Claims
- 1. A co-polymer dielectric thin film prepared by transport co-polymerization (“TCP”) of a first reactive intermediate with a second reactive intermediate, the first reactive intermediate is formed from a first co-precursor, and wherein a second reactive intermediate is formed from a second co-precursor;
the first co-precursor having a general structure as in (VI): 12wherein,
Ar is an aromatic or a fluorinated-aromatic group moiety; no or m are individually zero or a first integer, and (no+m) comprises an added integer of at least 2 but no more than a total number of sp2C substitution on the Ar; X′ and X″ are similar or different, and individually a hydrogen, a fluorine, an alkyl group, a fluorinated alkyl group, a phenyl group, or a fluorinated phenyl group; Y is a leaving group, and individually a —Cl, —Br, —I, —NR2, —N+R3, —SR, —SO2R, or —OR, wherein R is an alkyl, a fluorinated alkyl, aromatic, or fluorinated aromatic group; Z′ similar or different, and individually H or F; and the second co-precursor is a cage compound, fullerene, methylsilsequioxane, hydrosilsesquioxane, anadamantanyl, a cyclic compound, or a 2,2,-paracyclophane; and wherein, the TCP is performed under a vacuum with a low system-leakage-rate, an inert atmosphere, or both.
- 2. The co-polymer dielectric thin film of claim 1, wherein the second co-precursor comprises a 2,2,-paracyclophanes with a general structure (VII):
- 3. The co-polymer dielectric thin film of claim 1, wherein no of the first co-precursor equals 2, and the first reactive intermediate comprises the general structure (XV):
- 4. The co-polymer dielectric thin film of claim 1, wherein the second reactive intermediate comprises the general structure (XVI):
- 5. The co-polymer dielectric thin film of claim 1, wherein the co-polymer dielectric thin film comprises a co-Poly(Para-Xylylene) (“co-PPX”) having a general structure of (XVII):
- 6. The co-polymer dielectric thin film of claim 1, wherein the co-polymer dielectric thin film comprises a co-Poly(Para-Xylylene) (“co-PPX”) having a general structure of (XVII):
- 7. The co-polymer dielectric thin film of claim 1, wherein the aromatic or the fluorinated-aromatic group moiety Ar is selected from the group consisting of C6H4-nFn (n=0 to 4), CIOH6-nFn (n=0 to 6), C12H8-nFn (n=0 to 8), C14H8-nFn (n=0 to 8), C16H8-nFn (n=0 to 8), and C16H10-nFn (n=0 to 10).
- 8. The co-polymer dielectric thin film of claim 1, wherein the co-polymer dielectric thin film further comprise a melting temperature; a reversible crystal transformation temperature; an irreversible crystal transformation temperature; and a glass transition temperature, and wherein the melting temperature is greater than the reversible crystal transformation temperature, the reversible crystal transformation temperature is greater than the irreversible crystal transformation temperature, and the irreversible crystal transformation temperature is greater than the glass transition temperature.
- 9. The co-polymer dielectric thin film of claim 1, wherein the co-polymer dielectric thin film is a co-Poly(Para-Xylylene) (“Co-PPX”) having repeating-units selected from the group consisting of ((—CH2—C6H4—H2C—)a(—CF2—C6H4—F2C—)b)noo, ((—CF2—C6F4—F2C—)a —(CH2—C6F4—H2C—)b)noo, ((—CF2—C6H2F2—F2C—)a (—CF2—C6F4—H2C—)b)noo, wherein, “a” is an integer that ranges from 3 to 10; “b” is an integer that ranges from 20 to 100; and noo is an integer of at least 10.
- 10. The co-polymer dielectric thin film of claim 9, wherein a major composition of the co-PPX is a PPX-F and its derivatives, having a major repeating unit comprising (—CF2—C6Z4—F2C—), wherein Z is H or F.
- 11. The co-polymer dielectric thin film of claim 10, wherein the PPX-F content ranging from 65 to 95%.
- 12. The co-polymer dielectric thin film of claim 10, wherein the PPX-F content ranging from 75 to 90%.
- 13. The co-polymer dielectric thin film of claim 9, wherein aminor composition of the co-PPX is a PPX-N and its derivatives, having aminor repeating unit comprising (—CH2—C6Z4—H2C—) wherein Z is H or F.
- 14. The co-polymer dielectric thin film of claim 1 is transparent and semicrystalline.
