IP Library Granted Patent US 8,415,255
Granted Patent B2
US 8,415,255 · App. 12/063,010 · Granted Apr 9, 2013

Pore sealing and cleaning porous low dielectric constant structures

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Quick Facts
Patent No.
US 8,415,255
App. No.
12/063,010
Granted
Apr 9, 2013
Kind
B2
Abstract

A micellar solution is used to seal pores exposed at the bottom and sidewall surfaces of a structure etched in or through a porous low dielectric constant material. The micellar solution is also effective to clean away etch residues from the etched structure.

Claims (36)

1. A method of sealing pores of a porous dielectric material exposed at a surface of an etched structure, the method comprising:

applying to said etched structure a micellar solution comprising micelles of diameter equal to or greater than about 1.5 times the diameter of the pores in said porous dielectric material, the micelles to seal pores of the porous material and limit ingress of water into the pores.

2. The processing method of claim 1 , wherein said etched structure is formed in a porous dielectric material having a bulk dielectric constant equal to or less than about 3.0.

3. The processing method of claim 2 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, said one or more surfactants being selected in the group consisting of:

the cationic surfactants of the group consisting of: quaternary ammonium halides, quaternary ammonium salts, long chain amines, long chain diamines, long chain polyamines, salts of long chain amines, diamines and polyamines, polyoxyethylenated (or quaternized POE) long-chain amines, and amine oxides;

the anionic surfactants of the group consisting of: carboxylic acids and salts of carboxylic acids, amines and salts of amines, sulfonic acid and sulphuric/phosphoric acid ester and salts, fluorosurfactants;

the non-ionic surfactants of the group consisting of: alkylphenol ethoxylates, carboxylic acid esters, fluorosurfactants, polyoxyethylenated (POE) ethoxylates alcohols/glycols, POE polyoxypropylene glycol, POE mercaptans, alkanolamides, alkylpyrrolidones); and

zwitterionic surfactants of the group consisting of: alkyl amino and imino propionic acids, imidazoline carboxylates, alkylbetaines, amines and amine oxides.

4. A processing method according to claim 2 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, and a total amount of said one or more surfactants present in the micellar solution is about 0.05 to about 5.0% by weight compared to the total weight of the solution.

5. A processing method according to claim 2 , wherein the micellar solution is applied to the etched surface using post-etch wet cleaning apparatus having a micellar solution in the cleaning-fluid dispensing section thereof.

6. The processing method of claim 1 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, said one or more surfactants being selected in the group consisting of:

the cationic surfactants of the group consisting of: quaternary ammonium halides, quaternary ammonium salts, long chain amines, long chain diamines, long chain polyamines, salts of long chain amines, diamines and polyamines, polyoxyethylenated (or quaternized POE) long-chain amines, and amine oxides;

the anionic surfactants of the group consisting of: carboxylic acids and salts of carboxylic acids, amines and salts of amines, sulfonic acid and sulphuric/phosphoric acid ester and salts, fluorosurfactants;

the non-ionic surfactants of the group consisting of: alkylphenol ethoxylates, carboxylic acid esters, fluorosurfactants, polyoxyethylenated (POE) ethoxylates alcohols/glycols, POE polyoxypropylene glycol, POE mercaptans, alkanolamides, alkylpyrrolidones); and

zwitterionic surfactants of the group consisting of: alkyl amino and imino propionic acids, imidazoline carboxylates, alkylbetaines, amines and amine oxides.

7. A processing method according to claim 6 , wherein the total amount of said one or more surfactants present in the micellar solution is about 0.1 to about 3.0% by weight compared to the total weight of the solution.

8. A processing method according to claim 6 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, and a total amount of said one or more surfactants present in the micellar solution is about 0.05 to about 5.0% by weight compared to the total weight of the solution.

9. A processing method according to claim 6 , wherein the micellar solution is applied to the etched surface using post-etch wet cleaning apparatus having a micellar solution in the cleaning-fluid dispensing section thereof.

10. A processing method according to claim 1 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, and a total amount of said one or more surfactants present in the micellar solution is about 0.05 to about 5.0% by weight compared to the total weight of the solution.

11. A processing method according to claim 10 , wherein the micellar solution is applied to the etched surface using post-etch wet cleaning apparatus having a micellar solution in the cleaning-fluid dispensing section thereof.

12. A processing method according to claim 1 , wherein the micellar solution is applied to the etched surface using post-etch wet cleaning apparatus having a micellar solution in the cleaning-fluid dispensing section thereof.

13. The method of claim 1 , whereby the micelles block the pores at the surface, limiting ingress of water.

14. A method of manufacturing a semiconductor device, comprising the steps of:

forming a layer of porous dielectric material at at least one level on a semiconductor wafer;

etching at least one structure whereby to expose pores of said porous dielectric material at a surface or sidewall of the etched structure; and

applying to said at least one structure a micellar solution comprising micelles of diameter equal to or greater than about 1.5 times the diameter of the pores of said porous dielectric material, the micelles to seal the exposed pores of said porous dielectric material.

