according to claim 1 , wherein the at least one surfactant A has an equilibrium contact angle to the substrate of 0° to 30°.

3. The method according to claim 2 , wherein the at least one surfactant A is selected from the group comprising short branched perfluoroalkyl surfactants (A1), Silicon based surfactants (A2), alkoxy terminated copolymers of ethylene oxide and propylene oxide surfactants (A3), alkyl polyglycoside and sorbate surfactants (A4), alkyl amine oxide surfactants (A5), and acetylenic diol surfactants (A6).

4. The method according to claim 3 , wherein the short branched perfluoroalkyl surfactants (A1) comprise at least three short-chain perfluorinated groups R f selected from trifluoromethyl, pentafluoroethyl, 1-heptafluoropropyl, 2-heptafluoropropyl, and pentafluorosulfanyl.

5. The method according to claim 3 , wherein the silicon based surfactants (A2) are selected from the group comprising siloxane surfactants of general formula A-IIa and A-IIb:

wherein
u, v are an integers independently selected of from 0 to 5,
w is an integer of from 0 to 6,
x is an integer of from 1 to 22,
y is an integer of from 1 to 5,
R 10 is a selected from H or a C 1 to C 10 alkyl group, and
R 11 is selected from H, methyl or ethyl.

6. The method according to claim 3 , wherein the alkoxy terminated copolymers of ethylene oxide and propylene oxide surfactants (A3) have the general formula A-III
(R 12 —O) c -(EO) a (PO) b H  (A-III)

wherein
R 12 is a c-valent group selected from C 4 to C 30 alkyl, which may optionally be fluorinated or perfluorinated,
EO oxyethanediyl,
PO oxypropanediyl,
a is an integer of from 1 to 100,
b is an integer of from 0 to 100, and
c is an integer of from 1 to 6.

7. The method according to claim 3 , wherein the alkyl polyglycoside surfactants (A4) has the general formula A-IV
R 21 O(C n H 2n O) j (Z) k   (A-IV)

wherein
R 21 is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, in which the alkyl group contain from about 10 to 18,
n is preferably 2 or 3,
j is from 0 to 10,
k is from 1 to 8, and
Z is selected from a hexose, a glucose, a derivative of glucose, a sucrose.

8. The method according to claim 3 , wherein the alkyl amine oxide surfactants (A5) has the general formula A-V

wherein
R 41 is a C 6 to C 30 hydrophobic organic radical,
R 42 , R 43 are independently selected from C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl.

9. The method according to claim 3 , wherein the acetylenic diol surfactants (A6) has the general formula A-VI

wherein
R 51 and R 4 are linear or branched C 3 to C 10 alkyl,
R 52 and R 53 selected from H and linear or branched C 1 to C 5 alkyl, and
q, r, s and t are integers of from 0 to 20.

10. The method according to claim 1 , wherein the at least one hydrophobizer B is selected so that the contact angle of water to the substrate is increased by contacting the substrate with a solution of the at least one hydrophobizer B in water by at least 10° compared to the contact angle of water to substrate before such contacting.

11. The method according to claim 1 , wherein the hydrophobizer B has an equilibrium surface tension of 30 mN/m to 70 mN/m.

12. The method according to claim 1 , wherein the hydrophobizer B is cationic, amphiphilic or zwitterionic.

13. The method according to claim 1 , wherein the hydrophobizer B is selected from the group comprising quaternary alkyl ammonium compound (B1), gemini quaternary alkyl ammonium compound (B2), and polyamines (B3).

14. The method according to claim 13 , wherein the quaternary alkyl ammonium compound (B1) has the general formula B-I

wherein
R 1 is selected from moieties of the following formula:

R 2 , R 3 , R 4 are selected from R 1 and H,
R 5 is selected from H, OH and C 1 to C 10 alkyl,
z is an integer of from 1 to 18,
R 6 is selected from H and C 1 to C 10 alkyl.

15. The method according to claim 13 , wherein the gemini quaternary alkyl ammonium compounds B2 has the general formula B-II:

wherein
X is a divalent group, for each repeating unit 1 to n independently selected from
(a) a linear or branched C 1 to C 20 alkanediyl, which may optionally be substituted and which may optionally be interrupted by up to 5 heteroatoms selected from O and N,
(b) a C 5 to C 20 cycloalkanediyl, which may optionally be substituted and which may optionally be interrupted by up to 5 heteroatoms selected from O and N,
(c) a C 6 to C 20 organic group of formula —X 1 -A-X 2 —, wherein X 1 and X 2 are independently selected from a C 1 to C 7 linear or branched alkanediyl and A is selected from a C 5 to C 12 aromatic moiety or a C 5 to C 30 cycloalkanediyl, which H atoms may optionally be substituted and which C atoms may optionally be interrupted by up to 5 heteroatoms selected from O and N, and
(d) a polyoxyalkylene diradical of formula II:

wherein p is 0 or 1, r is an integer from 1 to 100; R 5 is selected from H and a linear or branched C 1 to C 20 alkyl group,

R 1 and R 2 are monovalent groups independently selected from H, linear or branched C 1 to C 20 alkyl, C 5 to C 20 cycloalkyl, C 5 to C 20 aryl, C 6 to C 20 alkylaryl, C 6 to C 20 arylalkyl, C 1 to C 20 hydroxyalkyl, or C 2 to C 4 oxyalkylene homo or copolymers, all of which may optionally be further substituted,
R 3 and R 4 are monovalent groups independently selected from a linear or branched C 5 to C 30 alkyl group, a C 5 to C 30 cycloalkyl, a C 1 to C 20 hydroxyalkyl, and a C 2 to C 4 oxyalkylene homo or copolymers, all of which may optionally be substituted, and wherein pair-wise R 3 -R 4 and adjacent R 4 -R 4 and R 3 -R 3 may optionally together form a bivalent group X as defined above, and may also be a continuation Q of the molecule by branching, and, if n is equal to or greater th

Assignees

• Basf Se

Inventors

• Klipp Andreas
• Honciuc Andrei
• OETTER Günter
• Bittner Christian

Classifications

• H10P76/204

  of organic photoresist masks · CPC title

• H10P70/20 Primary

  Cleaning during device manufacture · CPC title

• C11D1/94

  Mixtures with anionic, cationic or non-ionic compounds · CPC title

• G03F7/405

  Treatment with inorganic or organometallic reagents after imagewise removal · CPC title

• C11D11/0047

  Chemistry & Metallurgy · mapped topic