- 15. A method of preparing a co-polymer dielectric thin film for fabricating integrated circuits (“IC”), comprising the step of co-polymerizing a first reactive intermediate from a first co-precursor and a second reactive intermediate from a second co-precursor on a substrate;
the first co-precursor having a general structure as in (VI): 16wherein,
Ar is an aromatic or a fluorinated-aromatic group moiety; no or m are individually zero or a first integer, and (no+m) comprises an added integer of at least 2 but no more than a total number of sp2C substitution on the Ar; X′ and X″ are similar or different, and individually a hydrogen, a fluorine, an alkyl group, a fluorinated alkyl group, a phenyl group, or a fluorinated phenyl group; Y is a leaving group, and individually a —Cl, —Br, —I, —NR2, —N+R3, —SR, —SO2R, or —OR, wherein R is an alkyl, a fluorinated alkyl, aromatic, or fluorinated aromatic group; Z and Z′ are individually H or F; and the second co-precursor is a cage compound, fullerene, methylsilsequioxane, hydrosilsesquioxane, anadamantanyl, a cyclic compound, or a 2,2,-paracyclophane; and wherein, the TCP dielectric thin film is prepared from under a vacuum with a low system-leakage-rate, an inert atmosphere, or both; and the TCP is performed at a temperature equal to or below a melting temperature of the first reactive intermediate.
- 16. The method of claim 15, wherein the second co-precursor comprises a 2,2,-paracyclophanes with a general structure (VII):
- 17. The method of claim 15, wherein no of the first co-precursor equals 2, and the first reactive intermediate having the general structure of (XV) is generated:
- 18. The method claim 15, wherein the second reactive intermediate having the general structure of (XVI) is generated:
- 19. The method of claim 15, wherein the co-polymer dielectric thin film comprises a co-Poly(Para-Xylylene) (“co-PPX”) having a general structure of (XVII):
- 20. The method of claim 15, wherein the co-polymer dielectric thin film comprises a co-Poly(Para-Xylylene) (“co-PPX”) having a general structure of (XVII):
- 21. The method of claim 15, wherein the aromatic or the fluorinated-aromatic group moiety Ar is selected from the group consisting of C6H4-nFn (n=0 to 4), C10H6-nFn (n=0 to 6), C12H8-nFn (n=0 to 8), C14H8-nFn (n=0 to 8), C16H8-nFn (n=0 to 8), and C16H10-nFn (n=0 to 10).
- 22. The method of claim 15, wherein the co-polymer dielectric thin film has a melting temperature; a reversible crystal transformation temperature; an irreversible crystal transformation temperature; and a glass transition temperature, and wherein the melting temperature is greater than the reversible crystal transformation temperature, the reversible crystal transformation temperature is greater than the irreversible crystal transformation temperature, and the irreversible crystal transformation temperature is greater than the glass transition temperature.
- 23. The method of claim 15, wherein the co-polymer dielectric thin film is a co-Poly(Para-Xylylene) (“Co-PPX”) having repeating-units selected from the group consisting of ((—CH2—C6H4—H2C—)a(—CF2—C6H4—F2C—)b)noo, ((—CF2—C6F4—F2C—)a —(CH2—C6F4—H2C—)b)noo, ((—CF2—C6H2F2—F2C—)a (—CF2—C6F4—H2C—)b)noo, wherein, “a” is an integer that ranges from 3 to 10; “b” is an integer that ranges from 20 to 100; and noo is an integer of at least 10.
- 24. The method of claim 23, wherein a major composition of the co-PPX is a PPX-F and its derivatives, having a major repeating unit comprising (—CF2—C6Z4—F2C—), wherein Z is H or F.
- 25. The method of claim 24, wherein the PPX-F content ranging from 65 to 95%.
- 26. The method of claim 24, wherein the PPX-F content ranging from 75 to 90%.
- 27. The method of claim 21, wherein aminor composition of the co-PPX is a PPX-N and its derivatives, having aminor repeating unit comprising (—CH2—C6Z4—H2C—) wherein Z is H or F.
- 28. The method of claim 15, wherein the Co-PPX film is transparent and semicrystalline.
- 29. The method of claim 15, wherein the Co-PPX film is ((—CH2—C6H4—H2C—)a(—CF2—C6H4—F2C—)b)noo, wherein, “a” is an integer that ranges from 3 to 10; “b” is an integer that ranges from 20 to 100; and noo is an integer of at least 10.
