Titanium nitride hard mask and etch residue removal
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C09K-013/00
C09K-013/08
H01L-021/311
출원번호
US-0642831
(2015-03-10)
등록번호
US-9222018
(2015-12-29)
발명자
/ 주소
Casteel, Jr., William Jack
Inaoka, Seiji
Liu, Wen Dar
Chen, Tianniu
출원인 / 주소
Air Products and Chemicals, Inc.
대리인 / 주소
Yang, Lina
인용정보
피인용 횟수 :
2인용 특허 :
1
초록▼
Formulations for stripping titanium nitride (TiN or TiNxOy; x=0 to 1.3 and y=0 to 2) hard mask and removing titanium nitride etch residue are low pH (4) comprise a weakly coordinating anion having negative charge highly dispersed throughout its structure, amine salt buffer, a non-oxidizing trace met
Formulations for stripping titanium nitride (TiN or TiNxOy; x=0 to 1.3 and y=0 to 2) hard mask and removing titanium nitride etch residue are low pH (4) comprise a weakly coordinating anion having negative charge highly dispersed throughout its structure, amine salt buffer, a non-oxidizing trace metal ion, a non-ambient trace oxidizer, and the remaining being solvent selected from the group consisting of water, sulfolane, dimethyl sulfide, lactic acid, glycol, and mixtures thereof. The formulations contain no hydrogen peroxide, and are exposed to air. Bifluoride, corrosion inhibitors, surfactants may be added to the formulations. Systems and processes use the formulations for stripping titanium nitride hard mask and removing titanium nitride etch residue.
대표청구항▼
1. A composition for selectively removing titanium nitride (TiN or TiNxOy; where x=0 to 1.3 and y=0 to 2) from a semiconductor device comprising TiN or TiNxOy and a second material selected from the group consisting of Cu, W, low-k dielectric material, and combinations thereof, the composition compr
1. A composition for selectively removing titanium nitride (TiN or TiNxOy; where x=0 to 1.3 and y=0 to 2) from a semiconductor device comprising TiN or TiNxOy and a second material selected from the group consisting of Cu, W, low-k dielectric material, and combinations thereof, the composition comprising: a weakly coordinating anion having negative charge highly dispersed throughout its structure;an amine salt buffer;a non-oxidizing trace metal ion;a non-ambient trace oxidizer; andthe remaining being solvent selected from the group consisting of water, sulfolane, dimethyl sulfide, lactic acid, glycol, and mixtures thereof;whereinthe composition is hydrogen peroxide-free;the composition is exposed to air;the composition has a pH1:1. 2. The composition of claim 1, wherein the weakly coordinating anion is present in a range of 1 to 10 wt % and is selected from the group consisting of: p-toluenesulfonate (C7H8SO3−), sulfate (SO42−), nitrate (NO3−), triflate (CF3SO3−), fluorosulfate, perfluorosulfonates (RfSO3−; where Rf is a perfluoroalkylgroup from C1 to C4), perfluorosulfonimides; ((Rf)2NSO2−; where Rf is a perfluoroalkylgroup from C1 to C4), hexafluorosilicate (SiF62−), hexafluorotitanate (TiF62−), tetrafluoroborate (BF4−), hexafluorophosphate (PF6−), hexafluoroantimonate (SbF6−), perfluoroalkylaluminates ((RfO)4Al−, Rf is a perfluoroalkyl group), and combinations thereof. 3. The composition of claim 1, wherein the amine salt buffer is present in a range of 0.5 to 10 wt % and is selected from the group consisting of: ammonium chloride; ammonium bisulfate; ammonium phosphates; ammonium oxalate;ammonium perfluorosulfonates; ammonium tetrafluoroborate; ammonium hexafluorotitanate;ammonium hexafluorosilicate; ammonium salts of organic acid selected from ammonium citrate, ammonium acetate, ammonium lactate; and combinations thereof;wherein the ammonium having a form of N(R1R2R3R4)+; wherein R1, R2, R3, R4 is independently selected from the group consisting of H, CH3, C2H5 and C3H7. 4. The composition of claim 1, wherein the non-oxidizing trace metal ion is present at 10:1. 9. The composition of claim 1, wherein the weakly coordinating anion is hexafluorosilicate, the amine salt buffer is ammonium chloride; the non-oxidizing trace metal ion is Cu(II)Cl2; the non-ambient trace oxidizer is non-stoichiometric Fe(III)Cl3, and the removal selectivity of TiN or TiNxOy vs. the second material is >10:1. 10. The composition of claim 9 further comprises ammonium bifluoride and polyethyleneimine. 