Oxide/organic polymer multilayer thin films deposited by chemical vapor deposition

Abstract

Multilayer thin films consisting of alternating layers of oxide and organic polymer dielectric materials are manufactured by chemical vapor deposition using a CVD apparatus comprising separate precursor volatilization/dissociation areas. Methods are described for the manufacture of multilayered films. The electrical properties of the multilayered films make the films of embodiments of this invention suitable for use as dielectric materials for semiconductor manufacture. The multilayered films of embodiments this invention reduce RC delay and cross-talk, thereby permitting increased density, higher frequency performance and greater reliability of semiconductor devices for use in the electronics industry.

We claim:  
     
         1 . A method for forming a multilayered oxide/organic polymer film on a surface of a substrate in a chamber, comprising, in any order, the steps of: 
 (a) forming a film comprising an oxide film on said surface of said substrate; and    (d) forming a film comprising an organic polymer in contact with said oxide film.    
     
     
         2 . The method of  claim 1 , wherein the step of forming an oxide film comprises the steps of: 
 (a) vaporizing a precursor for the oxide film;    (b) dissociating said vaporized precursor for the oxide film;    (c) depositing said dissociated, vaporized precursor of the oxide film on the surface of said substrate to form an oxide polymer.    
     
     
         3 . The method of  claim 1 , wherein the step of forming an organic polymer film further comprises the steps of: 
 (a) vaporizing a precursor for the organic polymer film;    (b) dissociating said vaporized precursor for the organic polymer film;    (c) depositing said dissociated, vaporized precursor of the organic polymer film on the surface of said substrate to form an organic polymer.    
     
     
         4 . The method of  claim 2 , wherein the deposition temperature of said precursor for said oxide film is in the range of about 40° C. to about 170° C.  
     
     
         5 . The method of  claim 2 , wherein said precursor for said oxide film has a structure selected from the group consisting of:C—O—M—O—C′, C—M—O—C′ and C—M—C; wherein M is a metal atom, O is an oxygen atom, and C and C′ are organic moieties.  
     
     
         6 . The method of  claim 2 , wherein said precursor for said oxide film comprises a silicon atom.  
     
     
         7 . The method of  claim 2 , wherein said precursor for said oxide film has a metal atom selected from the group consisting of silicon, aluminum, yttrium, titanium, zirconium, tantalum, niobium, and zinc.  
     
     
         8 . The method of  claim 2 , wherein said oxide precursor is an alkoxysilane.  
     
     
         9 . The method of  claim 8 , wherein said oxide precursor is selected from the group consisting of DADBS and TEOS.  
     
     
         10 . The method of  claim 8 , wherein said oxide precursor is selected from the group consisting of tetraacetoxysilane, tetramethoxysilane, tetraallyloxysilane, tetra-n-butoxysilane, tetrakis(ethoxyethoxy)silane, tetrakis(2-ethylhexoxy)silane, tetrakis(2-methoxycryloxyethoxy)silane, tetrakis(methoxyethoxyethoxy)silane, tetrakis(methoxyethoxy)silane, tetrakis(methoxypropoxy)silane, and tetra-n-propoxysilane.  
     
     
         11 . The method of  claim 5 , wherein said oxide precursor is selected from the group consisting of aluminum (III) n-butoxide, yttrium isopropoxide, titanium-di-n-butoxide (bis-2,4-pentanedionate), zirconium isopropoxide, tantalum (V) n-butoxide, niobium (V) n-butoxide and zinc n-butoxide.  
     
     
         12 . The method of  claim 2 , wherein said step of dissociating said precursor is carried out using a resistive heater.  
     
     
         13 . The method of  claim 2 , wherein the step of dissociating said precursor is carried out at a temperature in the range of about 400° C. to about 800° C.  
     
     
         14 . The method of  claim 2 , wherein the step of dissociating said precursor is carried out at a temperature in the range of about 630° C. and about 650° C.  
     
     
         15 . The method of  claim 1 , wherein the steps of polymerizing are carried out at a pressure in the range of about 0.01 Torr to about 1.0 Torr.  
     
     
         16 . The method of  claim 1 , wherein the steps of polymerizing are carried out at a pressure in the range of about 0.03 Torr to about 0.2 Torr.  
     
     
         17 . The method of  claim 1 , wherein the steps of polymerizing are carried out at a pressure in the range of about 0.05 Torr to about 0.1 Torr.  
     
