Solid precursor-based delivery of fluid utilizing controlled solids morphology

Abstract

Apparatus and method for volatilizing a source reagent susceptible to particle generation or presence of particles in the corresponding source reagent vapor, in which such particle generation or presence is suppressed by structural or processing features of the vapor generation system. Such apparatus and method are applicable to liquid and solid source reagents, particularly solid source reagents such as metal halides, e.g., hafnium chloride. The source reagent in one specific implementation is constituted by a porous monolithic bulk form of the source reagent material. The apparatus and method of the invention are usefully employed to provide source reagent vapor for applications such as atomic layer deposition (ALD) and ion implantation.

What is claimed is: 
     
         1 . A vaporizer comprising a vaporizer vessel adapted to hold a source reagent, said vaporizer being adapted for heating of said vaporizer vessel and the source reagent therein, to generate vapor deriving from said source reagent, said vessel defining an enclosed interior volume, and having at least one port, whereby vapor deriving from said source reagent is dischargeable from said interior volume of the vessel, said vaporizer comprising at least one protrusion element in the interior volume adapted to contact the source reagent therein, wherein the source reagent comprises a monolithic porous solid source reagent body. 
     
     
         2 . The vaporizer of  claim 1 , wherein said at least one protrusion element is comprised by at least one tray. 
     
     
         3 . The vaporizer of  claim 2 , comprising multiple trays in the interior volume thereof. 
     
     
         4 . The vaporizer of  claim 3 , wherein the multiple trays are vertically spaced apart from one another. 
     
     
         5 . The vaporizer of  claim 3 , wherein each tray comprises multiple protrusion elements. 
     
     
         6 . The vaporizer of  claim 4 , wherein each tray comprises multiple protrusion elements. 
     
     
         7 . The vaporizer of  claim 1 , further comprising a cover securable to said vessel to enclose said interior volume, said cover including inlet and outlet ports, whereby carrier gas is introduceable to the interior volume through the inlet port, and a carrier gas mixture including the carrier gas and vapor deriving from the source reagent is dischargeable from the interior volume through said outlet port. 
     
     
         8 . The vaporizer of  claim 7 , wherein the inlet port is centrally located in the cover and a downtube communicating with inlet port is in a central portion of the interior volume and arranged to discharge carrier gas so that it flows over the monolithic porous solid source reagent body. 
     
     
         9 . The vaporizer of  claim 1 , wherein the source reagent comprises a material selected from the group consisting of: dimethyl hydrazine, trimethyl aluminum (TMA), hafnium tetrachloride (HfCl4), zirconium tetrachloride (ZrCl4), indium trichloride, indium monochloride, aluminum trichloride, titanium iodide, tungsten carbonyl, Ba(DPM)2, bis di pivaloyl methanato strontium (Sr(DPM)2), TiO(DPM)2, tetra di pivaloyl methanato zirconium (Zr(DPM)4), decaborane, octadecaborane, boron, magnesium, gallium, indium, antimony, copper, phosphorous, arsenic, lithium, sodium tetrafluoroborates, precursors incorporating alkyl-amidinate ligands, organometallic precursors, zirconium tertiary butoxide (Zr(t-OBu)4), tetrakisdiethylaminozirconium (Zr(Net2)4), tetrakisdiethylaminohafnium (Hf(NEt2)4), tetrakis (dimethylamino) titanium (TDMAT), tertbutyliminotris (deithylamino) tantalum (TBTDET), pentakis (demethylamino) tantalum (PDMAT), pentakis (ethylmethylamino) tantalum (PEMAT), tetrakisdimethylamino zirconium (Zr(NMe2)4), hafniumtertiarybutoxide (Hf(tOBu)4), xenon difluoride (XeF2), xenon tetrafluoride (XeF4), xenon hexafluoride (XeF6), metalorganic β-diketonate complexes, tungsten hexafluoride, cyclopentadienylcycloheptatrienyl-titanium (CpTiCht), cyclooctatetraenecyclo-pentadienyltitanium, biscyclopentadienyltitaniumdiazide, trimethyl gallium, trimethyl indium, aluminum alkyls, trimethylaluminum, triethylaluminum, trimethylamine alane, dimethyl zinc, tetramethyl tin, trimethyl antimony, diethyl cadmium, tungsten carbonyl, metal halides, gallium halides, indium halides, antimony halides, arsenic halides, aluminum iodide, titanium iodide; metalorganic complexes, In(CH3)2(hfac), dibromomethyl stibine, tungsten carbonyl, metalorganic alkoxide complexes, metalorganic carboxylate complexes, metalorganic aryl complexes and metalorganic amido complexes, and compatible combinations and mixtures of two or more of the foregoing. 
     
     
         10 . The vaporizer of  claim 1 , wherein the source reagent comprises zirconium tetrachloride (ZrCl4). 
     
     
         11 . The vaporizer of  claim 1 , wherein the source reagent comprises tetrachloride (HfCl4). 
     
     
         12 . The vaporizer of  claim 1 , wherein interior structure of said vessel comprises compartments. 
     
     
         13 . A method of providing source reagent for vaporization for use in a fluid-utilizing process, said method comprising providing the source reagent in a monolithic porous solid source reagent body for use in a vaporizer according to  claim 1 . 
     
