Methods of raising reflow temperature of glass alloys by thermal treatment in steam, and microelectronic structures formed thereby

• US 6,271,150 B1
• Filed: 11/30/1998
• Issued: 08/07/2001
• Est. Priority Date: 11/30/1998
• Status: Expired due to Term

• Current Assignee: MCNC, Inc., Micross Advanced Interconnect Technology LLC, North Carolina State University (University of North Carolina System)
• Original Assignee: MCNC, Inc., North Carolina State University (University of North Carolina System)
• Inventors: Croswell, Robert T., Simpson, Darrell L., Williams, C. Kenneth, Reisman, Arnold, Temple, Dorota
• Primary Examiner(s): Meier, Stephen D.
• Assistant Examiner(s): GOODWIN, DAVID J
• Application Number:
  US09/201,447
• Time in Patent Office: 981 Days
• Field of Search: 438/758, 438/760, 438/761, 438/763, 438/778, 438/781, 438/783, 438/795
• US Class Current: 438/760
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/02129 the material being boron or phosphorus doped silicon oxides, e.g. BPSG, BSG or PSG
• CPC Class Codes: H01L 21/022 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides adhesion layers or buffer layers H01L21/02304, H01L21/02362
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/02337 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/3105 After-treatment
• CPC Class Codes: H01L 21/31051 Planarisation of the insulating layers H01L21/31058 takes precedence
• CPC Class Codes: H01L 21/31604 Deposition from a gas or vapour H01L21/31691, H01L21/31695 take precedence
• CPC Class Codes: H01L 21/31625 Deposition of boron or phosphorus doped silicon oxide, e.g. BSG, PSG, BPSG
• CPC Class Codes: H01L 29/66181 Conductor-insulator-semiconductor capacitors, e.g. trench capacitors

Abstract

A layer of doped or undoped germanosilicate glass is formed on a substrate and the layer of germanosilicate glass is thermally treated in steam to remove germanium from the germanosilicate glass, and thereby raise the reflow temperature of the germanosilicate glass so treated. The layer of germanosilicate glass on the substrate may be a nonplanar layer of germanosilicate glass. When thermally treating the nonplanar layer of germanosilicate glass in steam, the layer of germanosilicate glass may be planarized simultaneously with the removal of germanium from the planarized germanosilicate glass. This process may be repeated to create a hierarchy of reflowed glass where each underlying layer reflows at a higher temperature than the next deposited glass layer. The steam thermal treatment step may be preceded by a thermal pretreatment of the layer of germanosilicate glass in at least one of a noble gas and nitrogen gas, to reflow the layer of germanosilicate glass. The thermal pretreating step may partially planarize the nonplanar layer of germanosilicate glass, and the thermal treating step may then fully planarize the partially planarized germanosilicate glass. Alternatively, the thermal pretreating step may fully planarize the layer of germanosilicate glass and the thermal treating step may then remove germanium from the fully planarized germanosilicate glass.

Claims

1. A method of forming a layer on a substrate comprising the steps of:

forming a layer of germanosilicate glass on a substrate;

pretreating the layer of germanosilicate glass in at least one of a noble gas and nitrogen gas to reflow the layer of germanosilicate glass; and

then

thermally treating the thermally pretreated layer of germanosilicate glass in steam to remove germanium from the germanosilicate glass and thereby raise the reflow temperature of the germanosilicate glass so treated.

2. A method according to claim 1:

wherein the forming step comprises the step of forming a nonplanar layer of germanosilicate glass on a substrate;

wherein the thermally pretreating step comprises the step of thermally pretreating the nonplanar layer of germanosilicate glass in at least one of a noble gas and nitrogen gas to reflow the nonplanar layer of germanosilicate glass and partially planarize the nonplanar layer of germanosilicate glass; and

wherein the thermally treating step comprises the step of thermally treating the partially planarized layer of germanosilicate glass in steam to remove germanium from the partially planarized germanosilicate glass and to fully planarize the partially planarized germanosilicate glass.

3. A method according to claim 1:

wherein the forming step comprises the step of forming a nonplanar layer of germanosilicate glass on a substrate;

wherein the thermally pretreating step comprises the step of thermally pretreating the nonplanar layer of germanosilicate glass in at least one of a noble gas and nitrogen gas to reflow the nonplanar layer of germanosilicate glass and fully planarize the nonplanar layer of germanosilicate glass; and

wherein the thermally treating step comprises the step of thermally treating the fully planarized layer of germanosilicate glass in steam to remove germanium from the fully planarized germanosilicate glass.

