Atomic layer deposition of aluminum oxide films for semiconductor devices using an aluminum alkoxide oxidizer
Method for gas phase atomic layer deposition (ALD) of aluminum oxide films on patterned substrates using a waterless oxidizer that includes an aluminum alkoxide gas. The method includes providing a substrate containing a dielectric layer and a metal layer or a semiconductor layer, and selectively depositing an aluminum oxide film on a surface of the dielectric layer relative to a surface of the metal layer or a surface of the semiconductor layer by a) exposing the substrate to an aluminum alkyl gas, an aluminum halide gas, or an aluminum hydride gas, and b) exposing the substrate to an aluminum alkoxide gas, where the aluminum alkoxide gas is the principal source of oxygen in the aluminum oxide film.
1 . A substrate processing method, comprising:
providing a substrate containing a dielectric layer and a metal layer or a semiconductor layer; and
selectively depositing an aluminum oxide film on a surface of the dielectric layer relative to a surface of the metal layer or a surface of the semiconductor layer by:
a) exposing the substrate to an aluminum alkyl gas, an aluminum halide gas, or an aluminum hydride gas,
b) exposing the substrate to an aluminum alkoxide gas, wherein the aluminum alkoxide gas is the principal source of oxygen in the aluminum oxide film, and
c) repeating steps a) and b) at least once to increase a thickness of the aluminum oxide film on the surface of the dielectric layer, wherein c) results in loss of deposition selectivity and forms a blanket aluminum oxide film on the surface of the dielectric layer and on the surface of the metal layer or on the surface of the semiconductor layer.
2 . The method of claim 1 , further comprising:
prior to selectively depositing the aluminum oxide film, exposing the substrate to a reactant gas containing a molecule that forms a self-assembled monolayer (SAM) on the surface of the metal layer or on the surface of the semiconductor layer.
3 . The method of claim 2 , wherein the molecule includes a head group, a tail group, and a functional end group, and wherein the head group includes a thiol, a silane, a phosphonate, or a carboxylate.
4 . The method of claim 1 , wherein the aluminum alkyl gas contains trimethyl aluminum (Al(CH 3 ) 3 ), triethyl aluminum (Al(CH 2 CH 3 ) 3 ), tripropyl aluminum (Al(CH 2 CH 2 CH 3 ) 3 ), or triisobutylaluminum (Al(CH 2 CH(CH 3 ) 2 ) 3 ), the aluminum halide gas contains AlCl 3 , AlF 3 , AlBr 3 , or AlI 3 , the aluminum hydride gas contains AlH 3 , and the aluminum alkoxide gas contains aluminum isopropoxide (Al(OCH(CH 3 ) 2 ) 3 ), aluminum trimethoxide (Al(OCH 3 ) 3 ), dimethylaluminum isopropoxide ((CH 3 ) 2 AlOCH(CH 3 ) 2 ), dimethylaluminum tertbutoxide ((CH 3 ) 2 AlOC(CH 3 ) 3 ), diethylaluminum isopropoxide ((CH 3 CH 2 ) 2 AlOCH(CH 3 ) 2 ), dimethylaluminum secbutoxide ((CH 3 ) 2 AlOCHCH 3 (CH 2 CH 3 )), aluminum triethoxide (Al(OCH 2 CH 3 ) 3 ), or diethylaluminum ethoxide ((CH 3 CH 2 ) 2 AlOCH 2 CH 3 ).
5 . A substrate processing method, comprising:
providing a substrate containing raised features having a sidewall and a top portion, and a bottom area between the raised features; and
selectively depositing an aluminum oxide film on the top portion and on an upper part of the sidewall of the raised features relative to the bottom area by:
a) exposing the substrate to an aluminum alkyl gas, an aluminum halide gas, or an aluminum hydride gas to form an adsorbed layer that is conformal on the raised features, and
b) exposing the substrate to an aluminum alkoxide gas, wherein the alkoxide gas is the principal source of oxygen in the aluminum oxide film, wherein during step b), the aluminum alkoxide gas does not reach the bottom area between the raised features.
6 . The method of claim 5 , further comprising:
c) repeating steps a) and b) at least once to increase a thickness of the aluminum oxide film.
7 . The method of claim 6 , wherein the aluminum oxide film pinches off an opening between the raised features and forms an airgap.
8 . The method of claim 5 , wherein the aluminum alkyl gas contains trimethyl aluminum (Al(CH 3 ) 3 ), triethyl aluminum (Al(CH 2 CH 3 ) 3 ), tripropyl aluminum (Al(CH 2 CH 2 CH 3 ) 3 ), or triisobutylaluminum (Al(CH 2 CH(CH 3 ) 2 ) 3 ), the aluminum halide gas contains AlCl 3 , AlF 3 , AlBr 3 , or AlI 3 , the aluminum hydride gas contains AlH 3 , and the aluminum alkoxide gas contains aluminum isopropoxide (Al(OCH(CH 3 ) 2 ), aluminum trimethoxide (Al(OCH 3 ) 3 ), dimethylaluminum isopropoxide ((CH 3 ) 2 AlOCH(CH 3 ) 2 ), dimethylaluminum tertbutoxide ((CH 3 ) 2 AlOC(CH 3 ) 3 ), diethylaluminum isopropoxide ((CH 3 CH 2 ) 2 AlOCH(CH 3 ) 2 ), dimethylaluminum secbutoxide ((CH 3 ) 2 AlOCHCH 3 (CH 2 CH 3 )), aluminum triethoxide (Al(OCH 2 CH 3 ) 3 ), or diethylaluminum ethoxide ((CH 3 CH 2 ) 2 AlOCH 2 CH 3 ).
