Multi-stage-heating thermal reactor for transport polymerization

Abstract

A multi-stage transport polymerization (“TP”) reactor useful for making a thin film for the fabrication of integrated circuits. One TP reactor has two distinct heating zones that facilitate the cracking of specific precursor materials. The multi-stage reactor comprises a first low temperature heating zone that heats incoming precursor materials to a temperature that is lower than the “cracking” temperature of the precursor. The second heating zone is maintained at a temperature useful for breaking the chemical bonds of a desired leaving groups in the selected precursor. Specialized heating bodies, which transfer heat to the precursor material in the low and high temperature zones, are used as elements of the invention that can simultaneously decrease the total volume and increase the inside surface area of the TP reactor. Chemistries of precursors used in the multi-stage reactor are also provided.

What is claimed is:  
     
         1 . A multi-stage transport polymerization (“TP”) reactor useful for making a thin film from a precursor comprising: 
 (a) a vacuum vessel having a first temperature zone interposed inside a second temperature zone;  
 (b) a pre-heater associated with the first temperature zone;  
 (c) a heater associated with the second temperature zone;  
 (d) a heater body within the vacuum vessel to transfer heat to the precursor and the pre-heated precursor;  
 (e) an inlet in fluid communication with the first temperature zone; and  
 (f) an outlet in fluid communication with the second temperature zone.  
 
     
     
         2 . The multi-stage TP reactor of  claim 1 , wherein the precursor entering from the inlet is preheated in the first temperature zone to give a pre-heated precursor; and the pre-heated precursor then passes into the second temperature zone and is further heated to a desired temperature to give a reactive intermediate; and the reactive intermediate then leaves the multi-stage TP reactor through the outlet.  
     
     
         3 . The multi-stage TP reactor of  claim 2 , wherein the vacuum vessel has a cylindrical shape with a first end and a second end.  
     
     
         4 . The multi-stage TP reactor of  claim 3 , wherein the inlet and outlet are located on the first end of the vacuum vessel.  
     
     
         5 . The multi-stage TP reactor of  claim 4 , wherein, precursor enters the first temperature zone through the inlet on the first end and traverses the low-temperature zone passing into the second-temperature zone through an opening in the first temperature zone at the second end; the pre-heated precursor is diverted in a retrograde path that traverses the second-temperature zone, wherein the reactive intermediate exits the two stage TP reactor through the outlet on the first end.  
     
     
         6 . The multi-stage TP reactor of  claim 1 , wherein the first temperature zone is a low-temperature zone.  
     
     
         7 . The multi-stage TP reactor of  claim 1 , wherein the second temperature zone is a high-temperature zone.  
     
     
         8 . The multi-stage TP reactor of  claim 1 , wherein the heater body is a heater element.  
     
     
         9 . The multi-stage TP reactor of  claim 1 , wherein the vacuum vessel is fabricated from an infrared (“IR”) transparent material.  
     
     
         10 . The multi-stage TP reactor of  claim 9 , wherein the IR transparent material is quartz.  
     
     
         11 . The multi-stage TP reactor of  claim 1 , wherein the vacuum vessel is fabricated from ceramic.  
     
     
         12 . The multi-stage TP reactor of  claim 11 , wherein the ceramic is silicon sarbide, silicon nitride, aluminum nitride, aluninum oxide, or aluminina carbide.  
     
     
         13 . The multi-stage TP reactor of  claim 1 , wherein the vacuum vessel is fabricated from an infrared (“IR”) absorbent material.  
     
     
         14 . The multi-stage TP reactor of  claim 1 , wherein the vacuum vessel further comprises an insulation jacket surrounding the vacuum vessel.  
     
     
         15 . The multi-stage TP reactor of  claim 1 , wherein the vacuum vessel has an internal volume of at least 20 cm 3 .  
     
     
         16 . The multi-stage TP reactor of  claim 1 , wherein the pre-heater utilizes irradiation energy, thermal energy, plasma energy, or microwave energy.  
     
     
         17 . The multi-stage TP reactor of  claim 1 , wherein the pre-heater comprises an infrared (“IR”) heater.  
     
     
         18 . The multi-stage TP reactor of  claim 17 , wherein the IR heater comprises a tungsten halogen lamp.  
     
     
         19 . The multi-stage TP reactor of  claim 17 , wherein the IR heater comprises a heating element coil of iron-chromium-aluminum.  
     
     
         20 . The multi-stage TP reactor of  claim 17 , wherein the IR heater comprises a heating element coil of nickel-chromium.  
     
     
         21 . The multi-stage TP reactor of  claim 1 , wherein the pre-heater comprises a resistive heater.  
     
     
         22 . The multi-stage TP reactor of  claim 21 , wherein the resistive heater is in physical contacts with the heater body.  
     