- 30. The method of claim 15, wherein the Co-PPX film is ((—CF2—C6F4—F2C—)a —(CH2—C6F4—H2C—)b)noo, wherein, “a” is an integer that ranges from 3 to 10; “b” is an integer that ranges from 20 to 100; and noo is an integer of at least 10.
- 31. The method of claim 15, wherein the Co-PPX film is ((—CF2—C6H2F2—F2C—)a (—CF2—C6F4—H2C—)b)noo, wherein, “a” is an integer that ranges from 3 to 10; “b” is an integer that ranges from 20 to 100; and noo is an integer of at least 10.
- 32. The method of claim 15, wherein the substrate temperature is below −30° C.
- 33. The method of claim 15, further comprising a feed rate for the first reactive intermediate and the second reactive intermediate of transport co-polymerization, the feed rate is below 0.2 mMol/minute for a 200 mm wafer
- 34. A method of stabilizing an as-deposited co-polymer dielectric thin film, comprising:
(a) heating the as-deposited co-polymer dielectric thin film under a vacuum, a reductive atmosphere, or both to give a heated-as-deposited dielectric thin film; (b) maintaining the heated-as-deposited co-polymer dielectric thin film at an isothermal temperature for a period of time to give an isothermal-heated-as-deposited co-polymer dielectric thin film; and (c) cooling the isothermal-heated-as-deposited co-polymer dielectric thin film to a cooling-temperature to give a stabilized-as-deposited thin film; wherein the as-deposited co-polymer dielectric thin film has a melting temperature, a reversible crystal transformation temperature, an irreversible crystal transformation temperature, and a glass transition temperature, and wherein the melting temperature is greater than the reversible crystal transformation temperature, the reversible crystal transformation temperature is greater than the irreversible crystal transformation temperature, and the irreversible crystal transformation temperature is greater than the glass transition temperature.
- 35. The method of claim 34, wherein heating the as-deposited co-polymer dielectric thin film occurs at a temperature between 200 to 50° C. below the reversible crystal transformation temperature and 20° to 50° C. below the melting temperature.
- 36. The method of claim 34, wherein the period of time is in a range of about 1 to 120 minutes.
- 37. The method of claim 34, wherein cooling the isothermal-heated-as-deposited co-polymer dielectric thin film occurs at a rate of about 30° to 100° C. per minute to a temperature of about 20° to 50° C. below the reversible crystal transformation temperature.
- 38. The method of claim 37, wherein the reductive atmosphere comprises hydrogen in a noble gas.
- 39. The method of claim 38, wherein the presence of hydrogen in the noble gas comprises at least 0.1% volume of hydrogen in a argon.
- 40. The method of claim 38, wherein the presence of hydrogen in the noble gas comprises at least 3% volume of hydrogen in a argon.
- 41. The method of claim 37, wherein the cooling of the isothermal-heated-as-deposited co-polymer dielectric thin film is at a rate of 50° to 100° C. per minute.
- 42. The method of claim 34, wherein the reductive-annealing is conducted before removing the stabilized-as-deposited co-polymer dielectric thin film from a deposition system.
- 43. The method of claim 34, further comprising the as-deposited co-polymer dielectric thin film reaching a fabrication-temperature equal to or higher than a maximum temperature (“Tmaxi”) of the as-deposited co-polymer dielectric thin film for a fabrication-time period between 10 and 60 minutes during fabrication of an integrated circuit (“IC”), wherein the as-deposited co-polymer dielectric thin film is used in the fabrication of the IC.
- 44. The method of claim 43, wherein the maximum temperature (“Tmax1”) of the as-deposited co-polymer dielectric thin film is equal or less than the reversible crystal transformation temperature (“T2”).
