METAL PEROXO COMPOUNDS WITH ORGANIC CO-LIGANDS FOR ELECTRON BEAM, DEEP UV AND EXTREME UV PHOTORESIST APPLICATIONS

• US 20130224652A1
• Filed: 02/27/2012
• Published: 08/29/2013
• Est. Priority Date: 02/27/2012
• Status: Active Grant

• Current Assignee: Globalfoundries US Incorporated (GlobalFoundries, Inc.)
• Original Assignee: International Business Machines Corporation
• Inventors: Bass, John David, Kim, Ho-Cheol, Miller, Robert Dennis, Song, Qing, Sundberg, Linda Karin, Wallraff, Gregory Michael
• Granted Patent: US 8,703,386 B2
• Time in Patent Office: Days
• US Class Current: 430/270.1
• CPC Class Codes: G03F 7/0042 with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists G03F7/075 takes precedence

Abstract

Compositions are disclosed having the formula (3):

[C′]_k[Ta(O₂)_x(L′)_y]  (3),

wherein x is an integer of 1 to 4, y is an integer of 1 to 4, Ta(O₂)_x(L′)_y has a charge of 0 to −3, C′ is a counterion having a charge of +1 to +3, k is an integer of 0 to 3, L′ is an oxidatively stable organic ligand having a charge of 0 to −4, and L′ comprises an electron donating functional group selected from the group consisting of carboxylates, alkoxides, amines, amine oxides, phosphines, phosphine oxides, arsine oxides, and combinations thereof. The compositions have utility as high resolution photoresists.

Claims

1. A composition of matter of formula (3):

[C′

]_k[Ta(O₂)_x(L′

)_y] 

 

(3),

wherein

x is an integer of 1 to 4,

y is an integer of 1 to 4,

Ta(O₂)_x(L′

)_y has a charge of 0 to −

3,

C′

is a counterion having a charge of +1 to +3,

k is an integer of 0 to 3,

L′

is an oxidatively stable organic ligand having a charge of 0 to −

4, and

L′

comprises an electron donating functional group selected from the group consisting of carboxylates, alkoxides, amines, amine oxides, phosphines, phosphine oxides, arsine oxides, and combinations thereof.

2. The composition of claim 1, wherein x is 3, y is 1, and k is 3.

3. The composition of claim 1, wherein L′

comprises a functional group selected from the group consisting of carboxylates and alkoxides.

4. The composition of claim 1, wherein L′

is a dianion selected from the group consisting of oxalate (C₂O₄<sup>−

2</sup>), lactate (C₃H₄O₃<sup>−

2</sup>), glycolate (C₂H₂O₃<sup>−

2</sup>), and combinations thereof.

5. The composition of claim 1, wherein C′

is ammonium (NH₄⁺).

6. The composition of claim 1, wherein the composition is [NH₄]₃[Ta(O₂)₃(C₂O₄)].

7. The composition of claim 1, wherein the composition further comprises 1 to 10 water molecules of hydration.

8. A photoresist composition comprising the composition of claim 1, wherein the photoresist composition is suitable for e-beam lithography, x-ray lithography, and/or lithography utilizing an ultraviolet radiation source having a wavelength that is between 10 nm to 400 nm.

9. A photoresist composition, comprising:

a solvent; and

a peroxo complex having a structure according to formula (1);

[C′

]_k[M′

_w(O₂)_x(L′

)_yO_u] 

 

(1),

wherein

w is 1 or 2,

x is an integer of 1 to 4,

y is an integer of 1 to 4,

u is 0 or 1,

M′

_w(O₂)_x(L′

)_yO_u has a charge of 0 to −

3,

C′

is an optional counterion having a charge of +1 to +3,

k is an integer of 0 to 3,

M′

is an ion of a metal selected from the group consisting of Ta, Nb, V, Mo, Co, Zn, Sb, Fe, W, Zr, Hf, Sn, Pb, Cr, Re, Ti, and combinations thereof,

M′

has an oxidation state of +1 to +6,

L′

is an oxidatively stable organic ligand having a charge of 0 to −

4, and

L′

comprises an electron donating functional group selected from the group consisting of carboxylates, alkoxides, amines, amine oxides, phosphines, phosphine oxides, arsine oxides, and combinations thereof.

10. The photoresist composition of claim 9, wherein M′

is selected from the group consisting of Ta, Ti, Nb, and combinations thereof.