     
         23 . The multi-stage TP reactor of  claim 1 , wherein the first temperature zone is maintained at a temperature in a range from about 350° C. to about 450° C.  
     
     
         24 . The multi-stage TP reactor of  claim 1 , wherein the first temperature zone further comprises a thermal couple.  
     
     
         25 . The multi-stage TP reactor of  claim 1 , wherein the heater utilizes irradiation energy, thermal energy, plasma energy, or microwave energy.  
     
     
         26 . The multi-stage TP reactor of  claim 1 , wherein the heater comprises an infrared (“IR”) heater.  
     
     
         27 . The multi-stage TP reactor of  claim 26 , wherein the IR heater comprises a tungsten halogen lamp.  
     
     
         28 . The multi-stage TP reactor of  claim 26 , wherein the IR heater comprises a heating element coil of iron-chromium-aluminum.  
     
     
         29 . The multi-stage TP reactor of  claim 26 , wherein the IR heater comprises a heating element coil of nickel-chromium.  
     
     
         30 . The multi-stage TP reactor of  claim 1 , wherein the heater comprises a resistive heater.  
     
     
         31 . The multi-stage TP reactor of  claim 30 , wherein the resistive heater is in physical contacts with the heater body.  
     
     
         32 . The multi-stage TP reactor of  claim 1 , wherein the second temperature zone is maintained at a temperature in a range from about 450° C. to about 580° C.  
     
     
         33 . The multi-stage TP reactor of  claim 1 , wherein the second temperature zone further comprises a thermal couple.  
     
     
         34 . The multi-stage TP reactor of  claim 1 , wherein the precursor has a general chemical structure:  
       
         
           
           
               
               
           
         
       
       wherein: n o  or m is individually zero or an integer, and (n o +m) comprises an integer of at least 2 but no more than a total number of sp 2 C—X substitution on the aromatic group (“Ar”), 
 Ar is an aromatic or a fluorinated-aromatic group,  
 Z′ and Z″ 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;  
 X is a leaving group, and individually a —COOH, —I, —NR 2 , —N + R 3 , —SR, or —SO 2 R, wherein R is an alkyl, a fluorinated alkyl, aromatic or fluorinated aromatic group, and  
 Y is a leaving group, and individually a —Cl, —Br, —I, —NR 2 , —N + R 3 , —SR, or —SO 2 R, or —OR, wherein R is an alkyl, a fluorinated alkyl, aromatic or fluorinated aromatic group  
 
     
     
         35 . The multi-stage TP reactor of  claim 34 , wherein a bonding energy between the leaving group (“(BE) L ”) and a core group of the precursor is less than 75 Kcal/mole, and the range of the (BE) L  is about 20 to 45 Kcal/mole lower than a bonding energy of a next weakest chemical bond energy (“(BE) c ”) present in the precursor.  
     
     
         36 . The multi-stage TP reactor of  claim 34 , wherein the high temperature zone is maintained within a temperature variation across to the gas diffusion direction, (“dTr”) that is equal to, or less than 5 times the differential bond energy (“dBE”) expressed as Kcal/mole, wherein dBE=(BE) L -(BE) c , and (BE) L  is a bonding energy of the desired leaving group, and (BE) c  is a bonding energy of a next weakest chemical bond energy that present in the precursor.  
     
     
         37 . The multi-stage TP reactor of  claim 1 , wherein the heater body has a total of surface area of at least 300 cm 2  for making the thin film on a 200 mm wafer.  
     
     
         38 . The multi-stage TP reactor of  claim 1 , wherein the heater body is fabricated from an IR absorbing material that can maintain uniform temperatures in the range from about 300° C. to about 700° C.  
     
     
         39 . The multi-stage TP reactor of  claim 38 , wherein the IR absorbing material is resistant to corrosion by halogens at temperatures ranging from about 300° C. to about 700° C.  
     
     
         40 . The multi-stage TP reactor of  claim 38 , wherein the IR absorbing material is silicon carbide, silicon nitride, aluminum nitride, or aluminum oxide.  
     
     
         41 . The multi-stage TP reactor of  claim 1 , wherein the heater body comprises a ceramic fin.  
     
     
         42 . The multi-stage TP reactor of  claim 1 , wherein the heater body comprises a ceramic disk.  
     
     
         43 . The multi-stage TP reactor of  claim 42 , wherein the ceramic disk is porous.  
     
     
         44 . The multi-stage TP reactor of  claim 1 , wherein the heater body comprises closely packed balls (“CPB”).  
     
     
         45 . The multi-stage TP reactor of  claim 44 , wherein the CPB are constructed from ceramic, silicon carbide, or alumina carbide.  
     
     
         46 . The multi-stage TP reactor of  claim 44 , wherein the CPB have a diameter that ranges from about 0.5 to 10 mm.  
     
