Method of forming a thin film and methods of manufacturing a gate structure and a capacitor using same

Abstract

A method of manufacturing a thin film includes providing a metal organic precursor onto a substrate where the metal organic precursor is heated to a temperature of about 60° C. to about 95° C. and has a saturated vapor pressure of about 1 Torr to about 5 Torr. An oxidizing agent including oxygen for oxidizing the metal organic precursor is provided onto the substrate. The metal organic precursor and the oxidizing agent are chemically reacted to form the thin film including metal oxide. The thin film is easily available in a gate insulation layer of a gate structure, a dielectric layer of a capacitor, and similar circuit components.

1 . A method of forming a thin film comprising:
 providing a metal organic precursor onto a substrate, wherein the metal organic precursor has a saturated vapor pressure of about 1 Torr to about 5 Torr when the metal organic precursor is heated to a temperature of about 60° C. to about 90° C.;   providing an oxidizing agent including oxygen onto the substrate, the oxidizing agent configured to oxidize the metal organic precursor; and   forming the thin film including a metal oxide on the substrate by chemically reacting the metal organic precursor with the oxidizing agent.   
     
     
         2 . The method of  claim 1 , wherein providing a metal organic precursor is represented by R3-N=M(N(R1)(R2))2 wherein R1, R2 and R3 independently represent hydrogen or an alkyl group having one to five carbon atoms, and M represents zirconium or hafnium. 
     
     
         3 . The method of  claim 1 , wherein the metal organic precursor comprises tertiary-butyl-imido bis-methyl-ethyl-amino hafnium [(t-BuN)Hf(N(CH3)(C2H5))2]. 
     
     
         4 . The method of  claim 1 , wherein the metal organic precursor comprises tertiary-butyl-imido bis-metyl-ethyl-amino zirconium [(t-BuN)Zr(N(CH3)(C2H5))2]. 
     
     
         5 . The method of  claim 1 , wherein the metal organic precursor is in a gaseous state having a saturated vapor pressure of about 3 Torr to about 5 Torr, the precursor formed by heating the precursor in a liquid state at a temperature of about 75° C. to about 85° C. in a canister. 
     
     
         6 . The method of  claim 1 , wherein the metal organic precursor is provided onto the substrate with at least one carrier gas selected from the group consisting essentially of argon gas, nitrogen gas and helium gas. 
     
     
         7 . The method of  claim 1 , further comprising:
 performing a first purge process on the substrate using a purge gas after the metal organic precursor is provided onto the substrate, and   performing a second purge process on the substrate using the purge gas after the oxidizing agent is provided onto the substrate.   
     
     
         8 . The method of  claim 7 , wherein the thin film is formed at a temperature of about 250° C. to about 400° C. under a pressure of about 0.5 Torr to about 3.0 Torr. 
     
     
         9 . The method of  claim 8 , wherein the metal organic precursor is provided onto the substrate by a liquid delivery system, the method further comprising vaporizing the metal organic precursor at a temperature of about 100° C. to about 150° C. in the liquid delivery system. 
     
     
         10 . A method of forming a thin film including metal-aluminum oxide, the method comprising:
 (a) providing a first reactive material including a metal organic precursor onto a substrate, the metal organic precursor having a saturated vapor pressure of about 1 Torr to about 5 Torr when the precursor is heated to a temperature of about 60° C. to about 95° C., the metal organic precursor represented by R3-N=M(N(R1)(R2))2 wherein R1, R2 and R3 independently represent hydrogen or an alkyl group having one to five carbon atoms, and M represents zirconium or hafnium.   (b) chemically adsorbing a first portion of the first reactive material onto the substrate and physically adsorbing a second portion of the first reactive material onto the substrate;   (c) providing an oxidizing agent including oxygen onto the substrate;   (d) forming a first solid material including a metal oxide on the substrate by chemically reacting the first portion of the first reactive material with the oxidizing agent;   (e) providing a second reactive material including an aluminum organic precursor onto the first solid material;   (f) chemically adsorbing a first portion of the second reactive material onto the first solid material and physically adsorbing a second portion of the second reactive material onto the first solid material;   (g) providing an oxidizing agent onto the first solid material; and   (h) forming a second solid material including aluminum oxide on the first solid material by chemically reacting the first portion of the second reactive material with the oxidizing agent,   
     
     
         11 . The method of  claim 10 , further comprising:
 removing the second portion of the first reactive material physically adsorbed on the substrate;   removing a portion of the oxidizing agent, the portion configured not reactive with the first portion of the first reactive material;   removing the second portion of the second reactive material physically adsorbed on the substrate; and   removing a portion of the oxidizing agent, the portion configured not reactive with the first portion of the second reactive material.   
     
     
         12 . The method of  claim 10 , wherein steps (a)-(d) are repeatedly performed at least once, respectively. 
     
     
         13 . The method of  claim 10 , wherein steps (e)-(h) are repeatedly performed at least once. 
     
     
         14 . The method of  claim 10 , wherein steps (a)-(h) are repeatedly performed at least once. 
     
     
         15 . The method of  claim 10 , wherein the metal organic precursor comprises tertiary-butyl-imido bis-methyl-ethyl-amino hafnium [(t-BuN)Hf(N(CH3)(C2H5))2] tertiary-butyl-imido bis-metyl-ethyl-amino zirconium [(t-BuN)Zr(N(CH3)(C2H5))2]. 
     
     
         16 . The method of  claim 10 , wherein the metal organic precursor comprises tertiary-butyl-imido bis-metyl-ethyl-amino zirconium [(t-BuN)Zr(N(CH3)(C2H5))2]. 
     
     
         17 . A method of manufacturing a gate structure of a semiconductor device, the method comprising:
 providing a metal organic precursor onto a substrate, wherein the metal organic precursor has a saturated vapor pressure of about 1 Torr to about 5 Torr when the metal organic precursor is heated to a temperature of about 60° C. to about 95° C. in a canister, the metal organic precursor represented by R3-N=M(N(R1)(R2))2 where R1, R2 and R3 independently represent hydrogen or an alkyl group having one to five carbon atoms, and M represents zirconium or hafnium;   providing an oxidizing agent including oxygen onto the substrate, the oxidizing agent configured to oxidize the metal organic precursor;   forming a gate insulation layer including a metal oxide on the substrate by chemically reacting the metal organic precursor with the oxidizing agent provided on the substrate;   forming a conductive layer on the gate insulation layer; and   forming the gate structure including a gate insulation layer pattern and a gate conductive pattern sequentially stacked on the substrate by patterning the conductive layer and the gate insulation layer.   
     
     
         18 . A method of manufacturing a capacitor, comprising:
 forming a lower electrode on a substrate;   providing a metal organic onto the substrate, wherein the metal organic precursor has a saturated vapor pressure of about 1 Torr to about 5 Torr when the metal organic precursor is heated up to a temperature of about 60° C. to about 95° C., the metal organic precursor represented by R3-N=M(N(R1)(R2))2 where R1, R2 and R3 independently represent hydrogen or an alkyl group having one to five carbon atoms, and M represents zirconium or hafnium;   providing an oxidizing agent including oxygen onto the substrate, the oxidizing agent configured to oxidize the metal organic precursor;   forming a dielectric layer including a metal oxide on the lower electrode by chemically reacting the metal organic precursor with the oxidizing agent provided on the substrate; and   forming an upper electrode on the dielectric layer.