Surface modification of CVD polymer films

• US 20050227055A1
• Filed: 02/18/2005
• Published: 10/13/2005
• Est. Priority Date: 08/19/2002
• Status: Active Grant

• Current Assignee: Rensselaer Polytechnic Institute
• Original Assignee: Rensselaer Polytechnic Institute
• Inventors: Lu, Toh-Ming, Yang, Guangrong, Senkevich, John Joseph
• Granted Patent: US 7,501,154 B2
• Time in Patent Office: Days
• US Class Current: 428/214
• CPC Class Codes: B05D 1/60 Deposition of organic layers from vapour phase vapour phase deposition in general C23C14/00, C23C16/00
• CPC Class Codes: C08G 2261/3424 non-conjugated, e.g. paracyclophanes or xylenes
• CPC Class Codes: C08G 61/025 Polyxylylenes
• CPC Class Codes: C09D 165/00 Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C09D107/00 - C09D157/00, C09D161/00 take precedence; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 165/04 Polyxylylenes
• 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 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/312 Organic layers, e.g. photoresist H01L21/3105, H01L21/32 take precedence; photoresists per se G03C
• CPC Class Codes: H01L 21/76828 thermal treatment
• CPC Class Codes: H01L 21/76829 characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
• CPC Class Codes: Y10T 428/24959 of adhesive layers
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

The present invention relates to a method for forming a conformal coating having a reactive surface. In the method, an ultrathin layer composed of a polymer having repeating units derived from unsubstituted p-xylylene, substituted p-xylylene, phenylene vinylene, phenylene ethynylene, 1,4-methylene naphthalene, 2,6-methylene naphthalene, 1,4-vinylene naphthalene, 2,6-vinylene naphthalene, 1,4-ethynylene naphthalene, 2,6-ethynylene naphthalene, combinations thereof, precursors therefor or combinations of precursors therefor, is deposited on a substrate by a thermal CVD process. The ultrathin layer is optionally exposed to a source of oxygen and then exposed to a reagent selected from ammonium hydroxide, tetramethylammonium hydroxide, ammonium sulfide, dimethyl sulfide, thioacetic acid, sodium hydrosulfide, sodium sulfide, hydrazine, acetamide and combinations thereof. The surface may be modified readily after the treatment.

Claims

1. A method for forming a conformal coating having a reactive surface, said method comprising

depositing on a substrate by a thermal CVD process an ultrathin layer having a thickness of less than 500 Å

and comprising a polymer having repeating units derived from unsubstituted p-xylylene, substituted p-xylylene, phenylene vinylene, phenylene ethynylene, 1,4-methylene naphthalene, 2,6-methylene naphthalene, 1,4-vinylene naphthalene, 2,6-vinylene naphthalene, 1,4-ethynylene naphthalene, 2,6-ethynylene naphthalene, combinations thereof, precursors therefor or combinations of precursors therefor, the ultrathin layer;

optionally, exposing the ultrathin layer to a source of oxygen; and

exposing the first layer to a reagent selected from ammonium hydroxide, tetramethylammonium hydroxide, ammonium sulfide, dimethyl sulfide, thioacetic acid, sodium hydrosulfide, sodium sulfide, hydrazine, acetamide and combinations thereof;

whereby a reactive surface comprising hydroxyl, amino, or thio groups or combinations thereof is formed on the ultrathin layer.

2. A method according to claim 1, wherein the ultrathin layer has a thickness of less than 200 angstroms.

3. A method according to claim 1, wherein the ultrathin layer has a thickness of less than 100 angstroms.

4. A method according to claim 1, wherein the ultrathin layer has a thickness of less than 50 angstroms.

5. A method according to claim 1, wherein the reagent is ammonium sulfide.

6. A method for bonding a first substrate to a second substrate, said method comprising

depositing directly on the first substrate by a thermal CVD process a first ultrathin layer having a thickness of less than 500 Å

and comprising a polymer having repeating units derived from unsubstituted p-xylylene, substituted p-xylylene, phenylene vinylene, phenylene ethynylene, 1,4-methylene naphthalene, 2,6-methylene naphthalene, 1,4-vinylene naphthalene, 2,6-vinylene naphthalene, 1,4-ethynylene naphthalene, 2,6-ethynylene naphthalene, combinations thereof, precursors therefor or combinations of precursors therefor, the ultrathin layer;

exposing the first ultrathin layer to a source of oxygen;

depositing directly on the second substrate by a thermal CVD process a second ultrathin layer having a thickness of less than 200 Å and

comprising a polymer having repeating units derived from unsubstituted p-xylylene, substituted p-xylylene, phenylene vinylene, phenylene ethynylene, 1,4-methylene naphthalene, 2,6-methylene naphthalene, 1,4-vinylene naphthalene, 2,6-vinylene naphthalene, 1,4-ethynylene naphthalene, 2,6-ethynylene naphthalene, combinations thereof, precursors therefor or combinations of precursors therefor, the ultrathin layer;

exposing the second ultrathin layer to a source of oxygen; and

contacting the surface of the first ultrathin layer with an opposing surface of the second ultrathin layer at a temperature of greater than 250°

C.;

whereby the first substrate is bonded to the second substrate via the first and second ultrathin layers.

