Method of forming dielectric films, new precursors and their use in semiconductor manufacturing

Patent metadata

Field	Value
Publication number	US-9583335-B2
Application number	US-201414187712-A
Country	US
Kind code	B2
Filing date	Feb 24, 2014
Priority date	Jun 2, 2006
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

Method of deposition on a substrate of a dielectric film by introducing into a reaction chamber a vapor of a precursor 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 , Zr(tBu 2 Cp)(NMe 2 ) 3 , Hf(MeCp)(NMe 2 ) 3 , Hf(EtCp)(NMe 2 ) 3 , HfCp(NMe 2 ) 3 , Hf(MeCp)(NEtMe) 3 , Hf(EtCp)(NEtMe) 3 , HfCp(NEtMe) 3 , Hf(MeCp)(NEt 2 ) 3 , Hf(EtCp)(NEt 2 ) 3 , HfCp(NEt 2 ) 3 , Hf(iPr 2 Cp)(NMe 2 ) 3 , Hf(tBu 2 Cp)(NMe 2 ) 3 , and mixtures thereof; and depositing the dielectric film on the substrate.

First claim

What is claimed is:

1. A method of depositing a dielectric film on a substrate, the method comprising introducing into a reaction chamber a vapor of a precursor 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 , Zr(tBu 2 Cp)(NMe 2 ) 3 , Hf(MeCp)(NMe 2 ) 3 , Hf(EtCp)(NMe 2 ) 3 , HfCp(NMe 2 ) 3 , Hf(MeCp)(NEtMe) 3 , Hf(EtCp)(NEtMe) 3 , HfCp(NEtMe) 3 , Hf(MeCp)(NEt 2 ) 3 , Hf(EtCp)(NEt 2 ) 3 , HfCp(NEt 2 ) 3 , Hf(iPr 2 Cp)(NMe 2 ) 3 , Hf(tBu 2 Cp)(NMe 2 ) 3 , and mixtures thereof; and
depositing the dielectric film on the substrate.

2. The method of claim 1 , wherein the dielectric film is M 1 O 2 , wherein M 1 is Hf, Zr, or mixtures thereof.

3. The method of claim 1 , wherein the dielectric film is M 1 O b N c , wherein 1.5≦b≦2.5, 0<c≦0.5, and M 1 is Hf, Zr, or mixtures thereof.

4. The method of claim 1 , wherein the dielectric film is (M 1 1-a M 2 a )O b N c , wherein 0≦a<1; 0<b≦3; 0<c≦0.5; M 1 is Hf, Zr, or mixtures thereof; and M 2 is selected from the group consisting of 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), a Lanthanide atoms, and a rare-earth atom.

5. The method of claim 1 , wherein the dielectric film is (M 1 1-a M 2 a )O b , wherein 0≦a<1; 0<b≦3; M 1 is Hf, Zr, or mixtures thereof; and M 2 is selected from the group consisting of 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), a Lanthanide atoms, and a rare-earth atom.

6. The method of claim 5 , further comprising introducing into a reaction chamber a vapor of a M 2 containing precursor to form the (M 1 1-a M 2 a )O b dielectric film, wherein the M 2 containing precursor is an aluminum derivative selected from the group consisting of an alkoxyalane having the formula AlR 1 x (OR 2 ) 3-x , wherein 0≦x≦3, R 1 represents a linear or branched alkyl group having 1 to 6 carbon atom, and R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; and an amidoalane having the formula AlR 3 y (NR 4 R 5 ) 3-y , wherein 0≦y≦3 and each R 3 , R 4 , and R 5 is independently selected from a hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms.

7. The method of claim 6 , wherein the M 2 containing precursor is trimethylaluminum [Al(CH 3 ) 3 ], dimethyl aluminum hydride [AlH(CH 3 ) 2 ], or AlMe 2 (OiPr).

8. The method of claim 5 , further comprising introducing into a reaction chamber a vapor of a M 2 containing precursor to form the (M 1 1-a M 2 a )O b dielectric film, wherein the M 2 containing precursor has the following formula:
(R 1 y Op) x (R 2 t Cp) z M 2 R′ 4-x-z

