Method of forming high-k dielectric films based on novel titanium, zirconium, and hafnium precursors and their use for semiconductor manufacturing

1. A method of forming on at least one substrate at least one metal containing dielectric film having the formula (M 1 1-a M 2 a ) O b N c , wherein:

0≦a<1

0<b≦3,

0≦c≦1,

M 1 being a metal and M 2 being selected from the group consisting of Mg, Ca, Zn, B, Al, In, Lanthanides, Si, Ge, Sn, Ti, Zr, Hf, V, Nb, and Ta;

said method comprising the steps of:

(a) providing a substrate into a reactor;

(b) introducing into said reactor at least one metal containing precursor selected from the group consisting of Hf(MeCp) 2 Me 2 , HfCp(MeCp)Cl 2 , Hf(MeCp) 2 Cl 2 , HfCp(MeCp)Me 2 , Hf(EtCp)(MeCp)Me 2 , Hf(MeCp) 2 (CO) 2 , Zr(MeCp) 2 Cl 2 , ZrCp(MeCp)Me 2 , Zr(EtCp)(MeCp)Me 2 , Zr(EtCp) 2 Me 2 , Zr(MeCp) 2 (CO) 2 and mixtures thereof;

(c) optionally introducing at least one M 2 containing precursor, M 2 being selected from the group consisting of Mg, Ca, Zn, B, Al, In, Lanthanides, Si, Ge, Sn, Ti, Zr, Hf, V, Nb, and Ta;

(d) providing at least one oxygen containing and/or nitrogen containing fluid into said reactor;

(e) reacting said at least one metal containing precursor with said at least one oxygen containing and/or nitrogen containing fluid; and

(f) depositing said (M 1 1-a M 2 a ) O b N c film onto said substrate at a temperature comprised between 100 to 500° C.

2. The method of claim 1 , wherein the oxygen containing fluid is selected from the group consisting of O 2 , O 3 , H 2 O, H 2 O 2 , oxygen-containing radicals, and mixtures thereof.

3. The method of claim 1 , wherein the nitrogen-containing fluid is selected from the group consisting of N 2 , NH 3 , hydrazine and its alkyl or aryl derivatives, nitrogen-containing radicals, and mixtures thereof.

4. The method of claim 1 , wherein the oxygen and nitrogen-containing fluid is selected from the group consisting of NO, NO 2 , N 2 O, N 2 O 5 , N 2 O 4 and mixtures thereof.

5. The method of claim 1 , wherein the pressure is comprised between 1 Pa and 100 000 Pa.

6. The method of claim 1 , wherein the metal containing precursor, the M 2 containing precursor and the oxygen containing and/or nitrogen containing fluid are introduced simultaneously into the reactor.

7. The method of claim 1 , further comprising the step of providing at least one metal containing precursor containing at least one of the following precursors: M 1 (NMe 2 ) 4 , M 1 (NEt 2 ) 4 , M 1 (NMeEt) 4 , M 1 (mmP) 4 , M 1 (OtBu) 4 , M 1 (OtBu) 2 (mmp) 2 and mixtures thereof.

8. The method of claim 7 , further comprising the steps of mixing together at least two different metal containing precursors A and B to provide a precursor mixture, A being selected from the group consisting of Hf(MeCp) 2 Me 2 , HfCp(MeCp)Cl 2 , Hf(MeCp) 2 Cl 2 , HfCp(MeCp)Me 2 , Hf(EtCp)(MeCp)Me 2 , Hf(MeCp) 2 (CO) 2 , Zr(MeCp) 2 Cl 2 , ZrCp(MeCp)Me 2 , Zr(EtCp)(MeCp)Me 2 , Zr(EtCp) 2 Me 2 , Zr(MeCp) 2 (CO) 2 and mixtures thereof and B being selected from the group consisting of M 1 (NMe 2 ) 4 , M 1 (NEt 2 ) 4 , M 1 (NMeEt) 4 , M 1 (mmp) 4 , M 1 (OtBu) 4 , M 1 (OtBu) 2 (mmp) 2 and mixtures thereof; and providing said metal precursor mixture into said reactor.

9. The method of claim 1 , wherein the at least one metal containing precursor introduced in step b) has a melting point below 50° C.

