Method of forming dielectric films, new precursors and their use in semiconductor manufacturing
Method of deposition on a substrate, of a metal containing dielectric film comprising a compound of the formula (I): (M 1 1-a M 2 a )O b N c , (I) wherein 0≦a<1, 0<b≦3, 0≦c≦1, M 1 represents a metal selected from (Hf), (Zr) and (Ti); and M 2 represents a metal atom atoms, which comprises the following steps: A step a) of providing a substrate into a reaction chamber; A step (b) of vaporizing a M 1 metal containing precursor of the formula (II): (R 1 y Op) x (R 2 t Cp) z M 1 R′ 4-x-z (II) wherein 0≦x≦3, preferably x=0 or 1, 0≦z≦3, preferably z=1 or 2, 1≦(x+z)≦4, 0≦y≦7, preferably y=2 0≦t≦5, preferably t=1, (R 1 y Op) represents a pentadienyl ligand, which is either unsubstituted or substituted; (R 2 t Cp) represents a cyclopentadienyl (Cp) ligand, which is either unsubstituted or substituted, to form a first gas phase metal source; A step c) of introducing the first gas phase metal source in the reaction chamber, in order to provoke their contact with said substrate, to generate the deposition of a metal containing dielectric film comprising a compound of the formula (I) as hereinbefore defined, on said substrate. Compound the formula (II 1 ): (R 2 t Cp)M 1 [N(R 39 )(R 40 )] 3 (II 1 ) corresponding to the formula (II) as hereinabove defined in Claim 1 , wherein x=0, z=1 and R′ represents the group N(R 39 )(R 40 ).
1. A method of deposition on a substrate, of at least one metal containing dielectric film comprising a compound of the formula (I):
(M 1 1-a M 2 a )O b N c , (I)
wherein:
0≦a<1,
0<b≧3;
0≦c≦1,
M 1 is zirconium (Zr); and
M 2 represents a metal atom selected from magnesium (Mg), calcium (Ca), zinc (Zn), boron (B), aluminum (Al), indium (In), silicon (Si), germanium (Ge), tin (Sn), hafnium (Hf), zirconium (Zr), titanium (Ti), vanadium (V), niobium (Nb), tantalum (Ta); and the Lanthanides atoms and rare-earth metal atoms,
which comprises the following steps:
a step a) of providing a substrate into a reaction chamber;
a step b) of vaporizing at least one M 1 metal containing precursor to form a first gas phase metal source, the at least one M 1 metal containing precursor is selected from the group consisting of Zr(MeCp)(NMe 2 ) 3 , Zr(EtCp)(NMe 2 ) 3 , ZrCp(NMe 2 ) 3 , Zr(MeCp)(NEtMe) 3 , Zr(EtCp)(NEtMe) 3 , ZrCp(NEtMe) 3 , Zr(MeCp)(NEt 2 ) 3 , Zr(EtCp)(NEt 2 ) 3 , ZrCp(NEt 2 ) 3 , Zr(iPr 2 Cp)(NMe 2 ) 3 , and Zr(tBu 2 Cp)(NMe 2 ) 3 ;
optionally a step b′) of vaporizing at least one M 2 metal containing precursor, M 2 being as hereinabove defined, to form an optional second gas phase metal source;
a step c) of introducing said first gas phase metal source and said optional second gas phase metal source, in the reaction chamber, in order to provoke their contact with said substrate, to generate the deposition of a metal containing dielectric film comprising a compound of the formula (I) as hereinbefore defined, on said substrate.
2. The method of claim 1 , wherein the vaporization step b) and the vaporization step b′) are combined in one vaporization step b″) of both sources.
3. The method of claim 1 , wherein the M 2 metal containing precursor, is selected from the group consisting of:
silicon derivatives or their germanium homologues;
silanol derivative of the formula (III 2 ):
Si(OH) x (OR 4 ) 4-x (III 2 )
wherein: 1≦x≦3 and R 4 represents a linear or branched alkyl group, having 1 to 6 carbon atoms;
aminosilane derivative of the formula (III 3 ):
SiH x (NR 5 R 6 ) 4-x (III 3 )
wherein; 0≦x≦3 and R 5 and R 6 are identical or different and independently represents an hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms;
aluminum derivatives;
amidoalane of the formula (IV 2 ):
AlR 11 (NR 12 R 13 ) 3-x (IV 2 )
wherein: 0≦x≦3 and R 12 and R 13 identical or different, represent an hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms, and R 11 , identical to or different from R 7 and, represents an hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms;
tantalum derivatives;
Niobium derivatives;
lanthanide derivatives;
divalent metal derivatives;
and other metal derivatives.
4. The method of claim 3 , wherein the metal containing dielectric film comprises a compound of the formula (I 3 ):
(M 1 1-a M 2 a )O b (I 3 )
corresponding to the formula (I), wherein 0≦a<1 and c=0, wherein the M 2 metal containing precursor is selected from the silicon derivatives or their germanium homologues, the tantalum derivatives, lanthanide derivatives, or the magnesium derivatives as hereabove defined.
