Deposition tool and method for depositing metal oxide films on organic materials

Abstract

An Atomic Layer Deposition (ALD) configured to deposit a metal oxide layer onto an organic photoresist on a substrate using a highly reactive organic metal precursor. By using a highly reactive metal precursor, the rate of growth of the metal oxide layer is very fast, creating a “seal” that effectively protects the organic photoresist from loss and degradation from subsequent exposure to oxygen species during subsequent ALD cycles. The ability to deposit metal oxide layers means metal oxide spacers can be used in multi-patterning, resulting in highly uniform, dense lines, and the elimination of photolithography-etch steps.

1 . An Atomic Layer Deposition (ALD) tool comprising:
 a processing chamber;   a substrate holder for holding a substrate with an organic photoresist formed thereon for processing in the processing chamber; and   a controller including executable instructions that are arranged to control the ALD tool during one or more ALD cycles, the control of the ALD during the one or more ALD cycles characterized by:   a first half-cycle using an organic metal precursor that is introduced into the processing chamber under the control of the controller, the organic metal precursor resulting in a deposition of a metal oxide layer onto the organic photoresist on the substrate; and   a second half-cycle using an oxygen species that is introduced into the processing chamber under the control of the controller, the oxygen species acting to degrade the organic photoresist,   wherein the organic metal precursor is sufficiently reactive to seal the organic photoresist with the deposited metal oxide layer in three ALD cycles or less.   
     
     
         2 . (canceled) 
     
     
         3 . (canceled) 
     
     
         4 . The ALD tool of  claim 2 , wherein the controller controls the deposition of the metal oxide layer at a rate of 1.0 Angstroms or more per ALD cycle. 
     
     
         5 . The ALD tool of  claim 1 , wherein the organic metal precursor introduced into the processing chamber under the control of the controller is a metal organic tin precursor. 
     
     
         6 . The ALD tool of  claim 1 , wherein the organic metal precursor introduced into the processing chamber under the control of the controller is an amino 10 type precursor. 
     
     
         7 . The ALD tool of  claim 6 , wherein the amino 10 type precursor is selected from a group including:
 (a) Dimethyl amino dimethyl tin (Me 2 Sn(NMe 2 ) 2      (b) Dimethylaminotrimethyltin (Me 3 Sn(MMe 2 )   (c) Tetrakisdimethylamino tin (Sn(Nme 2 ) 4 ;   (d) Tetrakisdimethylamino tin (Sn(Net2))4; or   (e) other amino metal organic tin precursors.   
     
     
         8 . The ALD tool of  claim 1 , wherein the organic metal precursor introduced into the processing chamber under the control of the controller is an methoxy type precursor. 
     
     
         9 . The ALD tool of  claim 8 , wherein the methoxy type precursor is selected from a group including:
 (a) Dibutyl dimethoxy tin (Bu 2 Sn(OMe) 2 ); or   (b) any methoxy or ethoxy tin precursor.   
     
     
         10 . The ALD tool of  claim 1 , wherein the organic photoresist is a carbon photoresist. 
     
     
         11 . The ALD tool of  claim 1 , wherein the organic photoresist is a polymeric photoresist. 
     
     
         12 . The ALD tool of  claim 1 , wherein the organic photoresist is a carbon mask film. 
     
     
         13 . The ALD tool of  claim 1 , wherein the organic photoresist is an Anti Reflective Layer (ARL). 
     
     
         14 . The ALD tool of  claim 1 , wherein the metal oxide layer introduced into the processing chamber under the control of the controller is a tin oxide (SnO 2 ) and the organic photoresist is a carbon photoresist. 
     
     
         15 . The ALD tool of  claim 1 , wherein the metal oxide layer introduced into the processing chamber under the control of the controller is a tin oxide (SnO 2 ) and the organic photoresist is a carbon Anti Reflective Layer (ARL). 
     
     
         16 . (canceled) 
     
     
         17 . The ALD tool of  claim 1 , wherein the ALD tool is a Plasma Enhanced ALD tool (PEALD) comprising an RF source for generating a plasma in the processing chamber. 
     
     
         18 . The ALD tool of  claim 1 , wherein the deposited metal oxide layer deposited under the control of the controller is used to form spacers on the substrate in a multi-patterning process flow. 
     
     
         19 . A multi-patterning method performed on a substrate, the method comprising forming metal oxide spacers on an organic photoresist on the substrate using an organic metal precursor. 
     
     
         20 . The multi-patterning method of  claim 19 , wherein forming the metal oxide spacers further comprises:
 using photolithography to pattern the organic photoresist to define mandrels on the substrate;   depositing a layer of metal oxide over the mandrels on the substrate; and   forming the metal oxide spacers on the substrate by removing substantially horizontal surfaces of the layer of the metal oxide and the mandrels from the substrate.   
     
     
         21 . The multi-patterning method of  claim 20 , further comprising:
 forming a Silicon Oxide (SiO 2 ) layer over the metal oxide spacers on the substrate; and   forming SiO 2  spacers on the substrate by removing horizontal portions of the Silicon Oxide (SiO 2 ) layer and the metal oxide spacers.   
     
     
         22 . The multi-patterning method of  claim 21 , wherein the metal oxide spacers have a pitch that is smaller than the mandrels and the SiO 2  spacers have a pitch that is smaller than the metal oxide spacers. 
     