     
         18 . The method of  claim 2 , wherein the precursor is transported to a dissociation chamber using a carrier gas.  
     
     
         19 . The method of  claim 18 , wherein said carrier gas is selected from the group consisting of nitrogen, argon and oxygen.  
     
     
         20 . The method of  claim 18 , wherein the oxide precursor is transported at a flow rate in the range of about 1 SCCM to about 1000 SCCM.  
     
     
         21 . The method of  claim 18 , wherein the oxide precursor is transported at a flow rate in the range of about 10 SCCM to about 100 SCCM.  
     
     
         22 . The method of  claim 18 , wherein the oxide precursor is transported at a flow rate of about 20 SCCM.  
     
     
         23 . The method of  claim 2 , wherein said step of polymerizing is carried out at a deposition rate of about 1 nm/min to about 2000 nm/min.  
     
     
         24 . The method of  claim 3 , wherein said precursor for said organic polymer film comprises a para(xylylene).  
     
     
         25 . The organic polymer of  claim 3  selected from the group consisting of poly(chloro-p-xylylene)(PPXC), poly(dichloro-p-xylylene(PPXDC) and poly(tetrafluoro-p-xylylene), poly(dimethoxy-p-xylylene), poly(sulfo-p-xylylene), poly(iodo-p-xylylene), poly(α, α, α′, α′, tetrafluoro-p-xylylene)(AF-4), poly(trifluoro-p-xylylene), poly(difluoro-p-xylylene) and poly(fluoro-p-xylylene).  
     
     
         26 . The organic polymer of  claim 3  comprising a polyimide.  
     
     
         27 . The organic polymer of  claim 26  further comprising N-phenylmaleimide.  
     
     
         28 . The organic polymer of  claim 3  comprising an organic copolymer.  
     
     
         29 . The organic copolymer of  claim 28  selected from the group consisting of poly(maleimide/parylene) copolymer, poly acenaphthalene/parylene copolymer, divinylbenzene/parylene copolymer, perfluorooctylmethacrylate (PFOMA)/parylene copolymer, 4-vinyl biphenyl/parylene copolymer, 9-vinylanthracene/parylene copolymer, maleic anhydride/parylene copolymer, N-vinyl pyrrolidone/parylene copolymer, 4-vinylpyridine/parylene copolymer, styrene/parylene copolymer, buckminsterfullerene/parylene copolymer, and trihydroperfluoroundecylmethacrylate/parylene copolymer.  
     
     
         30 . The organic polymer of  claim 3  comprising a cross-linked organic copolymer.  
     
     
         31 . The cross-linked organic copolymer of  claim 30  selected from the group consisting of 2, 3, 5, 7, tetravinyl, 1, 3, 5, 7, tetramethylcyclotetrasiloxane/parylene, 1, 3, 5, trivinyl, 1, 3, 5, trimethylcyclotrisiloxane/parylene, tetravinylsilane/parylene/parylene, and 1, 1, 3, 3, tetravinyldimethyldisiloxane/parylene.  
     
     
         32 . The method of  claim 1 , comprising forming a covalently bound oxide-organic polymer film.  
     
     
         33 . The covalently bound oxide-organic polymer film of  claim 32  selected from the group consisting of vinyl triethoxysilane/parylene, vinyl triacetoxysilane/parylene, and vinyl tri-t-butoxysilane.  
     
     
         34 . The method of  claim 3 , wherein said step of dissociating said precursor is carried out using a resistive heater.  
     
     
         35 . The method of  claim 3 , wherein the step of dissociating said precursor for said organic polymer is carried out at a temperature in the range of about 550° C. to about 750° C.  
     
     
         36 . The method of  claim 3 , wherein the precursor is transported to a dissociation chamber using a carrier gas.  
     
     
         37 . The method of  claim 36 , wherein said carrier gas is selected from the group consisting of nitrogen, argon and oxygen.  
     
     
         38 . The method of  claim 36 , wherein the precursor is transported at a flow rate in the range of about 1 SCCM to about 1000 SCCM.  
     
     
         39 . The method of  claim 36 , wherein the oxide precursor is transported at a flow rate in the range of about 10 SCCM to about 100 SCCM.  
     
     
         40 . The method of  claim 36 , wherein the oxide precursor is transported at a flow rate of about 20 SCCM.  
     
     
         41 . The method of  claim 3 , wherein said step of polymerizing is carried out at a deposition rate of about 1 nm/min to about 2000 nm/min.  
     