     
         14 . The method of  claim 13 , wherein the source reagent comprises a material selected from the group consisting of: dimethyl hydrazine, trimethyl aluminum (TMA), hafnium tetrachloride (HfCl4), zirconium tetrachloride (ZrCl4), indium trichloride, indium monochloride, aluminum trichloride, titanium iodide, tungsten carbonyl, Ba(DPM)2, bis di pivaloyl methanato strontium (Sr(DPM)2), TiO(DPM)2, tetra di pivaloyl methanato zirconium (Zr(DPM)4), decaborane, octadecaborane, boron, magnesium, gallium, indium, antimony, copper, phosphorous, arsenic, lithium, sodium tetrafluoroborates, precursors incorporating alkyl-amidinate ligands, organometallic precursors, zirconium tertiary butoxide (Zr(t-OBu)4), tetrakisdiethylaminozirconium (Zr(Net2)4), tetrakisdiethylaminohafnium (Hf(NEt2)4), tetrakis (dimethylamino) titanium (TDMAT), tertbutyliminotris (deithylamino) tantalum (TBTDET), pentakis (demethylamino) tantalum (PDMAT), pentakis (ethylmethylamino) tantalum (PEMAT), tetrakisdimethylamino zirconium (Zr(NMe2)4), hafniumtertiarybutoxide (Hf(tOBu)4), xenon difluoride (XeF2), xenon tetrafluoride (XeF4), xenon hexafluoride (XeF6), metalorganic β-diketonate complexes, tungsten hexafluoride, cyclopentadienylcycloheptatrienyl-titanium (CpTiCht), cyclooctatetraenecyclo-pentadienyltitanium, biscyclopentadienyltitaniumdiazide, trimethyl gallium, trimethyl indium, aluminum alkyls, trimethylaluminum, triethylaluminum, trimethylamine alane, dimethyl zinc, tetramethyl tin, trimethyl antimony, diethyl cadmium, tungsten carbonyl, metal halides, gallium halides, indium halides, antimony halides, arsenic halides, aluminum iodide, titanium iodide; metalorganic complexes, In(CH3)2(hfac), dibromomethyl stibine, tungsten carbonyl, metalorganic alkoxide complexes, metalorganic carboxylate complexes, metalorganic aryl complexes and metalorganic amido complexes, and compatible combinations and mixtures of two or more of the foregoing. 
     
     
         15 . The method of  claim 13 , wherein the source reagent comprises hafnium tetrachloride (HfCl4). 
     
     
         16 . The method of  claim 13 , wherein the source reagent comprises zirconium tetrachloride (ZrCl4). 
     
     
         17 . A method of producing vapor for use in a fluid-utilizing process, said method comprising heating a monolithic porous solid source reagent body to form vapor therefrom in a vaporizer according to  claim 1 . 
     
     
         18 . The method of  claim 17 , wherein the monolithic porous solid source reagent body comprises a material selected from the group consisting of: dimethyl hydrazine, trimethyl aluminum (TMA), hafnium tetrachloride (HfCl4), zirconium tetrachloride (ZrCl4), indium trichloride, indium monochloride, aluminum trichloride, titanium iodide, tungsten carbonyl, Ba(DPM)2, bis di pivaloyl methanato strontium (Sr(DPM)2), TiO(DPM)2, tetra di pivaloyl methanato zirconium (Zr(DPM)4), decaborane, octadecaborane, boron, magnesium, gallium, indium, antimony, copper, phosphorous, arsenic, lithium, sodium tetrafluoroborates, precursors incorporating alkyl-amidinate ligands, organometallic precursors, zirconium tertiary butoxide (Zr(t-OBu)4), tetrakisdiethylaminozirconium (Zr(Net2)4), tetrakisdiethylaminohafnium (Hf(NEt2)4), tetrakis (dimethylamino) titanium (TDMAT), tertbutyliminotris (deithylamino) tantalum (TBTDET), pentakis (demethylamino) tantalum (PDMAT), pentakis (ethylmethylamino) tantalum (PEMAT), tetrakisdimethylaminozirconium (Zr(NMe2)4), hafniumtertiarybutoxide (Hf(tOBu)4), xenon difluoride (XeF2), xenon tetrafluoride (XeF4), xenon hexafluoride (XeF6), metalorganic β-diketonate complexes, tungsten hexafluoride, cyclopentadienylcycloheptatrienyl-titanium (CpTiCht), cyclooctatetraenecyclo-pentadienyltitanium, biscyclopentadienyltitaniumdiazide, trimethyl gallium, trimethyl indium, aluminum alkyls, trimethylaluminum, triethylaluminum, trimethylamine alane, dimethyl zinc, tetramethyl tin, trimethyl antimony, diethyl cadmium, tungsten carbonyl, metal halides, gallium halides, indium halides, antimony halides, arsenic halides, aluminum iodide, titanium iodide; metalorganic complexes, In(CH3)2(hfac), dibromomethyl stibine, tungsten carbonyl, metalorganic alkoxide complexes, metalorganic carboxylate complexes, metalorganic aryl complexes and metalorganic amido complexes, and compatible combinations and mixtures of two or more of the foregoing. 
     
     
         19 . The method of  claim 17 , wherein said fluid-utilizing process comprises an atomic layer deposition process, and wherein said vapor is flowed from the vaporizer to the atomic layer deposition process. 
     
     
         20 . The method of  claim 17 , wherein said fluid-utilizing process comprises an ion implantation process, and wherein said vapor is flowed from the vaporizer to the ion implantation process.