COMPOSITION AND PROCESS FOR THE SELECTIVE REMOVE OF TiSiN

• US 20100065530A1
• Filed: 02/06/2008
• Published: 03/18/2010
• Est. Priority Date: 02/06/2007
• Status: Abandoned Application

• Current Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Liu, Jun, Bernhard, Bernhard D., Walker, Elizabeth, Cooper, Emanuel I.
• Application Number:
  US12/525,600
• Publication Number:
  US 20100065530A1
• Time in Patent Office: Days
• US Class Current: 216/13
• CPC Class Codes: H01L 21/32134 by liquid etching only
• CPC Class Codes: H10N 70/011 Manufacture or treatment of multistable switching devices
• CPC Class Codes: H10N 70/231 based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
• CPC Class Codes: H10N 70/8413 adapted for resistive heating

Abstract

An aqueous removal composition and process for removing heater material, including TiSiN, from a microelectronic device having said material thereon. The aqueous removal composition includes at least one fluoride source, at least one passivating agent, and at least one oxidizing agent. The composition selectively removes TiSiN relative to oxides and nitrides that are adjacently present.

Claims

1. An aqueous removal composition comprising at least one fluoride source, at least one passivating agent, and at least one oxidizing agent.

2. The aqueous removal composition of claim 1, wherein said aqueous removal composition etchingly removes heater material from a microelectronic device having same thereon, wherein the heater material comprises material selected from the group consisting of nc-MN/a-Si₃N₄, SiGe alloys, NiCr, Ta, AlTiN, and TaSiN, and combinations thereof, wherein M comprises a metal selected from the group consisting of Ti, W, V, Nb, Zr, and combinations thereof.

3. The aqueous removal composition of claim 1, wherein the at least one fluoride source, at least one passivating agent, and at least one oxidizing agent are present in amounts effective to achieve an etch rate of TiSiN in a range from about 100 Å

min<sup>−

1</sup> to about 200 Å

min<sup>−

1</sup> at temperatures in a range from about 30°

C. to about 70°

C.

4. The aqueous removal composition of claim 1, wherein pH is in a range from about 0 to about 4.5.

5. The aqueous removal composition of claim 1, wherein the at least one fluoride source comprises a fluoro-containing species selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium bifluoride, fluoroboric acid, fluorosilicic acid, and combinations thereof.

wherein the at least one passivating agent comprises a species selected from the group consisting of boric acid, 3-hydroxy-2-naphthoic acid, malonic acid, iminodiacetic acid, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (i.e., butyl carbitol), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof;

and

wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, oxone, oxone tetrabutylammonium salt, ferric nitrate, potassium iodate, potassium permanganate, nitric acid, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, sodium persulfate, potassium persulfate, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, urea hydrogen peroxide, peracetic acid, N-methylmorpholine-N-oxide (NMMO);

trimethylamine-N-oxide;

triethylamine-N-oxide;

pyridine-N-oxide;

N-ethylmorpholine-N-oxide;

N-methylpyrrolidine-N-oxide;

N-ethylpyrrolidine-N-oxide, and combinations thereof.

6. The aqueous removal composition of claim 1, comprising fluoroboric acid, boric acid, and hydrogen peroxide.

8. The aqueous removal composition of claim 1, wherein the composition is devoid of a species selected from the group consisting of oxalic acid, chlorine-containing compounds, monoethanolamine, monoethanolammonium salt, persulfate, abrasive material, and combinations thereof.

11. The aqueous removal composition of claim 1, further comprising at least one additional component selected from the group consisting of at least one buffering agent, at least one pH adjusting agent, at least one chelating agent, and combinations thereof.

12. The aqueous removal composition of claim 1, further comprising heater material residue.

26. The aqueous removal composition of claim 1, comprising boric acid.

27. The aqueous removal composition of claim 1, comprising fluoroboric acid.

28. The aqueous removal composition of claim 1, comprising hydrogen peroxide.

7. (canceled)

9. (canceled)

10. (canceled)

13-15. -15. (canceled)

16. A method of removing heater material from a microelectronic device having said material thereon, said method comprising contacting the microelectronic device with an aqueous removal composition for sufficient time and under sufficient contacting conditions to at least partially remove said material from the microelectronic device, wherein the aqueous removal composition includes at least one fluoride source, at least one passivating agent, and at least one oxidizing agent.

17. The method of claim 16, wherein the heater material comprises material selected from the group consisting of nc-MN/a-Si₃N₄, SiGe alloys, NiCr, Ta, AlTiN, and TaSiN, and combinations thereof, wherein M comprises a metal selected from the group consisting of Ti, W, V, Nb, Zr, and combinations thereof.

18. The method of claim 16, wherein said contacting comprises conditions selected from the group consisting of:

time of from about 1 minute to about 30 minutes;

temperature in a range of from about 40°

C. to about 70°

C.; and

combinations thereof.

19. The method of claim 16, wherein said removal composition has a pH in a range of from about 0 to about 4.5.

20. The method of claim 16, wherein the contacting comprises a process selected from the group consisting of:

spraying the removal composition on a surface of the microelectronic device;

dipping the microelectronic device in a sufficient volume of removal composition;

contacting a surface of the microelectronic device with another material that is saturated with the removal composition; and

contacting the microelectronic device with a circulating removal composition.

23. The method of claim 16, wherein the aqueous removal composition comprises fluoroboric acid, boric acid, and hydrogen peroxide

24. The method of claim 16, further comprising at least one additional component selected from the group consisting of at least one buffering agent, at least one pH adjusting agent, at least one chelating agent, and combinations thereof.

25. The method of claim 16, wherein the removal composition further comprises heater material residue.

21. (canceled)

22. (canceled)