7. A method according to claim 3:

wherein the forming step comprises the step of forming a nonplanar layer of doped germanosilicate glass on a substrate, the doped germanosilicate glass having lower reflow temperature than undoped germanosilicate glass; and

wherein the thermally treating step comprises the step of thermally treating the nonplanar layer of doped germanosilicate glass in steam to planarize the nonplanar layer of doped germanosilicate glass and to remove at least one of germanium and dopant from the germanosilicate glass and thereby raise the reflow temperature of the doped germanosilicate glass so treated.

4. A method of forming a layer on a substrate comprising the steps of:

forming a layer of germanosilicate glass on a substrate using Plasma Enhanced Chemical Vapor Deposition (PECVD) at about 200°

C.; and

thermally treating the layer of germanosilicate glass in steam to remove germanium from the germanosilicate glass and thereby raise the reflow temperature of the germanosilicate glass so treated.

5. A method of forming a layer on a substrate comprising the steps of:

forming a layer of germanosilicate glass having mole percentage of germanium dioxide of between about 60% and about 85% on a substrate; and

thermally treating the layer of germanosilicate glass in steam to remove germanium from the germanosilicate glass and thereby raise the reflow temperature of the germanosilicate glass so treated.

6. A method according to claim 5 wherein the forming step comprises the step of forming a layer of germanosilicate glass having mole percentage of germanium dioxide of between about 77% and about 83%.

8. A method of forming a layer on a substrate comprising the steps of:

forming a layer of boron doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 40% and about 85% and mole percentage of boron of between about 1% and about 4% relative to the total on a substrate; and

thermally treating the layer of doped germanosilicate glass in steam to remove at least one of germanium and dopant from the germanosilicate glass and thereby raise the reflow temperature of the doped germanosilicate glass so treated.

9. A method according to claim 8 wherein the forming step comprises the step of forming a layer of boron doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 77% and about 83% and mole percentage of boron of about 3% relative to the total.

10. A method of forming a layer on a substrate comprising the steps of:

forming a layer of phosphorous doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 60% and about 85% and mole percentage of phosphorous of between about 14% and about 44% relative to the total on a substrate; and

thermally treating the layer of doped germanosilicate glass in steam to remove at least one of germanium and dopant from the germanosilicate glass and thereby raise the reflow temperature of the doped germanosilicate glass so treated.

11. A method according to claim 10 wherein the forming step comprises the step of forming a layer of phosphorous doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 60% and about 85% and mole percentage of phosphorous of about 14% relative to the total.

12. A method of forming a layer on a substrate comprising the steps of:

forming a layer of boron and phosphorus doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 40% and about 85%, mole percentage of boron of between about 1% and about 4% relative to the total, and mole percentage of phosphorus of between about 5% and about 23% relative to the total on the substrate; and

thermally treating the layer of doped germanosilicate glass in steam to remove at least one of germanium and dopant from the germanosilicate glass and thereby raise the reflow temperature of the doped germanosilicate glass so treated.

13. A method according to claim 12 wherein the forming step comprises the step of forming a layer of boron and phosphorus doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 82% and about 85%, mole percentage of boron of between about 1% and about 3% relative to the total, and mole percentage of phosphorus of between about 11% and about 14% relative to the total.

14. A method of forming a plurality of germanosilicate glass layers on a substrate, comprising the steps of:

forming a layer of germanosilicate glass on a substrate;

thermally treating the layer of germanosilicate glass in steam to remove germanium from the germanosilicate glass and thereby raise the reflow temperature of the germanosilicate glass so treated; and

repeating the steps of forming and thermally treating to thereby create a hierarchy of thermally treated germanosilicate glass layers on the substrate, wherein each thermally treated germanosilicate glass layer has higher reflow temperature than the corresponding layer of germanosilicate glass as formed.

15. A method according to claim 14 wherein each of the repeated forming and thermally treating steps are performed under same conditions.

16. A method according to claim 14 wherein at least two of the repeated thermally treating steps are performed under differing thermal conditions.