10. The method of claim 9 , wherein the at least one metal containing precursor is liquid at room temperature.

11. The method of claim 1 , to form an M 1 oxide containing film wherein a=0, b being equal to about 2 and c=0.

12. The method of claim 1 , to form an M 1 oxynitride-containing dielectric film wherein a=0, 1.5≦b≦2.5 and 0<c≦0.5.

13. The method of claim 1 , to form an M 1 M 2 oxide containing dielectric film wherein 0≦a<1 and c=0, the M 2 containing precursor of step (c) being introduced into the reactor, said precursor being selected from the group consisting of Si, Mg and Ta.

14. The method of claim 13 , wherein the M 2 containing precursor is selected from the group consisting of disiloxane, trisilylamine, disilane, trisilane, an alkoxysilane having the formula SiH x (OR 1 ) 4-x , a silanol having the formula_Si(OH) x (OR 1 ) 4-x , an aminosilane having the formula SiH x (NR 1 R 2 ) 4-x , Ta(OMe) 5 , Ta(OEt) 5 , Ta(OR 1 ) 4 (O—C(R 2 )(R 3 )—CH 2 —OR 4 ), Ta(OR 1 ) 4 (O—C(R 2 )(R 3 )—CH 2 —N(R 4 )(R 5 )), Ta(NMe 2 ) 5 , Ta(NEt 2 ) 4 , Ta(NEt 2 ) 5 , Ta(═NR 1 )(NR 2 R 3 ) 3 , an alkylsilyl chain of the form SiR 7 R 8 R 9 where each R i is bonded to silicon, a IVA metal source wherein the M 2 source is different from the M 1 metal source introduced in step b) in the reactor, said IVA metal source being selected from the group consisting of M 1 (OR 1 ) 4 , M(NR 1 R 2 ) 4 , and adducts containing these species, a divalent metal A source having the formula A(—O—C(R 1 )—C(R 2 )—C(R 3 )—O—)(—O—C(R 4 )—C(R 5 )—C(R 6 )—O—), and a cyclopentadienyl divalent metal A source having the formula A(R 1 Cp)(R 2 Cp), wherein each R i is independently selected from the group consisting of H and a C1-C6 carbon chain.

15. The method of claim 1 , to form an M 1 M 2 oxynitride containing dielectric film wherein 0≦a<1 and 0<c≦0.5, the M 2 containing precursor of step (c) being introduced into the reactor, said precursor being selected from the group consisting of Si, Mg and Ta, and wherein in step (d) at least one oxygen containing precursor and at least one nitrogen containing precursor is introduced into the reactor.

16. The method of claim 15 , wherein the M 2 containing precursor is selected from the group consisting of disiloxane, trisilylamine, disilane, trisilane, an alkoxysilane having the formula SiH x (OR 1 ) 4-x , a silanol having the formula_Si(OH) x (OR 1 ) 4-x , an aminosilane having the formula SiH x (NR 1 R 2 ) 4-x , Ta(OMe) 5 , Ta(OEt) 5 , Ta(OR 1 ) 4 (O—C(R 2 )(R 3 )—CH 2 —OR 4 ), Ta(OR 1 ) 4 (O—C(R 2 )(R 3 )—CH 2 —N(R 4 )(R 5 )), Ta(NMe 2 ) 5 , Ta(NEt 2 ) 4 , Ta(NEt 2 ) 5 , Ta(═NR 1 )(NR 2 R 3 ) 3 , an alkylsilyl chain of the form SiR 7 R 8 R 9 where each R i is bonded to silicon, a IVA metal source wherein the M 2 source is different from the M 1 metal source introduced in step b) in the reactor, said IVA metal source being selected from the group consisting of M 1 (OR 1 ) 4 , M(NR 1 R 2 ) 4 , and adducts containing these species, a divalent metal A source having the formula A(—O—C(R 1 )—C(R 2 )—C(R 3 )—O—)(—O—C(R 4 )—C(R 5 )—C(R 6 )—O—), and a cyclopentadienyl divalent metal A source having the formula A(R 1 Cp)(R 2 Cp), wherein each R 1 and R 2 is independently selected from the group consisting of H and a C1-C6 carbon chain.