     
         42 . The method of  claim 1 , wherein multiple alternating layers of oxide and organic polymer are manufactured.  
     
     
         43 . The method of  claim 1 , wherein said organic polymer film is deposited on said surface of said substrate, and said oxide film is deposited over said organic polymer film.  
     
     
         44 . The method of  claim 1 , wherein the rates of deposition are in the range of about 1 nm/min to about 2000 nm/min.  
     
     
         45 . The method of  claim 1 , wherein between the steps of forming said oxide film and said organic polymer film, the deposition chamber is purged of previously dissociated precursors.  
     
     
         46 . The method of  claim 1 , wherein the weight percentage of organic polymer is in the range of about 10% to about 90%.  
     
     
         47 . A method for forming an oxide/organic polymer film on a substrate comprising the steps of: 
 (a) vaporizing a precursor selected from the group consisting of DADBS and TEOS;    (b) dissociating the vaporized precursor at a temperature in the range of about 400° C. to about 800° C.; and    (c) polymerizing the dissociated, vaporized precursor on the substrate at a temperature in the range of about liquid nitrogen temperature to about 170° C. to form an oxide film;    (d) vaporizing a precursor for a poly(para-xylylene);    (e) dissociating the vaporized precursor of step (d) a temperature in the range of about 500° C. to about 750° C.; and    (f) polymerizing the dissociated, vaporized precursor on the oxide film at a temperature in the range of about liquid nitrogen temperature to about 170° C.    
     
     
         48 . A method for forming a multilayered oxide/organic polymer film on a substrate, comprising the steps of: 
 (a) vaporizing DADBS;    (b) dissociating DADBS at a temperature in the range of about 630° C. to about 650° C.; and    (c) polymerizing the dissociated, vaporized DADBS on the substrate at a temperature in the range of about 70° C. to about 90° C. to form an oxide film, 
 wherein the step of polymerizing is carried out at a pressure in the range of about 0.05 Torr to about 0.1 Torr, and  
 wherein the rate of deposition of the silicon dioxide film is in the range of about 7 nm/min to about 100 nm/min.;  
   (d) vaporizing PPXC;    (e) dissociating vaporized PPXC at a temperature in the range of about 550° C. to about 750° C.;    (f) polymerizing the dissociated, vaporized PPXC on said oxide film; and    (g) repeating steps (a) through (f) until a desired number of layers of film are formed.    
     
     
         49 . A multilayer oxide/organic polymer film manufactured according to the method of  claim 1 .  
     
     
         50 . The film of  claim 49  having a dielectric constant of below about 3.8.  
     
     
         51 . The thin oxide film of  claim 49  comprising an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , Y 2 O 3 , TiO 2 , ZrO 2 , Ta 2 O 5 , Nb 2 O 5  and ZnO.  
     
     
         52 . The thin oxide film of  claim 49  comprising SiO 2  wherein said oxide film is made from a precursor selected from DADBS and TEOS.  
     
     
         53 . The thin oxide film of  claim 49  comprising SiO 2  made from a precursor selected from the group consisting of tetraacetoxysilane, tetramethoxysilane (TMOS), tetraallyloxysilane, tetra-n-butoxysilane, tetrakis(ethoxyethoxy)silane, tetrakis(2-ethylhexoxy)silane, tetrakis(2-methoxycryloxyethoxy)silane, tetrakis(methoxyethoxyethoxy)silane, tetrakis(methoxyethoxy)silane, tetrakis(methoxypropoxy)silane, and tetra-n-propoxysilane.  
     
     
         54 . The thin oxide film of  claim 49  made from a precursor selected from the group consisting of aluminum (III) n-butoxide, yttrium isopropoxide, titanium-di-n-butoxide (bis-2,4-pentanedionate), zirconium isopropoxide, tantalum (V) n-butoxide, niobium (V) n-butoxide and zinc n-butoxide.  
     
     
         55 . The film of  claim 49 , wherein the leakage current measured at 1 MV/cm is below about 8×10 −9  A/cm 2 .  
     
     
         56 . The film of  claim 49 , further being substantially free of water.  
     
     
         57 . The film of  claim 49 , further being substantially free of contaminants.  
     
     
         58 . The film of  claim 49 , wherein said oxide film has an average index of refraction of greater than about 1.433.  
     
     
         59 . The film of  claim 49 , further having an extinction coefficient measured at a wavelength of 330 nm of greater than about 5.41×10 −3 .