9 . A substrate processing method, comprising:
providing a substrate containing raised features having a sidewall and a top portion, and a bottom area between the raised features; and
selectively depositing an aluminum oxide film on the sidewall and on the bottom area relative to the top portion by:
a) exposing the substrate to an aluminum alkyl gas, an aluminum halide gas, or an aluminum hydride gas to form an adsorbed layer containing aluminum that is conformal on the raised features,
b) deactivating or removing the adsorbed layer containing aluminum on the top portion, and
c) exposing the substrate to an aluminum alkoxide gas, wherein the aluminum alkoxide gas is the principal source of oxygen in the aluminum oxide film, wherein c) is performed after b).
10 . The method of claim 9 , further comprising:
d) repeating steps a), b), and c) at least once to increase a thickness of the aluminum oxide film.
11 . The method of claim 9 , wherein the aluminum oxide film at least substantially fully fills a recessed feature between the raised features.
12 . The method of claim 9 , wherein the deactivating or removing the adsorbed layer includes exposing the substrate to a halogen-containing gas or an oxygen-containing gas.
13 . The method of claim 12 , wherein the halogen-containing gas contains Cl 2 , BCl 3 , CCl 4 , HCl, HBr, TiCl 4 , or a combination thereof, and the oxygen-containing gas contains O 3 , O 2 , H 2 O, H 2 O 2 , or a combination thereof.
14 . The method of claim 9 , wherein the aluminum alkyl gas contains trimethyl aluminum (Al(CH 3 ) 3 ), triethyl aluminum (Al(CH 2 CH 3 ) 3 ), tripropyl aluminum (Al(CH 2 CH 2 CH 3 ) 3 ), or triisobutylaluminum (Al(CH 2 CH(CH 3 ) 2 ) 3 ), the aluminum halide gas contains AlCl 3 , AlF 3 , AlBr 3 , or AlI 3 , the aluminum hydride gas contains AlH 3 , and the aluminum alkoxide gas contains aluminum isopropoxide (Al(OCH(CH 3 ) 2 ) 3 ), aluminum trimethoxide (Al(OCH 3 ) 3 ), dimethylaluminum isopropoxide ((CH 3 ) 2 AlOCH(CH 3 ) 2 ), dimethylaluminum tertbutoxide ((CH 3 ) 2 AlOC(CH 3 ) 3 ), diethylaluminum isopropoxide ((CH 3 CH 2 ) 2 AlOCH(CH 3 ) 2 ), dimethylaluminum secbutoxide ((CH 3 ) 2 AlOCHCH 3 (CH 2 CH 3 )), aluminum triethoxide (Al(OCH 2 CH 3 ) 3 ), or diethylaluminum ethoxide ((CH 3 CH 2 ) 2 AlOCH 2 CH 3 ).
15 . A substrate processing method, comprising:
providing a substrate containing raised features having a sidewall and a top portion, and a bottom area between the raised features; and
selectively depositing an aluminum oxide film on the sidewall and on the bottom area relative to the top portion by:
a) exposing the substrate to an aluminum alkyl gas, an aluminum halide gas, or an aluminum hydride gas to form an adsorbed layer containing aluminum that is conformal on the raised features,
b) deactivating or removing the adsorbed layer containing aluminum on the top portion, and
c) exposing the substrate to an aluminum alkoxide gas that reacts with the adsorbed layer containing aluminum that remains on the substrate following step b) to form the aluminum oxide film, wherein the aluminum alkoxide gas is the principal source of oxygen in the aluminum oxide film.
16 . The method of claim 15 , further comprising:
repeating steps a), b), and c) at least once to increase a thickness of the aluminum oxide film.
17 . The method of claim 15 , wherein the aluminum oxide film at least substantially fully fills a recessed feature between the raised features.
18 . The method of claim 15 , wherein the deactivating or removing the adsorbed layer includes exposing the substrate to a halogen-containing gas or an oxygen-containing gas.
19 . The method of claim 18 , wherein the halogen-containing gas contains Cl 2 , BCl 3 , CCl 4 , HCl, HBr, TiCl 4 , or a combination thereof, and the oxygen-containing gas contains O 3 , O 2 , H 2 O, H 2 O 2 , or a combination thereof.
20 . The method of claim 15 , wherein the aluminum alkyl gas contains trimethyl aluminum (Al(CH 3 ) 3 ), triethyl aluminum (Al(CH 2 CH 3 ) 3 ), tripropyl aluminum (Al(CH 2 CH 2 CH 3 ) 3 ), or triisobutylaluminum (Al(CH 2 CH(CH 3 ) 2 ) 3 ), the aluminum halide gas contains AlCl 3 , AlF 3 , AlBr 3 , or AlI 3 , the aluminum hydride gas contains AlH 3 , and the aluminum alkoxide gas contains aluminum isopropoxide (Al(OCH(CH 3 ) 2 ) 3 ), aluminum trimethoxide (Al(OCH 3 ) 3 ), dimethylaluminum isopropoxide ((CH 3 ) 2 AlOCH(CH 3 ) 2 ), dimethylaluminum tertbutoxide ((CH 3 ) 2 AlOC(CH 3 ) 3 ), diethylaluminum isopropoxide ((CH 3 CH 2 ) 2 AlOCH(CH 3 ) 2 ), dimethylaluminum secbutoxide ((CH 3 ) 2 AlOCHCH 3 (CH 2 CH 3 ), aluminum triethoxide (Al(OCH 2 CH 3 ) 3 ), or diethylaluminum ethoxide ((CH 3 CH 2 ) 2 AlOCH 2 CH 3 ) 2 ).