11. The photoresist composition of claim 9, wherein u is 0 and w is 1.

12. The photoresist composition of claim 11, wherein M′

is Ta.

13. The photoresist composition of claim 9, wherein the peroxo complex is selected from the group consisting of

[NH₄]₄[Ta₂(O₂)₂(C₃H₄O₃)₄O] wherein C₃H₄O₃ is lactate (C₃H₄O₃⁻

2),

[NH₄]₄[Ta₂(O₂)₂(C₂H₂O₃)₄O] wherein C₂H₂O₃ is glycolate (C₂H₂O₃<sup>−

2</sup>),

[NH₄]₄[Nb₂(O₂)₂(C₃H₄O₃)₄O] wherein C₃H₄O₃ is lactate (C₃H₄O₃<sup>−

2</sup>),

[NH₄]₃[Ta(O₂)₃(C₂O₄)] wherein C₂O₄ is oxalate (C₂O₄<sup>−

2</sup>),

[NH₄]₂[Ti(O₂)₂(C₂O₄)] wherein C₂O₄ is oxalate (C₂O₄<sup>−

2</sup>), and

combinations thereof.

14. The photoresist composition of claim 9, wherein the solvent is water.

15. The photoresist composition of claim 9, further comprising hydrogen peroxide.

16. A method, comprising:

i) providing a photoresist composition comprising;

a solvent; and

a peroxo complex having a structure according to formula (1);

[C′

]_k[M′

_w(O₂)_x(L′

)_yO_u] 

 

(1),

wherein

w is 1 or 2,

x is an integer of 1 to 4,

y is an integer of 1 to 4,

u is 0 or 1,

M′

_w(O₂)_x(L′

)_yO_u has a charge of 0 to −

3,

C′

is an optional counterion having a charge of +1 to +3,

k is an integer of 0 to 3,

M′

is an ion of a metal selected from the group consisting of Ta, Nb, V, Mo, Co, Zn, Sb, Fe, W, Zr, Hf, Sn, Pb, Cr, Re, Ti, and combinations thereof,

M′

has an oxidation state of +1 to +6,

L′

is an oxidatively stable organic ligand having a charge of 0 to −

4, and

L′

comprises an electron donating functional group selected from the group consisting of carboxylates, alkoxides, amines, amine oxides, phosphines, phosphine oxides, arsine oxides, and combinations thereof;

ii) disposing the photoresist composition on a surface of a substrate and removing the solvent, thereby forming a photoresist layer disposed on the substrate;

iii) imagewise exposing the photoresist layer to radiation selected from the group consisting of e-beam, x-ray, and ultraviolet (UV) radiation; and

iv) developing the exposed photoresist layer in an aqueous and/or organic developer, thereby forming a layered structure comprising a patterned photoresist layer disposed on the substrate, the patterned photoresist layer comprising topographical features comprising exposed photoresist.

17. The method of claim 16, wherein the solvent of the photoresist composition is water.

18. The method of claim 16, wherein the photoresist composition further comprises peroxide.

19. The method of claim 16, wherein the developer comprises water and a base.

20. The method of claim 16, wherein the photoresist layer is exposed imagewise using an ultraviolet radiation source at a wavelength that is between 10 nm and 200 nm.

21. The method of claim 16, wherein the photoresist layer is exposed imagewise using an ultraviolet radiation source at a wavelength of 13.5 nm.

22. The method of claim 16, wherein the method further comprises baking the disposed photoresist layer before said exposing.

23. The method of claim 16, wherein the method further comprises baking the disposed photoresist layer before said developing.

24. The method of claim 16, wherein the method further comprises transferring the pattern of features of the patterned photoresist layer to the substrate.

25. The method of claim 24, wherein the method further comprises baking the patterned photoresist layer before transferring features of the patterned photoresist layer to the substrate.

26. A photoresist composition, comprising:

a metal salt comprising a metal ion selected from the group consisting of titanium (IV), Niobium (V) and Tantalum (V);

an organic carboxylic acid in an amount of 0.5 to 3.0 molar equivalents relative to moles of the metal ion;

hydrogen peroxide in an amount of 1.0 to 10.0 molar equivalents relative to moles of the metal ion; and

a solvent.

27. The photoresist composition of claim 26, wherein the organic carboxylic acid is present in an amount of 0.75 to 1.5 molar equivalents relative to moles of the metal ion.

28. The photoresist composition of claim 26, wherein the organic carboxylic acid is present in an amount of 0.9 to 1.1 molar equivalents relative to moles of the metal ion.