15. The method of claim 14 , wherein said porous dielectric material is a material having a bulk dielectric constant equal to or less than about 3.0.

16. A semiconductor device manufacturing method according to claim 15 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, and a total amount of said one or more surfactants present in the micellar solution is about 0.05 to about 5.0% by weight compared to the total weight of the solution.

17. The semiconductor device manufacturing method of claim 14 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, said one or more surfactants being selected in the group consisting of:

the cationic surfactants of the group consisting of: quaternary ammonium halides, quaternary ammonium salts, long chain amines, long chain diamines, long chain polyamines, salts of long chain amines, diamines and polyamines, polyoxyethylenated (or quaternized POE) long-chain amines, and amine oxides;

the anionic surfactants of the group consisting of: carboxylic acids and salts of carboxylic acids, amines and salts of amines, sulfonic acid and sulphuric/phosphoric acid ester and salts, fluorosurfactants;

the non-ionic surfactants of the group consisting of: alkylphenol ethoxylates, carboxylic acid esters, fluorosurfactants, polyoxyethylenated (POE) ethoxylates alcohols/glycols, POE polyoxypropylene glycol, POE mercaptans, alkanolamides, alkylpyrrolidones; and

zwitterionic surfactants of the group consisting of: alkyl amino and imino propionic acids, imidazoline carboxylates, alkylbetaines, amines and amine oxides.

18. A semiconductor device manufacturing method according to claim 17 , wherein a total amount of said one or more surfactants present in the micellar solution is about 0.1 to about 3.0% by weight compared to the total weight of the solution.

19. A semiconductor device manufacturing method according to claim 17 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, and a total amount of said one or more surfactants present in the micellar solution is about 0.05 to about 5.0% by weight compared to the total weight of the solution.

20. A semiconductor device manufacturing method according to claim 14 , wherein the micellar solution comprises one or more surfactants present at a concentration higher than the respective critical micelle concentration thereof, and a total amount of said one or more surfactants present in the micellar solution is about 0.05 to about 5.0% by weight compared to the total weight of the solution.