- 45. A method of re-stabilizing an as-deposited etched-co-polymer dielectric thin film that was subjected to a reactive-plasma-etching-process, the method comprising:
(a) treating the etched-co-polymer dielectric thin film under an atmosphere with a non-oxidative plasma to form a treated-etched-dielectric thin film; (b) reductive-annealing the treated-etched-co-polymer dielectric thin film under a reducing atmosphere at a temperature in the range between −50 to +50° C. of a reversible crystal transformation temperature to form a reduced-etched-dielectric thin film; (c) maintaining the reduced-etched-co-polymer dielectric thin film at an isothermal temperature for a predetermined period of time to form an isothermal-reduced-etched-dielectric thin film; and (d) cooling the isothermal-reduced-etched-co-polymer dielectric thin film surface to temperatures at least 20 to 50° C. below a reversible crystal transformation temperature of the co-polymer film to form a re-stabilized-etched-dielectric thin film; wherein, a melting temperature of the as-deposited etched-co-polymer dielectric is greater than the reversible crystal transformation temperature, the reversible crystal transformation temperature is greater than an irreversible crystal transformation temperature, and the irreversible crystal transformation temperature is greater than a glass transition temperature for the as-deposited etched-co-polymer dielectric.
- 46. The method of claim 45, wherein the reactive-plasma-etching-process occurred under a reactive-atmosphere comprising nitrogen.
- 47. The method of claim 45, wherein the reactive-plasma-etching-process occurred under a reactive-atmosphere comprising oxygen.
- 48. The method of claim 45, wherein treating the etched-co-polymer dielectric thin film to the non-reactive plasma occurs in the presence of a noble gas.
- 49. The method of claim 48, wherein the noble gas is argon.
- 50. The method of claim 45, wherein the non-oxidative plasma is performed at a discharge power of about 10 to 100 Watts for a time period between 2 to 50 minutes.
- 51. The method of claim 45, wherein the non-oxidative plasma is performed at a discharge power of about 30 to 70 Watts for a time period between 5 to 30 minutes.
- 52. The method of claim 45, wherein reductive annealing is performed in the presence of a reductive gas sufficient to reduce an oxygenated sp2C and HC-sp3C bonds to sp2C—Z and HC-sp3Cα—X, wherein Z and X is H or F.
- 53. The method of claim 52, wherein the reductive gas comprises 1 to 10% hydrogen in argon.
- 54. The method of claim 52, wherein the reductive gas comprises 3 to 5% hydrogen in argon.
- 55. The method of claim 52, wherein the reductive gas comprises 1 to 10% fluorine in argon.
- 56. The method of claim 52, wherein the reductive gas comprises 3 to 5% fluorine in argon.
- 57. A stabilized co-polymer dielectric thin film comprising the co-polymer dielectric thin film prepared by transport co-polymerization of claim 1, and stabilized by the method comprising:
(a) heating the co-polymer dielectric thin film under a vacuum, a reductive atmosphere, or both to give a heated-as-deposited dielectric thin film; (b) maintaining the heated-as-deposited co-polymer dielectric thin film at an isothermal temperature for a period of time to give an isothermal-heated-as-deposited co-polymer dielectric thin film; and (c) cooling the isothermal-heated-as-deposited co-polymer dielectric thin film to a cooling-temperature to give a stabilized co-polymer dielectric thin film; wherein the co-polymer dielectric thin film has a melting temperature, a reversible crystal transformation temperature, an irreversible crystal transformation temperature, and a glass transition temperature, and wherein the melting temperature is greater than the reversible crystal transformation temperature, the reversible crystal transformation temperature is greater than the irreversible crystal transformation temperature, and the irreversible crystal transformation temperature is greater than the glass transition temperature.
- 58. A method of building a Damascene structure on the stabilized co-polymer dielectric thin film of claim 57 comprising:
(a) patterning a via in the stabilized-as-deposited co-polymer film by reactive-plasma etching to give an etched-stabilized-as-deposited-co-polymer dielectric thin film; (b) cleaning the etched-stabilized-as-deposited-co-polymer dielectric thin film with a wet chemical to give a clean-etched-stabilized-co-polymer dielectric thin film; (c) roughening a surface of the clean-etched-stabilized co-polymer dielectric thin film with a non-reactive plasma to form a rough-etched-as-deposited-co-polymer dielectric thin film useful for further coating; and (d) reductive-annealing the rough-etched-as-deposited-co-polymer dielectric thin film under a reducing atmosphere at a temperature in a range between −50 to +50° C. of a reversible crystal transformation temperature to give the Damascene structure on the stabilized-as-deposited co-polymer dielectric thin film.
- 59. The method of claim 58, wherein the reactive-plasma-etching-process occurred under a reactive-atmosphere comprising nitrogen.
- 60. The method of claim 58, wherein the reactive-plasma-etching-process occurred under a reactive-atmosphere comprising oxygen.
