IN SITU GENERATION OF RuO4 FOR ALD OF Ru AND Ru RELATED MATERIALS

• US 20100209598A1
• Filed: 02/13/2010
• Published: 08/19/2010
• Est. Priority Date: 02/13/2009
• Status: Active Grant

• Current Assignee: Entegris Incorporated
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Xu, Chongying, Cameron, Thomas M., Li, Weimin
• Granted Patent: US 8,663,735 B2
• Time in Patent Office: Days
• US Class Current: 427/124
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/4488 by in situ generation of reactive gas by chemical or electrochemical reaction
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01G 4/008 Selection of materials
• CPC Class Codes: H01G 4/1209 characterised by the ceramic dielectric material H01G4/1272, H01G4/1281 take precedence
• CPC Class Codes: H01G 4/33 Thin- or thick-film capacitors thin- or thick-film circuits H01L27/00; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor H01L28/40
• CPC Class Codes: H01L 21/02175 characterised by the metal H01L21/02197 takes precedence
• CPC Class Codes: H01L 21/02194 the material containing more than one metal element
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/31604 Deposition from a gas or vapour H01L21/31691, H01L21/31695 take precedence

Abstract

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.

Claims

1. A system for manufacturing a microelectronic device, comprising:

(A) a ruthenium tetraoxide (RuO₄) source, adapted for in situ generation of RuO₄, said source including;

(i) an oxic gas supply; and

(ii) a container holding at least one RuO₄ precursor selected from among Ru and RuO₂, said container being adapted for heating to temperature in a range of from 40°

C. to 400°

C., having an inlet for introducing an oxic gas into said container for reaction with said RuO₄ precursor to form gaseous RuO₄ and having an outlet for flowing gaseous RuO₄ out of the container; and

(B) a semiconductor manufacturing vapor deposition tool arranged to receive gaseous RuO₄ discharged from such container through said outlet, and to effect contacting of said gaseous RuO₄ with a microelectronic device substrate to deposit Ru and/or RuO₂ thereon.

2. The system of claim 1, further comprising at least one of (i) a heater arranged to heat the container to said temperature;

and (ii) an ozone generator as said oxic gas supply.

3. The system of claim 1, wherein the semiconductor manufacturing vapor deposition tool comprises a chemical vapor deposition apparatus, or an atomic layer deposition apparatus.

4. The system of claim 3, including an atomic layer deposition apparatus, and further comprising a strontium precursor source arranged to flow a strontium precursor vapor to the atomic layer deposition apparatus, and wherein the atomic layer deposition apparatus is arranged to deposit a strontium ruthenium oxide film on the microelectronic device substrate.

5. The system of claim 1, wherein the container includes support surface elements in its interior volume, in contact with said RuO₄ precursor.

6. The system of claim 5, wherein said support surface elements comprise plate members in contact with said RuO₄ precursor, or an array of trays on which said RuO₄ precursor is reposed.

7. The system of claim 1, wherein said RuO₄ precursor is present in said container in the form of a porous foam material.

8. A method of manufacturing a microelectronic device, comprising:

providing at least one RuO₄ precursor selected from among Ru and RuO₂;

contacting the RuO₄ precursor with an oxic gas at temperature temperature in a range of from 40°

C. to 400°

C. to form gaseous RuO₄; and

contacting the gaseous RuO₄ with a microelectronic device substrate under vapor deposition conditions to deposit Ru and/or RuO₂ thereon.

9. The method of claim 8, wherein the RuO₄ precursor comprises Ru, RuO₂ or Ru and RuO₂.

10. The method of claim 8, wherein the oxic gas is selected from the group consisting of oxygen, ozone, air, and nitrogen oxide.

11. The method of claim 8, wherein said contacting comprises chemical vapor deposition or atomic layer deposition.

12. The method of claim 11, 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 RuO₄, so as to form a strontium- and ruthenium-containing film on said microelectronic device substrate.

13. The method of claim 12, wherein said strontium-containing precursor vapor comprises vapor of a strontium precursor selected from the group consisting of Sr(ⁿPrMe₄Cp)₂, Sr(EtMe₄Cp)₂, Sr(thd)₂, and Sr(thd)₂.PMDETA.

14. The method of claim 12, wherein said strontium- and ruthenium-containing film comprises an SrRuO₃ film.

15. The method of claim 14, wherein said SrRuO₃ film forms an electrode of a capacitor on said microelectronic device substrate.

16. The method of claim 8, wherein said microelectronic device comprises a DRAM device.

17. A ruthenium tetraoxide supply apparatus, comprising a container holding at least one RuO₄ precursor selected from among Ru and RuO₂, said container being adapted for heating to temperature in a range of from 40°

C. to 400°

C., having an inlet for introducing an oxic gas into said container for reaction with said RuO₄ precursor to form gaseous RuO₄ and having an outlet for flowing gaseous RuO₄ out of the container.

18. The ruthenium tetraoxide supply apparatus of claim 17, further comprising a heater adapted to heat the container to said temperature in the range from 40°

C. to 400°

C.

19. The ruthenium tetraoxide supply apparatus of claim 17, further comprising an oxic gas source coupled with said container and arranged for flow of oxic gas from said oxic gas source through said container for contacting said at least one RuO₄ precursor therein.

20. The ruthenium tetraoxide supply apparatus of claim 18, further comprising an oxic gas source coupled with said container and arranged for flow of oxic gas from said oxic gas source through said container for contacting said at least one RuO₄ precursor therein.