wherein:
M 2 is Ti, Hf, or Zr;
0≦x≦3;
0≦z≦3;
1≦(x+z)≦4;
0≦y≦7;
0≦t≦5;
(R 1 y Op) represents a pentadienyl (Op) ligand substituted by y R 1 groups;
(R 2 t Cp) represents a cyclopentadienyl (Cp) ligand substituted by t R 2 groups;
each R 1 and R 2 is independently selected from the group consisting of chlorine; a linear or branched alkyl group having from one to four carbon atoms; a N-alkyl amino group, wherein the alkyl group is linear or branched and has from one to four carbon atoms; a N,N-dialkyl amino group wherein each alkyl group, identical or different from the other, is linear or branched and has from one to four carbon atoms; a linear or branched alkoxy group having from one to four carbon atoms; an alkylsilylamide group; an amidinate group; and a carbonyl group;
each R′ is independently selected from the group consisting of hydrogen; fluorine; chlorine; bromine; iodine; a linear or branched alkyl group having from one to four carbon atoms; a N-alkyl amino group, wherein the alkyl group is linear or branched and has from one to four carbon atoms; a N,N-dialkyl amino group, wherein each alkyl group, identical or different from the other, is linear or branched and has from one to four carbon atom; a linear or branched alkoxy group having from one to four carbon atoms; an alkylsilyl amino group, wherein the alkyl group is linear or branched and has from one to four carbon atoms; a dialkylsilyl amino group, wherein each alkyl group, identical or different from the other, is linear or branched and has from one to four carbon atoms; a trialkylsilyl amino group, wherein each alkyl group, identical or different from the other, is linear or branched and has from one to four carbon atoms; an amidinates group; and a carbonyl group.

9. The method of claim 8 , wherein the M 2 containing precursor is selected from the group consisting of HfCp 2 Cl 2 , Hf(MeCp) 2 Me 2 , HfCp(MeCp)Cl 2 , Hf(MeCp) 2 Cl 2 , HfCp(MeCp)Me 2 , Hf(EtCp)(MeCp)Me 2 , Hf(EtCp) 2 Me 2 , Hf(MeCp) 2 (CO) 2 , ZrCp 2 Cl 2 , Zr(MeCp) 2 Me 2 , ZrCp(MeCp)Cl 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 , 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 , Zr(tBu 2 Cp)(NMe 2 ) 3 , Hf(MeCp)(NMe 2 ) 3 , Hf(EtCp)(NMe 2 ) 3 , HfCp(NMe 2 ) 3 , Hf(MeCp)(NEtMe) 3 , Hf(EtCp)(NEtMe) 3 , HfCp(NEtMe) 3 , Hf(MeCp)(NEt 2 ) 3 , Hf(EtCp)(NEt 2 ) 3 , HfCp(NEt 2 ) 3 , Hf(iPr 2 Cp)(NMe 2 ) 3 , Hf(tBu 2 Cp)(NMe 2 ) 3 and mixtures thereof.

10. The method of claim 5 , further comprising introducing into a reaction chamber a vapor of a M 2 containing precursor to form the (M 1 1-a M 2 a )O b dielectric film, wherein the M 2 containing precursor is a niobium derivative selected from the group consisting of Nb(OMe) 5 ; Nb(OEt) 5 ; Nb(NMe 2 ) 5 ; Nb(NEt 2 ) 4 ; Nb(NEt 2 ) 5 ; 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 an hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms; 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 an hydrogen atom or a linear or branched alkyl having 1 to 6 carbon atoms; and 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.

11. The method of claim 10 , wherein the M 2 containing precursor is Nb(OMe) 5 , Nb(OEt) 5 , Nb(NMe 2 ) 5 , Nb(NEt 2 ) 4 , Nb(NEt 2 ) 5 , or Nb(OEt) 4 (OCMe 2 CH 2 —OMe).

12. The method of claim 5 , further comprising introducing into a reaction chamber a vapor of a M 2 containing precursor to form the (M 1 1-a M 2 a )O b dielectric film, wherein the M 2 containing precursor is a lanthanide derivative with at least one beta diketonate ligand or at least one cyclopentadienyl ligand.

13. The method of claim 1 , wherein the precursor is selected from ZrCp(NMe 2 ) 3 , HfCp(NMe 2 ) 3 , and mixtures thereof.

14. The method of claim 13 , wherein the dielectric film is M 1 O 2 , wherein M 1 is Hf, Zr, or mixtures thereof.

15. The method of claim 13 , wherein the dielectric film is (M 1 1-a M 2 a )O b , wherein 0≦a<1; 0<b≦3; M 1 is Hf, Zr, or mixtures thereof; and M 2 is selected from the group consisting of magnesium (Mg), calcium (Ca), zinc (Zn), boron (B), aluminum (Al),

Assignees

• L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude

Inventors

• Dussarrat Christian
• Blasco Nicolas
• Pinchart Audrey
• Lachaud Christophe

Classifications

• H10P14/69397

  the material containing two or more metal elements · CPC title

• H10P14/69396

  the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium · CPC title

• H10P14/69392

  the material containing hafnium, e.g. HfO2 · CPC title

• H10P14/6339

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• H10P14/6334

  using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition (deposition by physical ablation of a target H10P14/6329) · CPC title