     
         47 . The multi-stage TP reactor of  claim 44 , wherein the CPB are packed with a symmetric packing method.  
     
     
         48 . The multi-stage TP reactor of  claim 44 , wherein the CPB are packed with a face centered packing method.  
     
     
         49 . The multi-stage TP reactor of  claim 44 , wherein the CPB are packed with a packing density (“φ”) in the range from about 50% to about 74%.  
     
     
         50 . The multi-stage TP reactor of  claim 49 , wherein the packing density (“φ”) have open space between the heater balls that is less than the mean free path (“MFP”) of the precursor material, wherein the MFP is in a range from about 1 mm to about 20 mm.  
     
     
         51 . A multi-stage transport polymerization (“TP”) reactor useful for making a thin film from a precursor comprising: 
 (a) a vacuum vessel having a first temperature zone interposed inside a second temperature zone, the second temperature zone interposed inside a third temperature zone;  
 (b) a heater and thermal couple associated with maintaining the accurate temperature;  
 (c) a heater body within the vacuum vessel to transfer heat to the precursor and the pre-heated precursor;  
 (d) an inlet in fluid communication with the first temperature zone; and  
 (e) an outlet in fluid communication with the third temperature zone.  
 
     
     
         52 . The multi-stage TP reactor of  claim 51 , wherein the cold precursor entering from the inlet is preheated in the first temperature zone to give a pre-heated precursor; and the pre-heated precursor then passes into the second temperature zone and is further heated to a desired temperature before passing into the third temperature zone to give a reactive intermediate; and the reactive intermediate then leaves the the multi-stage TP reactor through the outlet.  
     
     
         53 . The multi-stage TP reactor of  claim 52 , wherein the vacuum vessel has a cylindrical shape with a first end and a second end.  
     
     
         54 . The multi-stage TP reactor of  claim 53 , wherein the inlet is located on the first end, and outlet is located on the second end of the vacuum vessel.  
     
     
         55 . The multi-stage TP reactor of  claim 54 , wherein, precursor enters the first temperature zone through the inlet on the first end and traverses the first-temperature zone passing into the second-temperature zone through an opening in the first temperature zone at the second end; the pre-heated precursor is diverted in a retrograde path that traverses the second-temperature zone, passing into the second-temperature zone through an opening in the second temperature zone at the first end, the heated precursor is diverted again into an antegrade path that traverses the third-temperature zone, wherein the reactive intermediate exits the multiple TP reactor through the outlet on the second end.  
     
     
         56 . The multi-stage TP reactor of  claim 51 , wherein the heater body is a heater element.  
     
     
         57 . The multi-stage TP reactor of  claim 51 , wherein the vacuum vessel is fabricated from an infrared (“IR”) transparent material.  
     
     
         58 . The multi-stage TP reactor of  claim 57 , wherein the IR transparent material is quartz or Pyrex glass.  
     
     
         59 . The multi-stage TP reactor of  claim 51 , wherein the vacuum vessel further comprises an insulation jacket surrounding the vacuum vessel.  
     
     
         60 . The multi-stage TP reactor of  claim 51 , wherein the pre-heater utilizes irradiation energy, thermal energy, plasma energy, or microwave energy.  
     
     
         61 . The multi-stage TP reactor of  claim 51 , wherein the heater comprises an infrared (“IR”) heater.  
     
     
         62 . The multi-stage TP reactor of  claim 51 , wherein the precursor has a general chemical structure:  
       
         
           
           
               
               
           
         
       
       wherein: n o  or m is individually zero or an integer, and (n o +m) comprises an integer of at least 2 but no more than a total number of sp 2 C—X substitution on the aromatic group (“Ar”), 
 Ar is an aromatic or a fluorinated-aromatic group,  
 Z′ and Z″ 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;  
 X is a leaving group, and individually a —COOH, —I, —NR 2 , —N + R 3 , —SR, or —SO2R, wherein R is an alkyl, a fluorinated alkyl, aromatic or fluorinated aromatic group, and  
 Y is a leaving group, and individually a —Cl, —Br, —I, —NR 2 , —N + R 3 , —SR, or —SO2R, or —OR, wherein R is an alkyl, a fluorinated alkyl, aromatic or fluorinated aromatic group  
 
     
     
         63 . The multi-stage TP reactor of  claim 62 , wherein a bonding energy between the leaving group (“(BE) L ”) and a core group of the precursor is less than 85 Kcal/Mole, and the range of the (BE) L  is about 25 to 40 Kcal/Mole lower than a bonding energy of a next weakest chemical bond energy (“(BE) c ”) present in the precursor.  
     
