Etching composition

• US 10,490,417 B2
• Filed: 03/17/2015
• Issued: 11/26/2019
• Est. Priority Date: 03/18/2014
• Status: Active Grant

• Current Assignee: Fujifilm Electronic Materials USA Incorporated (Fujifilm Holdings Corporation)
• Original Assignee: Fujifilm Electronic Materials USA Incorporated (Fujifilm Holdings Corporation)
• Inventors: Dory, Thomas, Kneer, Emil A., Takahashi, Tomonori
• Primary Examiner(s): Tran, Binh X
• Application Number:
  US14/659,663
• Publication Number:
  US 20150267112A1
• Time in Patent Office: 1,715 Days
• Field of Search: 252 791, 252 794, 216 96, 216106, 216108
• CPC Class Codes: C09K 13/06 with organic material
• CPC Class Codes: C23F 1/00 Etching metallic material by chemical means manufacture of printing surfaces B41C; manufacture of printed circuits H05K
• CPC Class Codes: C23F 1/32 Alkaline compositions C23F1/42 takes precedence
• CPC Class Codes: H01L 21/02057 Cleaning during device manufacture
• CPC Class Codes: H01L 21/32134 by liquid etching only

Abstract

This disclosure relates to etching compositions containing 1) at least one oxidizing agent; 2) at least one chelating agent; 3) at least one metal corrosion inhibitor; 4) at least one organic solvent; 5) at least one amidine base; and 6) water.

Claims

1. An etching composition, comprising:

1) at least one oxidizing agent comprising hydrogen peroxide, the at least one oxidizing agent being in an amount of from about 5% to about 20% by weight of the composition;

2) at least one chelating agent comprising diethylenetriaminepentaacetic acid, the at least one chelating agent being in an amount of from about 0.1% to about 1% by weight of the composition;

3) at least one metal corrosion inhibitor comprising substituted or unsubstituted benzotriazole, the at least one metal corrosion inhibitor being in an amount of from about 0.1% to about 1% by weight of the composition;

4) at least one organic solvent;

5) at least one amidine base comprising an amidine group in a fused non-aromatic ring, the at least one amidine base being in an amount of from about 0.3% to about 2% by weight of the composition; and

6) water;

wherein the composition has a pH of at least about 6.5 and at most about 9.5, and the composition does not contain an abrasive.

2. The composition of claim 1, wherein the composition has a pH higher than 7 and at most about 9.

3. The composition of claim 1, wherein the at least one oxidizing agent is from about 5% to about 15% by weight of the composition.

4. The composition of claim 1, wherein the at least one metal corrosion inhibitor comprises a benzotriazole optionally substituted by at least one substituent selected from the group consisting of alkyl groups, aryl groups, halogen groups, amino groups, nitro groups, alkoxy groups, and hydroxyl groups.

5. The composition of claim 4, wherein the substituted or unsubstituted benzotriazole is selected from the group consisting of benzotriazole, 5-aminobenzotriazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-benzotriazole, 5-methyl-1H-benzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butyl benzotriazole, 5-(1′

,1′

-dimethylpropyl)-benzotriazole, 5-(1′

,1′

,3′

-trimethylbutyl)benzotriazole, 5-n-octyl benzotriazole, and 5-(1′

,1′

,3′

,3′

-tetramethylbutyl)benzotriazole.

6. The composition of claim 1, wherein the at least one metal corrosion inhibitor is from about 0.1% to about 0.7% by weight of the composition.

7. The composition of claim 1, wherein the at least one organic solvent comprises a solvent selected from the group consisting of water soluble alcohols, water soluble ketones, water soluble esters, and water soluble ethers.

8. The composition of claim 1, wherein the at least one organic solvent is from about 1% to about 30% by weight of the composition.

9. The composition of claim 1, wherein the amidine base containing an amidine group in a fused non-aromatic ring is 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene.

10. The composition of claim 1, wherein the at least one amidine base is from about 0.3% to about 1% by weight of the composition.

11. The composition of claim 1, wherein the water is from about 35% to about 85% by weight of the composition.

12. The composition of claim 1, wherein the at least one chelating agent is from about 0.1% to about 0.7% by weight of the composition.

13. A method, comprising:

contacting a semiconductor substrate containing TiN features with a composition of claim 1 to remove the TiN features.

14. The method of claim 13, wherein the method does not substantially remove Co, SiN, or Cu in the semiconductor substrate.

15. The method of claim 13, further comprising rinsing the semiconductor substrate with a rinse solvent after the contacting step.

16. The method of claim 15, further comprising drying the semiconductor substrate after the rinsing step.