Polyparaxylylene film, production method therefor and semiconductor device

• US 20050014388A1
• Filed: 07/22/2002
• Published: 01/20/2005
• Est. Priority Date: 07/27/2001
• Status: Active Grant

• Current Assignee: Hitachi, Ltd.
• Original Assignee: Hitachi, Ltd.
• Inventors: Takahashi, Akio, Nakai, Harakazu, Chvalun, Sergei Nicolaevich, Pebalk, Andrei Vladimirovich, Nakai, Yoshiko, Kardash, Igor Yefimovich, Satsu, Yuichi, Mailyan, Karen Andranikovich
• Granted Patent: US 6,946,405 B2
• Time in Patent Office: Days
• US Class Current: 438/780
• CPC Class Codes: C08G 61/02 Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• CPC Class Codes: C08J 2365/04 Polyxylylenes
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08L 65/04 Polyxylenes
• CPC Class Codes: H01L 21/02118 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC polymers per se C08G, photoresist per se G03F
• CPC Class Codes: H01L 21/0212 the material being fluoro carbon compounds, e.g.(CFx) n, (CHxFy) n or polytetrafluoroethylene
• 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 21/02203 the layer being porous
• CPC Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/312 Organic layers, e.g. photoresist H01L21/3105, H01L21/32 take precedence; photoresists per se G03C
• CPC Class Codes: H01L 21/3127 Layers comprising fluoro (hydro)carbon compounds, e.g. polytetrafluoroethylene
• CPC Class Codes: H01L 21/7682 the dielectric comprising air gaps
• CPC Class Codes: H05K 3/4676 Single layer compositions
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer

Abstract

An organic polymer film of low dielectric constant and high heating resistance which is applicable as an insulating layer of a semiconductor devices is provided, as well as a manufacturing method for the film and a semiconductor device incorporating the film.

Claims

1-16. -16. (Canceled)

17. A film of porous poly-paraxylylene or a derivative thereof prepared by the process comprising:

subliming paraxylylene or a derivative cyclic dimer;

pyrolyzing the resulting product at 800 to 950°

C.;

polymerizing the product obtained by pyrolysis; and

heat-treating the resulting polymer.

18. A film of porous poly-paraxylylene or a derivative thereof in accordance with claim 17, wherein said film contains a porous structure of 10 to 50% by volume.

19. A method of manufacturing a film of porous poly-paraxylylene or a derivative thereof, comprising

subliming paraxylylene or a derivative cyclic dimer at 30 to 160°

C.;

pyrolyzing the resulting product at 800 to 950°

C.;

polymerizing the product obtained by pyrolysis at −

40 to +25°

C.; and

heat-treating the resulting polymer.

20. The method of manufacturing a film poly-paraxylylene or a derivative thereof in accordance with claim 19, wherein said sublimation, pyrolysis, and polymerization processes are performed at a vacuum pressure of 0.001 to 0.1 mmHg.

21. The method of manufacturing a film of poly-paraxylylene or a derivative thereof in accordance with claim 19, wherein the heat-treating process comprises alternately heating to increase the temperature and heating to maintain the temperature in a stepwise manner, wherein a final heating is made at 390 to 410°

C.

22. The method of manufacturing a film of poly-paraxylylene or a derivative thereof in accordance with claim 19, wherein the heat-treating process is performed at a vacuum pressure of 0.001 to 0.1 mmHg or in an inactive gas atmosphere.

23. The method of manufacturing a film of poly-paraxylylene or a derivative thereof in accordance with claim 19, wherein the heat-treating process comprises heating to increase the temperature to 170 to 220°

C. at a heating rate of 4°

C./minute or less, heating to maintain the temperature for at least 35 minutes at 170 to 220°

C., heating to increase the temperature to 350 to 390°

C. at a rate of 0.5°

C./minute or less, heating to maintain the temperature for at least 70 minutes at 350 to 390°

C., heating to increase the temperature to 390 to 410°

C. at a rate of 0.5°

C./minute or less, and heating to maintain the temperature for at least 70 minutes at 390 to 410°

C.

24. The method of manufacturing a film of poly-paraxylylene or a derivative film thereof in accordance with claim 23, wherein the heat-treating process comprises heating to increase the temperature to 190 to 210°

C. at a rate of 4°

C./minute or less, heating to maintain the temperature for at least 35 minutes at 190 to 210°

C., heating to increase the temperature to 370 to 380°

C. at a rate of 0.5°

C./minute or less, heating to maintain the temperature for at least 70 minutes at 370 to 380°

C., heating to increase the temperature to 390 to 410°

C. at a rate of 0.5°

C./minute or less, and heating to maintain the temperature for at least 70 minutes at 390 to 410°

C.

30. A semiconductor device whose semiconductor elements are electrically connected to thin-film wirings formed on an insulating film, wherein said insulating film is a poly-paraxylylene and its derivative film which is prepared by the method of claim 19 and contains a porous structure therein.

31. A semiconductor device in accordance with claim 30, wherein said film contains a porous structure of 25 to 50% by volume.

32. A multi-layer wiring substrate comprising laminate wiring layers having a conductive circuit on at least one side of an insulating base with an insulating layer therebetween, wherein at least one of said insulating base and said insulating layer is a film of poly-paraxylylene or a derivative thereof which is prepared by the method of claim 19 and contains a porous structure therein.

25. A film of porous poly-paraxylylene or a derivative thereof prepared by the process comprising:

subliming paraxylylene or a derivative cyclic dimer at 30 to 160°

C.;

pyrolyzing the resulting product at 800 to 950°

C.;

polymerizing the product obtained by pyrolysis at −

40 to +25°

C.; and

heat-treating the resulting polymer,

wherein the polymer is removed from a polymerization tank and heat-treated after said polymerization process.

26. A semiconductor device comprising semiconductor elements electrically connected to thin-film wirings formed on an insulating film, wherein said insulating film comprises porous poly-paraxylylene or a derivative thereof prepared by subliming paraxylylene or a derivative cyclic dimer, pyrolyzing the resulting product at 800 to 950°

C., polymerizing the product obtained by pyrolysis, and heat-treating the resulting polymer.

27. A semiconductor device in accordance with claim 26, wherein said insulating film comprises a fluorinated poly-paraxylylene film prepared by subliming a cyclophane compound, pyrolyzing said compound into paraxylylene monomer at 800 to 950°

C., polymerizing said paraxylylene monomer into poly-paraxylylene precipitate, and heat-treating the precipitate.

28. A semiconductor device in accordance with claim 26, wherein said heat-treating comprises alternately heating to increase the temperature and heating to maintain the temperature in a stepwise manner, wherein a final heating is made at 390 to 410°

C.

29. A semiconductor device in accordance with claim 26, wherein said insulating film is prepared by a method comprising:

subliming paraxylylene or a derivative cyclic dimer at 30 to 160°

C.;

pyrolyzing the resulting product at 800 to 950°

C.;

polymerizing the product obtained by pyrolysis at −

40 to +25°

C.; and

heat-treating the resulting polymer.