     
         64 . The multi-stage TP reactor of  claim 62 , wherein the high temperature zone is maintained within a temperature variation of a gas diffusion direction (“dTr”) that is equal to, or less than 5 times the dimmer bond energy (“dBE”) expressed as Kcal/mole, wherein dBE=(BE) L -(BE) c , and (BE) L  is a bonding energy of the desired leaving group, and (BE) c  is a bonding energy of a next weakest chemical bond energy that present in the precursor.  
     
     
         65 . The multi-stage TP reactor of  claim 51 , wherein the heater body is fabricated from an IR absorbing material that can maintain uniform temperatures in the range from about 300° C. to about 700° C.  
     
     
         66 . The multi-stage TP reactor of  claim 65 , wherein the IR absorbing material is resistant to corrosion by halogens at temperatures ranging from about 300° C. to about 700° C.  
     
     
         67 . The multi-stage TP reactor of  claim 65 , wherein the IR absorbing material is SiC, silicon nitride, aluminum nitride, or aluminum oxide.  
     
     
         68 . The multi-stage TP reactor of  claim 51 , wherein the heater body comprises a ceramic fin.  
     
     
         69 . The multi-stage TP reactor of  claim 51 , wherein the heater body comprises a ceramic disk.  
     
     
         70 . The multi-stage TP reactor of  claim 69 , wherein the ceramic disk is porous.  
     
     
         71 . The multi-stage TP reactor of  claim 51 , wherein the heater body comprises closely packed balls (“CPB”).  
     
     
         72 . The multi-stage TP reactor of  claim 71 , wherein the CPB are constructed from ceramic, silicon carbide, or alumina carbide.  
     
     
         73 . The multi-stage TP reactor of  claim 71 , wherein the CPB have a diameter that ranges from about 0.5 to 10 mm.  
     
     
         74 . The multi-stage TP reactor of  claim 71 , wherein the CPB are packed with a packing density (“φ”) in the range from about 50% to about 74%.  
     
     
         75 . A reactor cleaning subsystem (“RCS”) for the multi-stage transport polymerization (“TP”) reactor of  claim 1  comprising: 
 (a) a gas-inlet in fluid communication with the multi-stage TP reactor;  
 (b) a discharging-outlet in fluid communication with the multi-stage TP reactor; and  
 (c) an IR heater associated with the multi-stage TP-reactor.  
 
     
     
         76 . The RCS of  claim 75 , wherein the IR heater heats the heater body inside the vacuum vessel, a heated gas is passed through the gas-inlet to bum off organic residues inside the multi-stage TP-reactor, and oxidized gas flows through the discharging outlet into an exhaust.  
     
     
         77 . The RCS of  claim 76 , further comprising a connector valve in fluid communication with the gas-inlet, wherein a mass flow controller (“MFC”) having fluid communication with the connector-valve is connected to a heated gas supply.  
     
     
         78 . The RCS of  claim 77 , further comprising a by-pass valve in fluid communication with the discharge-outlet, wherein a by-pass line having fluid communication with the by-pass valve is connected to the exhaust.  
     
     
         79 . The RCS of  claim 78 , wherein the heated gas supply is pressurized oxygen.  
     
     
         80 . The RCS of  claim 79 , wherein the pressurized oxygen is in the range from about 1 to 20 psi.  
     
     
         81 . The RCS of  claim 78 , wherein the heated gas supply is pressurized air.  
     
     
         82 . The RCS of  claim 78 , wherein the heated gas supply is maintained at a temperature within at least 100° C. of a temperature in the first-temperature zone of the multi-stage TP reactor to prevent thermal shock or cracking of the heater bodies inside the reactor.  
     
     
         83 . The RCS of  claim 78 , wherein an inside temperature of the multistage TP reactor is maintained at a temperature of at least 400° C. during the RCS cleaning process.  
     
     
         84 . A method of cleaning an organic residue inside the multi-stage transport polymerization (“TP”) reactor of  claim 1  using a reactor cleaning subsystem (“RCS”) comprising: 
 (a) heating the heater body to a desired temperature with a resist heater;  
 (b) introducing a heated gas into the TP reactor through the inlet;  
 (c) burning the organic residue with the heated gas to give an oxidized gas; and  
 (d) discharging the oxidized gas from the reactor.  
 
     
     
         85 . The method of  claim 84 , wherein an inside temperature of the multistage TP reactor is at least 400° C. during the RCS cleaning process.  
     
     
         86 . The method of  claim 84 , wherein the heated gas supply is maintained at a temperature within at least 100° C. of a temperature in the first-temperature zone of the multi-stage TP reactor to prevent thermal shock or cracking of the heater bodies inside the reactor.  
     
     
         87 . The method of  claim 84 , wherein the heated gas supply is pressurized oxygen.  
     
     
         88 . The method of  claim 87 , wherein the pressurized oxygen is in the range from about 1 to 20 psi.  
     
     
         89 . The method of  claim 84 , wherein the heated gas supply is pressurized air.