11. A system for selectively removing titanium nitride (TiN or TiNxOy, where x=0 to 1.3 and y=0 to 2) from a surface of a microelectronic device, comprising: the semiconductor device comprising TiN or TiNxOy and a second material selected from Cu, W, low-k dielectric material and combinations thereof,a composition for selectively removing the TiN or TiNxOy from the semiconductor device comprising: a weakly coordinating anion having negative charge highly dispersed throughout its structure;an amine salt buffer;a non-oxidizing trace metal ion;a non-ambient trace oxidizer; andthe remaining being solvent selected from the group consisting of water, sulfolane, dimethyl sulfide, lactic acid, glycol, and mixtures thereof;whereinthe composition is hydrogen peroxide-free;the composition is exposed to air;the composition has a pH1:1;andwherein TiN or TiNxOy is in direct contact with the composition and the TiN or TiNxOy is not in direct in contact with W if the second material is W. 12. The system of claim 11, wherein the weakly coordinating anion is present in a range of 1 to 10 wt % and is selected from the group consisting of: p-toluenesulfonate (C7H8SO3−), sulfate (SO42−), nitrate (NO3−), triflate (CF3SO3−), fluorosulfate, perfluorosulfonates (RfSO3−; where Rf is a perfluoroalkylgroup from C1 to C4), perfluorosulfonimides; ((Rf)2NSO2−; where Rf is a perfluoroalkylgroup from C1 to C4), hexafluorosilicate (SiF62−), hexafluorotitanate (TiF62−), tetrafluoroborate (BF4−), hexafluorophosphate (PF6−), hexafluoroantimonate (SbF6−), perfluoroalkylaluminates ((RfO)4Al−, Rf is a perfluoroalkyl group), and combinations thereof. 13. The system of claim 11, wherein the amine salt buffer is present in a range of 0.5-10 wt % and is selected from the group consisting of: ammonium chloride; ammonium bisulfate; ammonium phosphates; ammonium oxalate; ammonium perfluorosulfonates; ammonium tetrafluoroborate; ammonium hexafluorotitanate; ammonium hexafluorosilicate; ammonium salts of organic acid selected from ammonium citrate, ammonium acetate, ammonium lactate; andcombinations thereof; wherein the ammonium having a form of N(R1R2R3R4)+;wherein R1, R2, R3, R4 is independently selected from the group consisting of H, CH3, C2H5, and C3H7. 14. The system of claim 11, wherein the non-oxidizing trace metal ion is in an amount of 10:1. 19. The system of claim 11, wherein the weakly coordinating anion is hexafluorosilicate, the amine salt buffer is ammonium chloride; the non-oxidizing trace metal ion is Cu(II)Cl2; the non-ambient trace oxidizer is non-stoichiometric Fe(III)Cl3, and the removal selectivity of TiN or TiNxOy vs. the second material is >10:1. 20. The system of claim 19, wherein the composition further comprises ammonium bifluoride, and polyethyleneimine. 21. A process of selectively removing titanium nitride (TiN or TiNxOy, where x=0 to 1.3 and y=0 to 2) comprising: providing a semiconductor device comprising TiN or TiNxOy and a second material selected from Cu, W, low-k dielectric material;contacting the semiconductor device with a composition comprising: a weakly coordinating anion having negative charge highly dispersed throughout its structure;an amine salt buffer;a non-oxidizing trace metal ion;a non-ambient trace oxidizer; andthe remaining being solvent selected from the group consisting of water, sulfolane, dimethyl sulfide, lactic acid, glycol, and mixtures thereof;whereinthe composition is hydrogen peroxide-free;the composition is exposed to air; andthe composition has a pH1:1. 22. The process of claim 21, wherein the weakly coordinating anion is present in a range of 1 to 10 wt % and is selected from the group consisting of: p-toluenesulfonate (C7H8SO3−), sulfate (SO42−), nitrate (NO3−), triflate (CF3SO3−), fluorosulfate, perfluorosulfonates (RfSO3−; where Rf is a perfluoroalkylgroup from C1 to C4), perfluorosulfonimides; ((Rf)2NSO2−; where Rf is a perfluoroalkylgroup from C1 to C4), hexafluorosilicate (SiF62−), hexafluorotitanate (TiF62−), tetrafluoroborate (BF4−), hexafluorophosphate (PF6−), hexafluoroantimonate (SbF6−), perfluoroalkylaluminates ((RfO)4Al−, Rf is a perfluoroalkyl group), and combinations thereof. 23. The process of claim 21, wherein the amine salt buffer is present in a range of 0.5-10 wt % and is selected from the group consisting of: ammonium chloride; ammonium bisulfate; ammonium phosphates; ammonium oxalate; ammonium perfluorosulfonates; ammonium tetrafluoroborate; ammonium hexafluorotitanate; ammonium hexafluorosilicate; ammonium salts of organic acid selected from ammonium citrate, ammonium acetate, ammonium lactate; and combinations thereof; wherein the ammonium having a form of N(R1R2R3R4)+; wherein R1, R2, R3, R4 is independently selected from the group consisting of H, CH3, C2H5, and C3H7. 24. The process of claim 21, wherein the non-oxidizing trace metal ion is 10:1. 29. The process of claim 21, wherein the weakly coordinating anion is hexafluorosilicate, the amine salt buffer is ammonium chloride; the non-oxidizing trace metal ion is Cu(II)Cl2; the non-ambient trace oxidizer is non-stoichiometric Fe(III)Cl3, and the removal selectivity of TiN or TiNxOy vs. the second material is >10:1. 30. The process of claim 29, wherein the composition further comprises ammonium bifluoride, and polyethyleneimine.
연구과제 타임라인
LOADING...
LOADING...
LOADING...
LOADING...
LOADING...
이 특허에 인용된 특허 (1)
Cernat,Mihaela; Lee,Shihying, Reducing oxide loss when using fluoride chemistries to remove post-etch residues in semiconductor processing.
※ AI-Helper는 부적절한 답변을 할 수 있습니다.