17. A method according to claim 14:

wherein the thermally treating step is preceded by the step of thermally pretreating the layer of germanosilicate glass in at least one of a noble gas and nitrogen gas to reflow the layer of germanosilicate glass; and

wherein the repeating step comprises the steps of repeating the steps of forming, thermally pretreating and thermally treating to thereby create a plurality of thermally treated reflowed germanosilicate glass layers on the substrate, wherein each thermally treated reflowed germanosilicate glass layer has higher reflow temperature than the corresponding layer of germanosilicate glass as formed.

18. A method according to claim 17:

wherein the forming step comprises the step of forming a nonplanar layer of germanosilicate glass on a substrate;

wherein the thermally pretreating step comprises the step of thermally pretreating the nonplanar layer of germanosilicate glass in at least one of a noble gas and nitrogen gas to reflow the nonplanar layer of germanosilicate glass and partially planarize the nonplanar layer of germanosilicate glass; and

wherein the thermally treating step comprises the step of thermally treating the partially planarized layer of germanosilicate glass in steam to remove germanium from the partially planarized germanosilicate glass and to fully planarize the partially planarized germanosilicate glass.

19. A method according to claim 17:

wherein the forming step comprises the step of forming a nonplanar layer of germanosilicate glass on a substrate;

wherein the thermally pretreating step comprises the step of thermally pretreating the nonplanar layer of germanosilicate glass in at least one of a noble gas and nitrogen gas to reflow the nonplanar layer of germanosilicate glass and fully planarize the nonplanar layer of germanosilicate glass; and

wherein the thermally treating step comprises the step of thermally treating the fully planarized layer of germanosilicate glass in steam to remove germanium from the fully planarized germanosilicate glass.

20. A method according to claim 14 wherein the forming step comprises the step of forming a layer of germanosilicate glass on a substrate using Plasma Enhanced Chemical Vapor Deposition (PECVD) at about 200°

C.

21. A method according to claim 14 wherein the forming step comprises the step of forming a layer of germanosilicate glass having mole percentage of germanium dioxide of between about 60% and about 85%.

22. A method according to claim 14 wherein the forming step comprises the step of forming a layer of germanosilicate glass having mole percentage of germanium dioxide of between about 77% and about 83%.

23. A method according to claim 14:

wherein the forming step comprises the step of forming a layer of doped germanosilicate glass on a substrate, the doped germanosilicate glass having lower reflow temperature than undoped germanosilicate glass; and

wherein the thermally treating step comprises the step of thermally treating the layer of doped germanosilicate glass in steam to remove at least one of germanium and dopant from the germanosilicate glass and thereby raise the reflow temperature of the doped germanosilicate glass so treated.

24. A method according to claim 23 wherein the forming step comprises the step of forming a layer of boron doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 40% and about 85% and mole percentage of boron of between about 1% and about 4% relative to the total.

25. A method according to claim 23 wherein the forming step comprises the step of forming a layer of boron doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 77% and about 83% and mole percentage of boron of about 3% relative to the total.

26. A method according to claim 23 wherein the forming step comprises the step of forming a layer of phosphorous doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 60% and about 85% and mole percentage of phosphorous of about 14% and about 44% relative to the total.

27. A method according to claim 23 wherein the forming step comprises the step of forming a layer of phosphorous doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 60% and about 85% and mole percentage of phosphorous of about 14% relative to the total.

28. A method according to claim 23 wherein the forming step comprises the step of forming a layer of boron and phosphorus doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 40% and about 85%, mole percentage of boron of between about 1% and about 4% relative to the total, and mole percentage of phosphorus of between about 5% and about 23% relative to the total.

29. A method according to claim 23 wherein the forming step comprises the step of forming a layer of boron and phosphorus doped germanosilicate glass having mole percentage of germanium dioxide relative to silicon dioxide of between about 82% and about 85%, mole percentage of boron of between about 1% and about 3% relative to the total, and mole percentage of phosphorus of between about 11% and about 14% relative to the total.

30. A method according to claim 14:

wherein the thermally treating step is followed by the step of forming a conductive layer on the thermally treated layer of germanosilicate glass; and

wherein the repeating step comprises the step of repeating the steps of forming a layer of germanosilicate glass, thermally treating and forming a conductive layer to thereby create a hierarchy of thermally treated germanosilicate glass layers on the substrate, that are separated by conductive layers, wherein each thermally treated germanosilicate glass layer has higher reflow temperature than the corresponding layer of germanosilicate glass as formed.