     
         23 . The multi-patterning method of  claim 20 , wherein depositing the layer of metal oxide further comprises performing three or fewer Atomic Layer Deposition (ALD) cycles on the substrate, each ALD cycle resulting in a metal oxide film having a thickness of 1.0 Angstroms or more. 
     
     
         24 . The multi-patterning method of  claim 23 , wherein each ALD cycle further comprises:
 depositing the metal oxide film, forming the metal oxide layer, during a first half-cycle; and   exposing the substrate to an oxygen species during a second half-cycle,   wherein the metal oxide film deposited during the first half-cycle aids in preventing the oxygen species degrading the mandrels during the second half-cycle.   
     
     
         25 . The multi-patterning method of  claim 21 , wherein the organic metal precursor is a metal organic tin precursor. 
     
     
         26 . The multi-patterning method of  claim 25 , wherein the organic metal precursor is an amino 10 type precursor. 
     
     
         27 . The multi-patterning method of  claim 26 , wherein the amino 10 type precursor is selected from a group including:
 (a) Dimethylaminodimethyltin (Me 2 Sn(NMe 2 ) 2      (b) Dimethylaminotrimethyltin (Me 3 Sn(MMe 2 )   (c) Tetrakis dimethylamino tin Sn(Nme 2 ) 4      (d) Tetrakisdiethylamino tin (Sn(Net2)4); or   (e) any metal organic amino tin precursor.   
     
     
         28 . The multi-patterning method of  claim 21 , wherein the organic metal precursor is an methoxy type precursor. 
     
     
         29 . The multi-patterning method of  claim 28 , wherein the methoxy type precursor is selected from a group including:
 (a) Dibutyl dimethoxy tin (Bu 2 Sn(OMe) 2 );   (b) any other methoxy or ethoxy tin precursor.   
     
     
         30 . The multi-patterning method of  claim 21 , wherein the organic photoresist is one of the following:
 (a) a carbon photoresist;   (b) a polymeric photoresist;   (c) a carbon mask film; or   (d) a carbon Anti Reflective Layer (ARL).   
     
     
         31 . The multi-patterning method of  claim 19 , wherein the metal oxide layer is a tin oxide (SnO 2 ) and the organic photoresist is a carbon photoresist. 
     
     
         32 . The multi-patterning method of  claim 19 , wherein the metal oxide layer is a tin oxide (SnO 2 ) and the photoresist is a carbon Anti Reflective Layer (ARL). 
     
     
         33 . The multi-patterning method of  claim 23 , wherein each ALD cycle is performed at a temperature ranging from room to 125° C. 
     
     
         34 . The multi-patterning method of  claim 23 , wherein depositing the metal oxide film during the first-half cycle further comprises introducing an organic metal precursor into a processing chamber at a flow rate ranging from 0.1 to 0.5 liters per minute. 
     
     
         35 . The multi-patterning method of  claim 34 , further comprising ranging a duration of the first half cycle from 1.0 to 3.0 seconds. 
     
     
         36 . The ALD tool of  claim 1 , wherein the metal oxide layer introduced into the processing chamber under the control of the controller is selected from the group including:
 (a) tin oxide;   (b) titanium dioxide;   (c) hafnium dioxide;   (d) zirconium dioxide; or   (e) tantalum oxide.   
     
     
         37 . (canceled) 
     
     
         38 . An Atomic Layer Deposition (ALD) tool comprising:
 a processing chamber;   a substrate holder for holding a substrate with an organic photoresist formed thereon for processing in the processing chamber; and   a controller including executable instructions that are arranged to control the ALD tool during one or more ALD cycles, the control of the ALD during the one or more ALD cycles characterized by:   a first half-cycle using a metal organic tin precursor that is introduced into the processing chamber under the control of the controller, the metal organic tin precursor resulting in a deposition of a tin oxide (SnO 2 ) layer onto the organic photoresist on the substrate; and   a second half-cycle using an oxygen species that is introduced into the processing chamber under the control of the controller, the oxygen species acting to degrade the organic photoresist,   wherein the metal organic tin precursor is sufficiently reactive to seal the organic photoresist with the deposited tin oxide (SnO 2 ) layer in three ALD cycles or less.   
     
     
         39 . The ALD tool of  claim 38 , wherein the organic photoresist is one of the following:
 (a) a carbon photoresist.   (b) a polymeric photoresist.   (c) a carbon mask film; or   (d) an Anti Reflective Layer (ARL).   
     
     
         40 . The ALD tool of  claim 38 , wherein the organic metal precursor introduced into the processing chamber under the control of the controller is an amino 10 type precursor selected from a group including:
 (a) Dimethyl amino dimethyl tin (Me 2 Sn(NMe 2 ) 2      (b) Dimethylaminotrimethyltin (Me 3 Sn(MMe 2 )   (c) Tetrakisdimethylamino tin (Sn(Nme 2 ) 4 ;   (d) Tetrakisdimethylamino tin (Sn(Net2))4; or   (e) other amino metal organic tin precursors.   
     
     
         41 . The ALD tool of  claim 1 , wherein the organic metal precursor introduced into the processing chamber under the control of the controller is an methoxy type precursor selected from a group including:
 (a) Dibutyl dimethoxy tin (Bu 2 Sn(OMe) 2 ); or   (b) any methoxy or ethoxy tin precursor.