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1. (WO2012125401) NOVEL ETCHING COMPOSITION
Note: Text based on automatic Optical Character Recognition processes. Please use the PDF version for legal matters

WHAT IS CLAIMED IS:

1. An etching composition, comprising:

at least one sulfonic acid, the at least one sulfonic acid being from about 25% by weight to about 95% by weight of the composition;

at least one compound containing a halide anion, the halide anion being chloride or bromide and the halide anion being from about 0.01% by weight to about 0.5% by weight of the composition;

at least one compound containing a nitrate or nitrosyl ion, the nitrate or nitrosyl ion being from about 0.1 % by weight to about 20% by weight of the composition; and

at least about 3% by weight of water.

2. The composition of claim 1 , wherein the at least one sulfonic acid comprises a compound of formula (1):

R1SO3H (1),

in which R1 is substituted or unsubstituted C1-C12 linear or branched alkyl, substituted or unsubstituted C3-C12 cyclic alkyl, C1-C12 linear or branched fluoroalkyl ether, or C3-C12 cyclic fluoroalkyl ether.

3. The composition of claim 2, wherein R1 is C1-C12 linear or branched alkyl or C3-C12 cyclic alkyl, each of which is optionally substituted with halogen, C1-C4 alkyl, sulfonic acid, or phenyl optionally substituted with C1-C4 alkyl or hydroxy.

4. The composition of claim 3, wherein the at least one sulfonic acid is methanesulfonic acid.

5. The composition of claim 1 , wherein the at least one sulfonic acid comprises a compound of formula (2):


,

in which

each of R2, R3, and R4, independently, is C1-C12 linear or branched alkyl, C3-C12 cyclic alkyl, F, Cl, Br, OH, NO2, SO3H, or CO2H;

R5 is H; and

each of a, b, c, and n, independently, is 0, 1 , 2, or 3 provided that the sum of a, b, and c is n.

6. The composition of claim 5, wherein each of R2, R3, and R4, independently, is C1-C2 alkyl, Cl, NO2, OH, F, or CO2H; and n is 0 or 1.

7. The composition of claim 1 , wherein the at least one sulfonic acid comprises a naphthalenesulfonic acid optionally substituted with C1-C12 linear or branched alkyl or SO3H.

8. The composition of claim 1 , wherein the composition comprises a first sulfonic acid and a second sulfonic acid.

9. The composition of claim 8, wherein the first sulfonic acid comprises a compound of formula (1):

R1SO3H (1),

in which R1 is unsubstituted C1-C4 linear or branched alkyl.

10. The composition of claim 8, wherein the second sulfonic acid comprises a compound of formula (2):


,

in which

each of R2, R3, and R4, independently, is C1-C12 linear or branched alkyl, C3-C12 cyclic alkyl, F, Cl, or Br;

R5 is H; and

each of a, b, c, and n, independently, is 0, 1 , 2, or 3 provided that the sum of a, b, and c is n.

11. The composition of claim 8, wherein the second sulfonic acid comprises a compound of formula (1):

R'SO3H (1)

in which R1 is substituted or unsubstituted C6-C12 linear or branched alkyl, substituted or unsubstituted C6-C12 cyclic alkyl, C1-C12 linear or branched perfluoroalkyl, C3-C12 cyclic perfluoroalkyl, C1 -C12 linear or branched fluoroalkyl ether, C3-C12 cyclic fluoroalkyl ether, or substituted or unsubstituted C7-C12 alicyclic groups.

12. The composition of claim 8, wherein the second sulfonic acid comprises a naphthalenesulfonic acid optionally substituted with C1 -C12 linear or branched alkyl or SO3H.

13. The composition of any of claims 1-12, wherein the composition comprises from 60% by weight to about 95% by weight of the at least one sulfonic acid.

14. The composition of any of claims 1-13, wherein the at least one compound containing a halide ion comprises hydrogen chloride, hydrogen bromide, ammonium chloride, ammonium bromide, a quaternary ammonium chloride, a quaternary ammonium bromide, an amine hydrochloride, an amine

hydrobromide, a nitrogen based aromatic and pseudoaromatic hydrochloride, a nitrogen based aromatic and pseudoaromatic hydrobromide, a

phosphonium chloride, a phosphonium bromide, a metal chloride, or a metal bromide.

15. The composition of claim 14, wherein the at least one compound containing a halide ion comprises hydrogen chloride, ammonium chloride, ammonium bromide, or a quaternary ammonium chloride.

16. The composition of any of claims 1-15, wherein the composition comprises from about 0.01 % by weight to about 0.3% by weight of the halide anion.

17. The composition of any of claims 1-16, wherein the at least one compound containing a nitrate or nitrosyl ion comprises nitric acid, ammonium nitrate, a quaternary ammonium nitrate, a substituted ammonium nitrate, a nitrogen based aromatic and pseudoaromatic reaction product with nitric acid, a phosphonium nitrate, a metal nitrate, nitrosyl chloride, nitrosyl bromide, nitrosyl fluoride, nitrosyl tetrafluoroborate, or nitrosyl hydrogen sulfate.

18. The composition of claim 17, wherein the at least one compound containing a nitrate or nitrosyl ion comprises nitric acid.

19. The composition of any of claims 1-18, wherein the composition comprises from about 0.5% by weight to about 10% by weight of the nitrate or nitrosyl ion.

20. The composition of any of claims 1-19, wherein the composition comprises from about 3% by weight to about 40% by weight of water.

21. The composition of any of claims 1 -20, wherein the composition has a pH of at most about 2.

22. The composition of any of claims 1 -21 , wherein the composition comprises from 60% by weight to about 90% by weight of the at least one sulfonic acid, from about 0.01 % by weight to about 0.3% by weight of the halide anion, and from about 0.5% by weight to about 10% by weight of the nitrate or nitrosyl ion.

23. The composition of claim 22, wherein the composition comprises from 65% by weight to about 90% by weight of the at least one sulfonic acid, from about 0.01 % by weight to about 0.2% by weight of the halide anion, and from about 0.5% by weight to about 5% by weight of the nitrate or nitrosyl ion.

24. The composition of any of claims 1-23, wherein the composition does not include a stabilizer.

25. A method, comprising:

etching a metal film on a semiconductor substrate with the composition of any of claims 1-24; and

rinsing the etched metal film with a rinse solvent.

26. The method of claim 25, wherein the metal film is partially exposed to the composition.

27. The method of claim 25, wherein the metal film is completely exposed to the composition.

28. The method of any of claims 25-27, wherein the metal film comprises Pt, Au, Pd, Ir, Ni, Mo, Rh, Re, a lanthanide metal, or an alloy thereof.

29. The method of claim 28, wherein the metal film comprises Ni or an alloy of Pt and Ni.

30. The method of any of claims 25-29, wherein the rinse solvent comprises water.

31. A kit, comprising:

at least one sulfonic acid in a first container;

at least one compound containing a halide ion in a second container, the halide anion being chloride or bromide; and

at least one compound containing a nitrate or nitrosyl ion in a third container;

wherein the second container is different from the third container.

32. The kit of claim 31 , wherein the first container is the same as the second or third container.

33. The kit of claim 31 , wherein the first container is different from the second and third containers.