Methods for improving selectivity of electroless deposition processes
Methods for improving selective deposition of a capping layer on a patterned substrate are presented, the method including: receiving the patterned substrate, the patterned substrate including a conductive region and a dielectric region; forming a molecular masking layer (MML) on the dielectric region; preparing an electroless (ELESS) plating bath, where the ELESS plating bath includes: a cobalt (Co) ion source: a complexing agent: a buffer: a tungsten (W) ion source: and a reducing agent; and reacting the patterned substrate with the ELESS plating bath for an ELESS period at an ELESS temperature and an ELESS pH so that the capping layer is selectively formed on the conductive region. In some embodiments, methods further include a pH adjuster for adjusting the ELESS pH to a range of approximately 9.0 pH to 9.2 pH. In some embodiments, the pH adjuster is tetramethylammonium hydroxide (TMAH). In some embodiments, the MML is hydrophilic.
1. A method for improving selective deposition of a capping layer on a patterned substrate, the method comprising:
receiving the patterned substrate, the patterned substrate comprising a conductive region and a dielectric region followed by;
forming a molecular masking layer (MML) on the dielectric region followed by;
removing unattached MML by pre-cleaning, followed by;
before reacting and/or contacting the patterned substrate with a plating bath, preparing an electroless (ELESS) plating bath, wherein the ELESS plating bath comprises:
a stabilizer comprising 2-mercapto benzothiazole (MBT) having a concentration of 0.1 ppm;
a cobalt (Co) ion source:
a complexing agent:
a buffer:
a tungsten (W) ion source:
a reducing agent; and
a surfactant comprising Hexadecyl trimethyl ammonium bromide (HTAB) having a concentration of 2 ppm, followed by;
reacting the patterned substrate with the ELESS plating bath for an ELESS period at an ELESS temperature and an ELESS pH such that the capping layer is selectively formed on the conductive region,
wherein the MML comprises a silanol having the formula:
R—X—Si(OH) 3 , wherein
R is a hydrophobic group having a formula O(C 2 H 4 O) m CH 3 where m=an integer greater than zero; and
X is an organic having a formula (CH 2 ) n where n=an integer greater than zero.
2. The method of claim 1 , wherein the ELESS plating bath is prepared to further comprise a pH adjuster for adjusting the ELESS pH to a range of approximately 9.0 to 9.2.
3. The method of claim 2 wherein the pH adjuster is tetramethylammonium hydroxide (TMAH).
4. The method of claim 1 , wherein the MML is hydrophilic.
5. The method of claim 1 , wherein the MML comprises polyvinyl alcohol (PVA).
6. The method of claim 5 , wherein the PVA includes a co-polymer selected from the group consisting of: co-ethylene, co-cation, co-siloxane, co-anion (88% hydrolyzed), and coanion (80% hydrolyzed).
7. The method of claim 1 , wherein the pre-cleaning includes pre-cleaning the patterned substrate for a pre-cleaning period; and rinsing the patterned substrate for a rinsing period.
8. The method of claim 1 , further comprising cross-linking the MML by a thermal cure wherein the thermal cure occurs over a cross-linking period of approximately 300 seconds at a cross-linking temperature of approximately less than 120 degree C. to 300 degree C.
9. The method of claim 1 , further comprising cross-linking the MML utilizing a cross-linking agent selected from the group consisting of: glutaraldehyde, dialdehydes, sulfuric acid (H 2 SO 4 ), maleic acid, citric acid, tetrabutylammonium acetate, and ascorbic acid, wherein the cross-linking occurs over a crosslinking period in a range of approximately 30 seconds to 600 seconds.
10. A method for improving selective deposition of a CoWPB capping layer on a patterned substrate, the method comprising:
receiving the patterned substrate comprising a conductive region and a dielectric region followed by;
forming a molecular masking layer (MML) on the dielectric region, wherein the MML comprises a silanol having the formula:
R—X—Si(OH) 3 , wherein
R is a hydrophobic group having a formula O(C 2 H 4 O) m CH 3 where m=an integer greater than zero; and
X is an organic having a formula (CH) n where n=an integer greater than zero followed by;
removing unattached MML by pre-cleaning, followed by;
before reacting and/or contacting the patterned substrate with a plating bath, preparing an electroless (ELESS) plating bath, wherein the ELESS plating bath comprises:
a cobalt (Co) ion source of an approximately 0.02M to 0.10M solution of Co(OH) 2 :
a complexing agent of an approximately 0.1M to 0.50M solution of citric acid:
a buffer of an approximately 0.1M to 0.50M solution of boric acid:
a tungsten (W) ion source of an approximately 0.01M to 0.1M solution of WO 3 in tetramethylammonium hydroxide (TMAH):
a reducing agent of an approximately 0.01M to 0.1M solution of p-dimethylamine borane (DMAB) and an approximately 0.1M to 0.5M solution of hypophosphourous acid; and
a stabilizer comprising 2-mercapto benzothiazole (MBT) having a concentration of 0.1 ppm;
a surfactant comprising Hexadecyl trimethyl ammonium bromide (HTAB) having a concentration of 2 ppm, followed by;
reacting the patterned substrate with the ELESS plating bath for an ELESS period at an ELESS temperature and an ELESS pH such that the CoWPB capping layer is selectively formed on the conductive region.
11. The method of claim 10 , wherein the ELESS plating bath is prepared to further comprise a pH adjuster for adjusting the ELESS pH to a range of approximately 9.0 to 9.2.
12. The method of claim 10 , wherein the ELESS temperature is in a range of approximately 700 C to 800 C, and the ELESS time period is approximately 30 seconds.