In situ generation of RuO4 for ALD of Ru and Ru related materials
View Patent ↗Apparatus and method for generating ruthenium tetraoxide in situ for use in vapor deposition, e.g., atomic layer deposition (ALD), of ruthenium-containing films on microelectronic device substrates. The ruthenium tetraoxide can be generated on demand by reaction of ruthenium or ruthenium dioxide with an oxic gas such as oxygen or ozone. In one implementation, ruthenium tetraoxide thus generated is utilized with a strontium organometallic precursor for atomic layer deposition of strontium ruthenate films of extremely high smoothness and purity.
1. A method of manufacturing a microelectronic device, comprising:
providing at least one RuO 4 precursor selected from among Ru and RuO 2 ;
contacting the RuO 4 precursor with an oxic gas at temperature in a range of from 40° C. to 400° C. to form gaseous RuO 4 ; and
contacting the gaseous RuO 4 with a microelectronic device substrate under vapor deposition conditions to deposit Ru and/or RuO 2 thereon.
2. The method of claim 1 , wherein the RuO 4 precursor comprises Ru, RuO 2 or Ru and RuO 2 .
3. The method of claim 1 , wherein the oxic gas is selected from the group consisting of oxygen, ozone, air, and nitrogen oxide.
4. The method of claim 1 , wherein said contacting comprises chemical vapor deposition or atomic layer deposition.
5. The method of claim 4 , wherein said contacting comprises atomic layer deposition, further comprising contacting the microelectronic device substrate with a strontium-containing precursor vapor, alternatingly and repetitively with said contacting of said microelectronic device substrate with said gaseous RuO 4 , so as to form a strontium- and ruthenium-containing film on said microelectronic device substrate.
6. The method of claim 5 , wherein said strontium-containing precursor vapor comprises vapor of a strontium precursor selected from the group consisting of Sr( n PrMe 4 Cp) 2 , Sr(EtMe 4 Cp) 2 , Sr(thd) 2 , and Sr(thd) 2 .PMDETA.
7. The method of claim 5 , wherein said strontium- and ruthenium-containing film comprises an SrRuO 3 film.
8. The method of claim 7 , wherein said SrRuO 3 film forms an electrode of a capacitor on said microelectronic device substrate.
9. The method of claim 1 , wherein said microelectronic device comprises a DRAM device.