Method for depositing a film
An atomic layer deposition method for depositing a film into surface features of a substrate is disclosed. The method may include the step of placing the substrate having surface features into a reactor. An organic passivation agent may be introduced into the reactor, which may react with a portion of exposed hydroxyl radicals within the surface features. Subsequently, unreacted organic passivation agent may be purged, and then a precursor may be introduced. The precursor may react with the remaining exposed hydroxyl radicals that did not interact with the organic passivation agent. Subsequently, the unreacted precursor may be purged, and an oxygen source or a nitrogen source may be introduced into the reactor to form a film within the surface features.
1 . An atomic layer deposition method for depositing a film into surface features of a substrate, the method comprising:
a) placing the substrate having surface features into a reactor, the surface features having exposed hydroxyl groups, wherein the surface features comprise vias, trenches, or vias and trenches, and wherein said vias and said trenches are formed with a material selected from the group consisting of silicon, silicon oxide, silicon nitride, carbon doped silicon oxide, or a combination thereof;
b) heating the reactor to one or more temperatures ranging from ambient temperature to about 700° C. and optionally maintaining the reactor at a pressure of 100 torr or less;
c) introducing into the reactor at least one organic passivation agent to react with a portion of the exposed hydroxyl groups of the surface features, wherein the organic passivation agent comprises at least one compound selected from the group consisting of tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetra-n-propyl orthocarbonate, trimethyl orthoacetate, triethyl orthoacetate, 1,1,1-triethoxypentane, 1,1,1-triethoxyheptane, triethyl orthobenzoate, 2,2-diethoxypropane, 1,1-diethoxy-1-phenylethane, 4,4-diethoxyheptane, 4,4-diethoxynonane, trimethyl orthoformate, triethyl orthoformate, and tri-n-propyl orthoformate;
d) purging unreacted organic passivation agent from the reactor using inert gas;
e) introducing a precursor gas having at least one organoamino group to react with any unreacted hydroxyl groups of the surface features, wherein the precursor is selected from the group consisting of di-iso-propylaminosilane, di-sec-butylaminosilane, bis(diethylamino)silane, bis(dimethylamino)silane, bis(ethylmethylamino)silane, bis(tert-butylamino)silane, di-iso-propylaminomethylsilane, di-sec-butylaminomethylsilane, dimethylaminodimethylsilane, dimethylaminotrimethylsilane, bis(dimethylamino)methylsilane, tetrakis(dimethylamino)silane, tris(dimethylamino)silane, iso-propylaminotrimethylsilane, tert-butylaminotrimethylsilane, iso-butylaminotrimethylsilane, cyclohexaminotrimethylsilane, pyrrolidinotrimethylsilane, 2-methylpyrrolidinotrimethylsilane, 2,5-dimethylpyrrolidinotrimethylsilane, piperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, 1-methylpiperazinotrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, and imidazolyltrimethylsilane; di-iso-propylaminodisilane, and di-sec-butylaminodisilane; di-iso-propylaminotrisilylamine, diethylaminotrisilylamine, iso-propylaminotrisilylamine, and cyclohexylmethylaminotrisilylamine; 1-dimethylamino-pentamethyldisiloxane, 1-diethylamino-pentamethyldisiloxane, 1-ethylmethylamino-pentamethyldisiloxane, 1,3-bis(dimethylamino)tetramethyldisiloxane, 1-dimethylamino-heptamethyltrisiloxane, and 1,5-bis(dimethylamino)hexamethyltrisiloxane; 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-iso-propylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-iso-propylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-iso-propylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-iso-propylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane; tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium, and tetrakis(ethylmethylamino)titanium; tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe2)3), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMeEt)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMeEt)3), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMeEt)3), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NEt2)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NEt2)3), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp2Hf(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NMe2)2), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp2Hf(NMeEt)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NMeEt)2), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NMeEt)2), bis(cyclopentadienyl)bis(dimethylamino)hafnium ((Cp2Hf(NEt2)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NEt2)3), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NEt2)2), (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(diethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino], and bis(ethylmethylamino)hafnium; tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium(TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMe2)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMe2)3), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpZr(NMe2)3), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMeEt)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMeEt)3), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpZr(NMeEt)3), cyclopentadienyltris(dimethylamino)zirconium (CpHf(NEt2)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NEt2)3), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpZr(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp)2Zr(NMe2)2), bis(cyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NMeEt)2), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NMeEt)2), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp)2Zr(NMeEt)2), bis(cyclopentadienyl)bis(dimethylamino)zirconium ((Cp2Zr(NEt2)2), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NEt2)3), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp)2Zr(NEt2)2), (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)zirconium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)zirconium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(diethylamino)zirconium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(diethylamino)zirconium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)zirconium, and (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)zirconium; (tert-butylimino)tris(dimethylamino)tantalum, (tert-butylimino)tris(diethylamino)tantalum, and (tert-butylimino)tris(ethylmethylamino)tantalum; bis(tert-butylimino)bis(dimethylamino)tungsten, bis(tert-butylimino)bis(diethylamino)tungsten, and bis(tert-butylimino)bis(ethylmethylamino)tungsten; bis(tert-butylimino)bis(dimethylamino)molybdenum, bis(tert-butylimino)bis(diethylamino)molybdenum, and bis(tert-butylimino)bis(ethylmethylamino)molybdenum; and tris(dimethylamino)aluminum, tris(diethylamino)aluminum, and tris(ethylmethylamino)aluminum;
f) purging unreacted precursor from the reactor using inert gas;
g) introducing an oxygen source or a nitrogen source into the reactor; and
h) purging unreacted oxygen source or nitrogen source and any by-products with inert gas,
wherein steps c through h are repeated until the surface features are filled bottom-up.
2 . The method according to claim 1 , wherein the organic passivation agent comprises triethylorthoacetate.
3 . The method according to claim 1 , wherein the oxygen source is selected from the group consisting of oxygen, oxygen plasma, water vapor plasma, a mixture of water and organic amine, hydrogen peroxide, nitrous oxide, ozone, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof.
4 . The method according to claim 1 , wherein the nitrogen source is selected from the group consisting of ammonia, hydrazine, methylhydrazine, 1,1-dimethylhydrazine, N 2 plasma, ammonia plasma, hydrogen/nitrogen plasma, and combinations thereof.
5 . The method according to claim 1 , wherein the surface features have a depth to width aspect ratio of at least 2:1 or higher.
6 . The method according to claim 5 , wherein the aspect ratio is at least 4:1.
7 . The method according to claim 5 , wherein the surface features have a width of 100 nm or less.
8 . The method according to claim 1 , wherein the surface features are vias.
9 . The method according to claim 1 , wherein the surface features are trenches.
10 . The method according to claim 1 , wherein the surface features are vias and trenches.
11 . The method according to claim 1 , wherein the film produced each time after performing steps c) through h) is thicker toward a bottom of the surface features than toward a top of the surface feature.