- 61. The method of claim 58, wherein treating the etched-stabilized co-polymer dielectric thin film to the non-reactive plasma occurs in the presence of a noble gas.
- 62. The method of claim 61, wherein the noble gas is argon.
- 63. The method of claim 62, wherein the argon has 20 to 2000 mTorrs of pressure.
- 64. The method of claim 62, wherein the argon has 50 to 500 mTorrs of pressure.
- 65. The method of claim 58, wherein the non-reactive plasma is performed at a discharge power of about 0.1 to 1.0 W/cm2 for a time period between 2 to 50 minutes.
- 66. The method of claim 58, wherein the non-reactive plasma is performed at a discharge power of about 0.04 to 0.4 W/cm2 for a time period between 5 to 30 minutes.
- 67. The method of claim 58, wherein reductive annealing is performed in the presence of a reductive gas sufficient to reduce an oxygenated sp2C and HC-sp3C bonds to sp2C—Z and HC-sp3Cα—X, wherein Z and X is H or F.
- 68. The method of claim 67, wherein the reductive gas comprises 1 to 10% hydrogen in argon.
- 69. The method of claim 67, wherein the reductive gas comprises 3 to 5% hydrogen in argon.
- 70. The method of claim 67, wherein the reductive gas comprises 1 to 10% fluorine in argon.
- 71. The method of claim 67, wherein the reductive gas comprises 3 to 5% fluorine in argon.
- 72. A method of building a Damascene structure on the stabilized co-polymer dielectric thin film of claim 57 comprising:
(a) patterning a via in the co-polymer film by reductive-plasma etching of an underlying stabilized dielectric thin film to give an etched-stabilized-as-deposited dielectric thin film; (b) cleaning the etched-stabilized dielectric thin film with a wet chemical to give a clean-etched-stabilized dielectric thin film; (c) roughening a surface of the clean-etched-stabilized dielectric thin film with a non-reactive plasma as an option, wherein the non-reactive plasma depletes oxidized surface groups and roughens the surface of the etched-stabilized dielectric thin film to give a rough-etched-as-deposited dielectric thin film useful for further coating.
- 73. The method of claim 72, wherein the reductive-plasma-etching-process occurred under a reductive-atmosphere comprising hydrogen in a noble gas.
RELATED APPLICATIONS
[0001] This application is a continuation-in-part of the Lee, et al., U.S. patent application, Ser. No. 10/126,919, entitled “Process Modules for Transport Polymerization of Low ε Thin Films,” and filed on Apr. 19, 2002. The Ser. No. 10/126,919 application is a continuation-in-part of the Lee, et al., U.S. patent application, Ser. No. 10/125,626, entitled “Multi-Stage-Heating Thermal Reactor for Transport Polymerization,” and filed on Apr. 17, 2002. The Ser. No. 10/125,626 application is a continuation-in-part of the Lee, et al., U.S. patent application, Ser. No. 10/115,879, entitled “UV Reactor for Transport Polymerization,” and filed on Apr. 4, 2002. The Ser. No. 10/115,879 application is a continuation-in-part of the Lee, et al., U.S. patent application, Ser. No. 10/116,724, entitled “Chemically and Electrically Stabilized Polymer Films,” and filed on Apr. 4, 2002. The Ser. No. 10/116,724 application is a continuation-in-part of the Lee, et al., U.S. patent application, Ser. No. 10/029,373, entitled “Dielectric Thin Films from Fluorinated Benzocyclobutane Precursors,” and filed on Dec. 19, 2001. The Ser. No. 10/029,373 application is a continuation-in-part of the Lee, et al., U.S. patent application, Ser. No. 10/028,198, entitled “Dielectric Thin Films from Fluorinated Precursors,” and filed on Dec. 19, 2001. The Ser. No. 10/028,198 application is a continuation-in-part of the Lee, et al., U.S. patent application Ser. No. 09/925,712, entitled “Stabilized Polymer Film and its Manufacture,” and filed on Aug. 9, 2001. The Ser. No. 09/925,712 application is a continuation-in-part of the Lee, et al., U.S. patent application Ser. No. 09/795,217, entitled “Integration of Low E Thin films and Ta into Cu Dual Damascene,” and filed on Feb. 26, 2001. The entirety of each of the applications or patents listed above is hereby specifically incorporated by reference.
Continuation in Parts (8)
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