7. A method according to claim 6, wherein the first substrate is bonded to the second substrate under pressure.

8. A method for forming a metallized layer on substrate , said method comprising

depositing on a substrate by a thermal CVD process an ultrathin layer having a thickness of less than 500 Å

and comprising a polymer having repeating units derived from unsubstituted p-xylylene, substituted p-xylylene, phenylene vinylene, phenylene ethynylene, 1,4-methylene naphthalene, 2,6-methylene naphthalene, 1,4-vinylene naphthalene, 2,6-vinylene naphthalene, 1,4-ethynylene naphthalene, 2,6-ethynylene naphthalene, combinations thereof, precursors therefor or combinations of precursors therefor, the ultrathin layer;

exposing the ultrathin layer to a source of oxygen; and

depositing a metal layer comprising Be, B, Mg, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Ta or a combination thereof directly on the ultrathin layer.

9. A method according to claim 8, additionally comprising, before depositing the metal layer, exposing the ultrathin layer to a reagent selected from ammonium hydroxide, tetramethylammonium hydroxide, ammonium sulfide, dimethyl sulfide, thioacetic acid, sodium hydrosulfide, sodium sulfide, hydrazine and acetamide, whereby hydroxyl, amino, thio groups, or a combination thereof, are attached to the surface of the ultrathin layer.

10. A method according to claim 8, wherein the metal layer comprises Al, Ti, Cr, or Ta.

11. A method according to claim 8, wherein the metal layer comprises Ti.

12. A 3D integrated structure comprising an upper level device bonded to a lower level device by a polymer having repeating units derived from unsubstituted p-xylylene, substituted p-xylylene, phenylene vinylene, phenylene ethynylene, 1,4-methylene naphthalene, 2,6-methylene naphthalene, 1,4-vinylene naphthalene, 2,6-vinylene naphthalene, 1,4-ethynylene naphthalene, 2,6-ethynylene naphthalene or a combination thereof and disposed on opposing surfaces of said upper level device and said lower level device.

13. A structure comprising a layer comprising a polymer having repeating units derived from unsubstituted p-xylylene, substituted p-xylylene, phenylene vinylene, phenylene ethynylene, 1,4-methylene naphthalene, 2,6-methylene naphthalene, 1,4-vinylene naphthalene, 2,6-vinylene naphthalene, 1,4-ethynylene naphthalene, 2,6-ethynylene naphthalene or a combination thereof disposed directly on a substrate and a surface comprising at least one functional group selected from peroxy, hydroxyl, amino, mercapto and combinations thereof.

14. A structure according to claim 13, wherein said polymer has repeating units derived from unsubstituted p-xylylene or substituted p-xylylene.

15. A structure according to claim 13, wherein said polymer has repeating units derived from unsubstituted p-xylylene or substituted p-xylylene.

16. A structure comprising a substrate, a first layer comprising an polymer deposited by CVD and having repeating units derived from unsubstituted p-xylylene, substituted p-xylylene, phenylene vinylene, phenylene ethynylene, 1,4-methylene naphthalene, 2,6-methylene naphthalene, 1,4-vinylene naphthalene, 2,6-vinylene naphthalene, 1,4-ethynylene naphthalene, 2,6-ethynylene naphthalene or a combination thereof, a surface comprising at least one functional group selected from peroxy, hydroxyl, amino, mercapto and combinations thereof, a thickness of less than 500 angstroms and disposed directly on the substrate and

a second layer comprising Be, B, Mg, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Ta or a combination thereof, disposed directly on the first layer.

17. A structure according to claim 16, wherein the second layer comprises Al, Ti, Cr, or Ta.

18. A structure according to claim 16, wherein the second layer comprises Ti.

19. A structure according to claim 16, wherein the first layer has a thickness of less than 200 angstroms.

20. A structure according to claim 16, wherein the first layer has a thickness of less than 100 angstroms.

21. A structure according to claim 16, wherein the first layer has a thickness of less than 50 angstroms.