In situ acyclic diamino carbene (ADC) deposition
Methods of selectively depositing a passivation layer on a metal surface of a semiconductor substrate are described. Exemplary methods may include exposing the semiconductor substrate having a metal surface and a non-metal surface to a first precursor to form a first portion of the passivation layer on the metal surface, the first precursor including an isonitrile. The exemplary methods may further include exposing the semiconductor substrate comprising a metal surface and a non-metal surface to a second precursor to form the passivation layer on the metal surface. The second precursor may include an amine, an alcohol, or a thiol.
1 . A method of selectively depositing a passivation layer on a semiconductor substrate, the method comprising:
exposing the semiconductor substrate comprising a metal surface and a non-metal surface to a first precursor to form a first portion of the passivation layer on the metal surface, the first precursor comprising an isonitrile of general formula (I):
wherein R 1 comprises one or more of a linear alkyl, branched alkyl, cyclic alkyl, substituted or unsubstituted benzyl, silyl, and substituted or unsubstituted aryl groups; and
exposing the semiconductor substrate comprising a metal surface and a non-metal surface to a second precursor to form the passivation layer on the metal surface, the second precursor having a general formula (II):
wherein R 2 comprises one or more of a linear or branched C 1-24 alkyl, substituted linear or branched C 1-24 alkyl, substituted or unsubstituted C 5-7 cyclic alkyl, and benzyl substituted with alkyl, alkoxy, or thio, and X comprises —NH—, —O—, or —S—.
2 . The method of claim 1 , wherein the second precursor is an amine.
3 . The method of claim 2 , wherein the first precursor and the second precursor react via a nucleophilic addition to form a complex on the metal surface, the complex comprising an acyclic diamino carbene (ADC) of general formula (III):
4 . The method of claim 3 , wherein the ADC of general formula (III) is formed in situ on the metal surface.
5 . The method of claim 2 , wherein the second precursor of general formula (II) is selected from the group consisting of:
wherein n 1 is an integer in a range from 1 to 12, n 2 is an integer in a range from 1 to 3, R 3 is a substituted linear or branched alkyl, R 4 is alkyl or alkoxy, and m is an integer in a range of from 1 to 5.
6 . The method of claim 2 , wherein the second precursor of general formula (II) is a highly nucleophilic amine or a secondary amine.
7 . The method of claim 6 , wherein the highly nucleophilic amine comprises one or more t-BuNH 2 groups.
8 . The method of claim 1 , wherein the second precursor is an alcohol or a thiol.
9 . The method of claim 8 , wherein the first precursor and the second precursor react via a nucleophilic addition to form a complex on the metal surface, the complex comprising a species of general formula (IV):
wherein Y is O if the second precursor is an alcohol or S if the second precursor is a thiol.
10 . The method of claim 9 , wherein the complex of general formula (IV) is formed in situ on the metal surface.
11 . The method of claim 1 , wherein the first precursor comprises one or more of a linear, branched or cyclic alkyl substituted with one or more electron withdrawing group (EWG) selected from the group consisting of —NO 2 , —CF 3 and sulfonyl or an aromatic ring substituted with one or more electron withdrawing group (EWG) selected from the group consisting of —NO 2 , —CF 3 and sulfonyl.
12 . The method of claim 1 , wherein the isonitrile of general formula (I) is selected from the group consisting of:
13 . The method of claim 1 , further comprising removing one or more of a first precursor effluent comprising the first precursor from the substrate and a second precursor effluent comprising the second precursor from the substrate.
14 . A method of selectively depositing a passivation layer on a semiconductor substrate, the method comprising:
a first process cycle comprising exposing the semiconductor substrate comprising a metal surface and a non-metal surface to a first precursor to form a first portion of the passivation layer on the metal surface, the first precursor comprising an isonitrile of general formula (I):
R 1 comprising one or more of a linear alkyl, branched alkyl, cyclic alkyl, substituted or unsubstituted benzyl, silyl, and substituted or unsubstituted aryl groups and exposing the semiconductor substrate comprising a metal surface and a non-metal surface to a second precursor to form the passivation layer on the metal surface, the second precursor having a general formula (II):
R 2 comprising one or more of a linear or branched C 1-24 alkyl, substituted linear or branched C 1-24 alkyl, substituted or unsubstituted C 5-7 cyclic alkyl, and benzyl substituted with alkyl, alkoxy, or thio, and X comprising —NH—, —O—, or —S—; and
repeating the first process cycle n number of times wherein n is an integer in a range of from 1 to 100 to form the metal layer saturated with the passivation layer.
15 . The method of claim 14 , wherein the first precursor and the second precursor react via a nucleophilic addition to form a complex on the metal surface, the complex comprising an acyclic diamino carbene (ADC) of general formula (III):
and the complex is formed in situ on the metal surface.
16 . The method of claim 14 , wherein the first precursor and the second precursor react via a nucleophilic addition to form a complex on the metal surface, the complex comprising a species of general formula (IV):
wherein Y is O if the second precursor is an alcohol or S if the second precursor is a thiol,
and the complex is formed in situ on the metal surface.
17 . The method of claim 14 , wherein the first precursor comprises a linear, branched or cyclic alkyl substituted with one or more electron withdrawing group (EWG) selected from the group consisting of —NO 2 , —CF 3 and sulfonyl or the aromatic ring substituted with one or more electron withdrawing group (EWG) selected from the group consisting of —NO 2 , —CF 3 and sulfonyl.
18 . The method of claim 14 , wherein the isonitrile of general formula (I) is selected from the group consisting of:
19 . The method of claim 14 , wherein the second precursor of general formula (II) is selected from the group consisting of:
wherein n 1 is an integer in a range from 1 to 12, n 2 is an integer in a range from 1 to 3, R 3 is a substituted linear or branched alkyl, R 4 is alkyl or alkoxy, and m is an integer in a range of from 1 to 5.
20 . The method of claim 14 , wherein the second precursor of general formula (II) is a highly nucleophilic amine comprising one or more t-BuNH 2 groups or a secondary amine.