Assignments (31)
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 11759915 AND REPLACE IT WITH APPLICATION 11759935 PREVIOUSLY RECORDED ON REEL 040925 FRAME 0001. ASSIGNOR(S) HEREBY CONFIRMS THE RELEASE OF SECURITY INTEREST. Recorded Feb 17, 2020
From: MORGAN STANLEY SENIOR FUNDING, INC.
To: NXP, B.V. F/K/A FREESCALE SEMICONDUCTOR, INC.
Reel/Frame 052917/0001 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 11759915 AND REPLACE IT WITH APPLICATION 11759935 PREVIOUSLY RECORDED ON REEL 040928 FRAME 0001. ASSIGNOR(S) HEREBY CONFIRMS THE RELEASE OF SECURITY INTEREST. Recorded Jan 17, 2020
From: MORGAN STANLEY SENIOR FUNDING, INC.
To: NXP B.V.
Reel/Frame 052915/0001 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 11759915 AND REPLACE IT WITH APPLICATION 11759935 PREVIOUSLY RECORDED ON REEL 037486 FRAME 0517. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT AND ASSUMPTION OF SECURITY INTEREST IN PATENTS. Recorded Dec 10, 2019
From: CITIBANK, N.A.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 053547/0421 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 12298143 PREVIOUSLY RECORDED ON REEL 042762 FRAME 0145. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT SUPPLEMENT. Recorded Oct 22, 2019
From: NXP B.V.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 051145/0184 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 12298143 PREVIOUSLY RECORDED ON REEL 038017 FRAME 0058. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT SUPPLEMENT. Recorded Oct 22, 2019
From: NXP B.V.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 051030/0001 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 12298143 PREVIOUSLY RECORDED ON REEL 042985 FRAME 0001. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT SUPPLEMENT. Recorded Oct 22, 2019
From: NXP B.V.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 051029/0001 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 12298143 PREVIOUSLY RECORDED ON REEL 039361 FRAME 0212. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT SUPPLEMENT. Recorded Oct 22, 2019
From: NXP B.V.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 051029/0387 →
RELEASE OF SECURITY INTEREST Recorded Sep 10, 2019
From: MORGAN STANLEY SENIOR FUNDING, INC.
To: NXP B.V.
Reel/Frame 050745/0001 →
RELEASE OF SECURITY INTEREST Recorded Sep 10, 2019
From: MORGAN STANLEY SENIOR FUNDING, INC.
To: NXP B.V.
Reel/Frame 050744/0097 →
CORRECTIVE ASSIGNMENT TO CORRECT THE TO CORRECT THE APPLICATION NO. FROM 13,883,290 TO 13,833,290 PREVIOUSLY RECORDED ON REEL 041703 FRAME 0536. ASSIGNOR(S) HEREBY CONFIRMS THE THE ASSIGNMENT AND ASSUMPTION OF SECURITY INTEREST IN PATENTS.. Recorded Feb 20, 2019
From: MORGAN STANLEY SENIOR FUNDING, INC.
To: SHENZHEN XINGUODU TECHNOLOGY CO., LTD.
Reel/Frame 048734/0001 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 12681366 PREVIOUSLY RECORDED ON REEL 038017 FRAME 0058. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT SUPPLEMENT. Recorded May 9, 2017
From: NXP B.V.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 042985/0001 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 12681366 PREVIOUSLY RECORDED ON REEL 039361 FRAME 0212. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT SUPPLEMENT. Recorded May 9, 2017
From: NXP B.V.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 042762/0145 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE PATENTS 8108266 AND 8062324 AND REPLACE THEM WITH 6108266 AND 8060324 PREVIOUSLY RECORDED ON REEL 037518 FRAME 0292. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT AND ASSUMPTION OF SECURITY INTEREST IN PATENTS. Recorded Feb 1, 2017
From: CITIBANK, N.A.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 041703/0536 →
CORRECTIVE ASSIGNMENT TO CORRECT THE NATURE OF CONVEYANCE LISTED CHANGE OF NAME SHOULD BE MERGER AND CHANGE PREVIOUSLY RECORDED AT REEL: 040652 FRAME: 0180. ASSIGNOR(S) HEREBY CONFIRMS THE MERGER AND CHANGE OF NAME. Recorded Jan 12, 2017
From: FREESCALE SEMICONDUCTOR INC.
To: NXP USA, INC.
Reel/Frame 041354/0148 →
CHANGE OF NAME Recorded Nov 8, 2016
From: FREESCALE SEMICONDUCTOR INC.
To: NXP USA, INC.
Reel/Frame 040652/0180 →
RELEASE OF SECURITY INTEREST Recorded Nov 7, 2016
From: MORGAN STANLEY SENIOR FUNDING, INC.
To: NXP B.V.
Reel/Frame 040928/0001 →
RELEASE OF SECURITY INTEREST Recorded Sep 21, 2016
From: MORGAN STANLEY SENIOR FUNDING, INC.
To: NXP, B.V., F/K/A FREESCALE SEMICONDUCTOR, INC.
Reel/Frame 040925/0001 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE APPLICATION 12092129 PREVIOUSLY RECORDED ON REEL 038017 FRAME 0058. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT SUPPLEMENT. Recorded Jul 14, 2016
From: NXP B.V.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 039361/0212 →
SUPPLEMENT TO THE SECURITY AGREEMENT Recorded Jun 16, 2016
From: FREESCALE SEMICONDUCTOR, INC.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 039138/0001 →
SECURITY AGREEMENT SUPPLEMENT Recorded Mar 7, 2016
From: NXP B.V.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 038017/0058 →
ASSIGNMENT AND ASSUMPTION OF SECURITY INTEREST IN PATENTS Recorded Jan 13, 2016
From: CITIBANK, N.A.
To: MORGAN STANLEY SENIOR FUNDING, INC.
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ASSIGNMENT AND ASSUMPTION OF SECURITY INTEREST IN PATENTS Recorded Jan 12, 2016
From: CITIBANK, N.A.
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 037486/0517 →
PATENT RELEASE Recorded Dec 21, 2015
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: FREESCALE SEMICONDUCTOR, INC.
Reel/Frame 037354/0688 →
PATENT RELEASE Recorded Dec 21, 2015
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: FREESCALE SEMICONDUCTOR, INC.
Reel/Frame 037356/0553 →
PATENT RELEASE Recorded Dec 21, 2015
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: FREESCALE SEMICONDUCTOR, INC.
Reel/Frame 037356/0143 →
SECURITY AGREEMENT Recorded Nov 6, 2013
From: FREESCALE SEMICONDUCTOR, INC.
To: CITIBANK, N.A., AS NOTES COLLATERAL AGENT
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SECURITY AGREEMENT Recorded Jun 18, 2013
From: FREESCALE SEMICONDUCTOR, INC.
To: CITIBANK, N.A., AS NOTES COLLATERAL AGENT
Reel/Frame 030633/0424 →
SECURITY AGREEMENT Recorded May 13, 2010
From: FREESCALE SEMICONDUCTOR, INC.
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 024397/0001 →
SECURITY AGREEMENT Recorded Mar 15, 2010
From: FREESCALE SEMICONDUCTOR, INC.
To: CITIBANK, N.A.
Reel/Frame 024085/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 26, 2010
From: SHARMA, BALGOVIND K.
To: FREESCALE SEMICONDUCTOR, INC.
Reel/Frame 023844/0534 →
SECURITY AGREEMENT Recorded Jul 7, 2008
From: FREESCALE SEMICONDUCTOR, INC.
To: CITIBANK, N.A.
Reel/Frame 021194/0593 →