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

• US 8,399,056 B2
• Filed: 06/02/2006
• Issued: 03/19/2013
• Est. Priority Date: 06/02/2006
• Status: Active Grant

• Current Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Blasco, Nicolas, Dussarrat, Christian
• Primary Examiner(s): CHEN, BRET P
• Application Number:
  US12/303,165
• Publication Number:
  US 20090311879A1
• Time in Patent Office: 2,482 Days
• Field of Search: 427/255.31, 427/355.36, 427/255.394, 427/255.33, 427/255.34, 427/255.35, 427/255.26, 117/84
• US Class Current: 427/255.31
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C07F 7/00 Compounds containing elements of Groups 4 or 14 of the Periodic Table
• CPC Class Codes: C07F 7/003 without C-Metal linkages
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/308 Oxynitrides
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/403 of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/407 of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• CPC Class Codes: H01L 21/02159 the material containing zirconium, e.g. ZrSiOx
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02192 the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
• CPC Class Codes: H01L 21/02194 the material containing more than one metal element
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02216 : the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02271 : deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/0228 : deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/3141 : Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/31641 : Deposition of Zirconium oxides, e.g. ZrO2
• CPC Class Codes: H01L 21/31645 : Deposition of Hafnium oxides, e.g. HfO2

Abstract

A method of forming on at least one support at least one metal containing dielectric films having the formula (M¹_1-a M²_a) O_b N_c, wherein: 0≦a<1, 01 and M² being metals Hf, Zr or Ti using precursors with pentadienyl ligands and/or cyclopentadienyl ligands.

Claims

1. A method of forming on at least one substrate at least one metal containing dielectric film having the formula (M¹_1-a M²_a) O_b N_c, wherein:

0≦

a<

1

0<

b≦

3,

0≦

c≦

1,

M¹ being a metal and M² 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)₂Me₂, HfCp(MeCp)Cl₂, Hf(MeCp)₂Cl₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(MeCp)₂(CO)₂, Zr(MeCp)₂Cl₂, ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂ and mixtures thereof;

(c) optionally introducing at least one M² containing precursor, M² 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 (M¹_1-a M²_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 O₂, O₃, H₂O, H₂O₂, oxygen-containing radicals, and mixtures thereof.

3. The method of claim 1, wherein the nitrogen-containing fluid is selected from the group consisting of N₂, NH₃, 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, NO₂, N₂O, N₂O₅, N₂O₄ 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 M² 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:

M¹(NMe₂)₄, M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmP)₄, M¹(OtBu)₄, M¹(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)₂Me₂, HfCp(MeCp)Cl₂, Hf(MeCp)₂Cl₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(MeCp)₂(CO)₂, Zr(MeCp)₂Cl₂, ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂ and mixtures thereof and B being selected from the group consisting of M¹(NMe₂)₄, M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmp)₄, M¹(OtBu)₄, M¹(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 M¹oxide containing film wherein a=0, b being equal to about 2 and c=0.

12. The method of claim 1, to form an M¹oxynitride-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 M¹M² oxide containing dielectric film wherein 0≦

a<

1 and c=0, the M² 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 M² containing precursor is selected from the group consisting of disiloxane, trisilylamine, disilane, trisilane, an alkoxysilane having the formula SiH_x(OR¹)_4-x, a silanol having the formula_Si(OH)_x(OR¹)_4-x, an aminosilane having the formula SiH_x(NR¹R²)_4-x, Ta(OMe)₅, Ta(OEt)₅, Ta(OR¹)₄(O—

C(R²)(R³)—

CH₂—

OR⁴), Ta(OR¹)₄(O—

C(R²)(R³)—

CH₂—

N(R⁴)(R⁵)), Ta(NMe₂)₅, Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═

NR¹)(NR²R³)₃, an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each Rⁱ is bonded to silicon, a IVA metal source wherein the M² source is different from the M¹ metal source introduced in step b) in the reactor, said IVA metal source being selected from the group consisting of M¹(OR¹)₄, M(NR¹R²)₄, and adducts containing these species, a divalent metal A source having the formula A(—

O—

C(R¹)—

C(R²)—

C(R³)—

O—

)(—

O—

C(R⁴)—

C(R⁵)—

C(R⁶)—

O—

), and a cyclopentadienyl divalent metal A source having the formula A(R¹Cp)(R²Cp), wherein each Rⁱ is independently selected from the group consisting of H and a C1-C6 carbon chain.

15. The method of claim 1, to form an M¹M² oxynitride containing dielectric film wherein 0≦

a<

1 and 0<

c≦

0.5, the M² 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 M² containing precursor is selected from the group consisting of disiloxane, trisilylamine, disilane, trisilane, an alkoxysilane having the formula SiH_x(OR¹)_4-x, a silanol having the formula_Si(OH)_x(OR¹)_4-x, an aminosilane having the formula SiH_x(NR¹R²)_4-x, Ta(OMe)₅, Ta(OEt)₅, Ta(OR¹)₄(O—

C(R²)(R³)—

CH₂—

OR⁴), Ta(OR¹)₄(O—

C(R²)(R³)—

CH₂—

N(R⁴)(R⁵)), Ta(NMe₂)₅, Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═

NR¹)(NR²R³)₃, an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each Rⁱ is bonded to silicon, a IVA metal source wherein the M² source is different from the M¹ metal source introduced in step b) in the reactor, said IVA metal source being selected from the group consisting of M¹(OR¹)₄, M(NR¹R²)₄, and adducts containing these species, a divalent metal A source having the formula A(—

O—

C(R¹)—

C(R²)—

C(R³)—

O—

)(—

O—

C(R⁴)—

C(R⁵)—

C(R⁶)—

O—

), and a cyclopentadienyl divalent metal A source having the formula A(R¹Cp)(R²Cp), wherein each R¹ and R² is independently selected from the group consisting of H and a C1-C6 carbon chain.