31. A method of forming a plurality layers on a substrate, comprising the steps of:

forming a layer of glass on a substrate, the glass including at least two compounds in solid solution, one of which is volatilized by steam;

thermally treating the layer of glass in steam to remove at least some of the compound which is volatilized by steam from the glass and thereby raise the reflow temperature of the glass so treated; and

repeating the steps of forming and thermally treating to thereby create a hierarchy of thermally treated glass layers on the substrate, wherein each thermally treated glass layer has higher reflow temperature than the corresponding layer of glass as formed.

32. A method according to claim 31 wherein each of the repeated forming and thermally treating steps are performed under same conditions.

33. A method according to claim 31 wherein at least two of the repeated thermally treating steps are performed under differing thermal conditions.

34. A method according to claim 31:

wherein the thermally treating step is followed by the step of forming a conductive layer on the thermally treated layer of glass; and

wherein the repeating step comprises the step of repeating the steps of forming a layer of glass, thermally treating and forming a conductive layer to thereby create a plurality of thermally treated glass layers on the substrate, that are separated by conductive layers, wherein each thermally treated glass layer has higher reflow temperature than the corresponding layer of glass as formed.

35. A method according to claim 31 wherein a first one of the thermally treated glass layers has higher dielectric constant than a second one of the thermally treated glass layers.

36. A method according to claim 35 wherein the first one of the thermally treated glass layers comprises at least one of germanotitanate and germanostannate glass and wherein the second one of the thermally treated glass layers comprises germanosilicate glass.

37. A method of forming a layer on a substrate comprising the steps of:

forming a layer of germanium-containing glass on a substrate;

thermally pretreating the layer of germanium-containing glass in at least one of a noble gas and nitrogen gas to reflow the layer of germanium-containing glass and then

thermally treating the layer of germanium-containing glass in steam to remove germanium from the germanium-containing glass and thereby raise the reflow temperature of the germanium-containing glass so treated.

38. A method according to claim 37:

wherein the forming step comprises the step of forming a nonplanar layer of germanium-containing glass on a substrate;

wherein the thermally pretreating step comprises the step of thermally pretreating the nonplanar layer of germanium-containing glass in at least one of a noble gas and nitrogen gas to reflow the nonplanar layer of germanium-containing glass and partially planarize the nonplanar layer of germanium-containing glass; and

wherein the thermally treating step comprises the step of thermally treating the partially planarized layer of germanium-containing glass in steam to remove germanium from the partially planarized germanium-containing glass and to fully planarize the partially planarized germanium-containing glass.

39. A method according to claim 37:

wherein the forming step comprises the step of forming a nonplanar layer of germanium-containing glass on a substrate;

wherein the thermally pretreating step comprises the step of thermally pretreating the nonplanar layer of germanium-containing glass in at least one of a noble gas and nitrogen gas to reflow the nonplanar layer of germanium-containing glass and fully planarize the nonplanar layer of germanium-containing glass; and

wherein the thermally treating step comprises the step of thermally treating the fully planarized layer of germanium-containing glass in steam to remove germanium from the fully planarized germanium-containing glass.

41. A method according to claim 37 wherein the forming step comprises the step of lining a trench in the substrate with a layer of germanium-containing glass.

42. A method according to claim 37 wherein the thermally treating step is followed by the step of forming a contact on the layer of thermally treated germanium-containing glass, opposite the substrate, to thereby form a capacitor.

44. A method according to claim 41 wherein the thermally treating step is followed by the step of:

forming a contact on the layer of thermally treated germanium-containing glass in the trench, opposite the substrate, to thereby form a capacitor.

40. A method of forming a layer on a substrate comprising the steps of:

forming a layer of germanium-containing glass on a substrate; and

thermally treating the layer of germanium-containing glass in steam to remove germanium from the germanium-containing glass and thereby raise the reflow temperature of the germanium-containing glass so treated;

wherein the germanium-containing glass comprises at least one of germanotitanate glass and germanostannate glass.

43. A method according to claim 40 wherein the thermally treating step is followed by the step of forming a contact on the layer of thermally treated germanium-containing glass, opposite the substrate, to thereby form a capacitor.