5. The method of claim 3 , wherein the metal containing dielectric film comprises a compound of the formula (I 4 ):
(M 1 1-a M 2 a )O b N c (I 4 )
corresponding to the formula (I), wherein 0≦a<1 and 0<c≦0.5, wherein the M 2 metal containing precursor is selected from the silicon derivatives or their germanium homologues, the tantalum derivatives, lanthanide derivatives, or the magnesium derivatives as hereabove defined, and at least one oxygen containing precursor and at least one nitrogen containing precursor is introduced into the reactor.
6. The method of claim 3 , wherein the silicon derivatives or their germanium homologues are selected from the group consisting of disiioxane, digermoxane, trisilylamine, trigermylamine, disilane, digermane, trisilane, trigermane, alkoxysilane having the formula Si H x (OR 3 ) 4-x , and alkoxygermane having the formula Ge H x (OR 3 ) 4-x , wherein: 0≦x≦3 and R 3 represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms.
7. The method of claim 3 , wherein the silanol derivative is Si(OH)(OtBu) 3 .
8. The method of claim 3 , wherein the aminosilane derivative is selected from the group consisting of tris(dimethylamino)silane [SiH(NMe 2 ) 3 ], bis(tertbutylamino)silane [SiH 2 (NHtBu) 2 ], bis(diethylamino)silane [SiH 2 (NEt 2 ) 2 ], and mixtures thereof.
9. The method of claim 3 , wherein the aluminum derivative is selected from the group consisting of trimethylaluminum [Al(CH 3 ) 3 ], dimethyl aluminum hydride [AlH(CH 3 ) 2 ], and alkoxyalane having the formula AlR 8 x (OR 7 ) 3-x , wherein 0≦x≦3, R 7 represents a linear or branched alkyl group having 1 to 6 carbon atom, and R 8 , identical to or different from R 7 , represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
10. The method of claim 9 , wherein the aluminum derivative is AlMe 2 (OiPr).
11. The method of claim 3 , wherein the tantalum derivative is selected from the group consisting of Ta(OMe) 5 ; Ta(OEt) 5 ; Ta(NMe 2 ) 5 ; Ta(NEt 2 ) 5 ; a tantalum derivative having the formula Ta(OR 14 ) 4 [O—C(R 15 )(R 16 )—CH 2 —OR 17 ],
wherein R 14 , R 15 , R 16 and R 17 , identical or different, independently represent a hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms; a tantalum derivative having the formula Ta(OR 18 ) 4 [O—C(R 19 )(R 20 )—CH 2 —N(R 21 )(R 22 )], wherein R 18 , R 19 , R 21 and R 22 , identical or different, independently represent a hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms; and a tantalum derivative having the formula Ta(═NR 24 )(NR 25 R 26 ) 3 , wherein R 24 , R 25 and R 26 , identical or different, independently represent an hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms.
12. The method of claim 11 , wherein the tantalum derivative is Ta(OEt) 4 (OCMe 2 CH 2 —OMe).
13. The method of claim 3 , wherein the niobium derivative is selected from the group consisting of Nb(OMe) 5 ; Nb(OEt) 5 ; Nb(NMe 2 ) 5 ; Nb(NEt 2 ) 4 ; Nb(NEt 2 ) 5 ; a niobium derivative having the formula Nb(OR 27 ) 4 (O—C(R 28 )(R 29 )—CH 2 —OR 30 ),
wherein R 27 , R 28 , R 29 and R 30 , identical or different, independently represent a hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms; a niobium derivative having the formula Nb(OR 31 ) 4 [O—C(R 32 )(R 33 )—CH 2 —N(R 34 )(R 35 )], wherein R 31 , R 32 , R 33 , R 34 and R 35 , identical or different, independently represent a hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms; and a niobium derivative having the formula Nb(═NR 36 )(NR 37 R 38 ) 3 , wherein R 36 , R 37 and R 38 , identical or different, independently represent an hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms.
14. The method of claim 13 , wherein the niobium derivative is Nb(OEt) 4 (OCMe 2 CH 2 —OMe).
15. The method of claim 3 , wherein the M 2 metal containing precursor is a hafnium derivative.
16. The method of claim 1 , which further comprises:
A step d), wherein the at least one M 1 metal containing precursor and optionally the at least one M 2 metal containing precursor, is mixed to at least one reactant species prior to step c).
17. The method of claim 1 , which further comprises:
a step d′) wherein the at least one M 1 metal containing precursor and optionally the at least one M 2 metal containing precursor, is mixed to at least one reactant species in the reaction chamber.
18. The method of claim 1 , wherein the metal containing dielectric film comprises a compound of the formula (I 1 ):
M 1 O 2 (I 1 )
corresponding to the formula (I), wherein a=0, b=2 and c=0.
19. The method of claim 1 , wherein the metal containing dielectric film comprises a compound of the formula (I 2 ):
M 1 O b N c , (I 2 )
corresponding to the formula (I), wherein a=0, 1.5≦b≦2.5 and 0<c≦0.5.
20. The method of claim 1 , wherein the at least one M 1 metal containing precursor is ZrCp(NMe 2 ) 3 .
21. The method of claim 1 , wherein the at least one M 1 metal containing precursor is Zr(MeCp)(NMe 2 ) 3 .
22. The method of claim 1 , wherein the at least one M metal containing precursor is Zr(EtCp)(NMe 2 ) 3 .