METHOD OF FORMING HIGH-K DIELECTRIC FILMS BASED ON NOVEL TITANIUM, ZIRCONIUM, AND HAFNIUM PRECURSORS AND THEIR USE FOR SEMICONDUCTOR MANUFACTURING

• US 20090311879A1
• Filed: 06/02/2006
• Published: 12/17/2009
• 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: Dussarrat, Christian, Blasco, Nicolas
• Granted Patent: US 8,399,056 B2
• Time in Patent Office: Days
• US Class Current: 438/785
• 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

1-21. -21. (canceled)

22. :

A method of forming on at least one support at least one metal containing dielectric films having the formula (M¹_1-a, a M²_a) O_b N_c, wherein;

0≦

a<

1

0<

b≦

3, preferably 1.5≦

b≦

2.5

0≦

c≦

1, preferably 0≦

c≦

0.5

M¹ and M² being metals

said method comprising the steps of;

(a) providing a substrate into a reactor; and

(b) introducing into said reactor at least one metal containing precursor having the formula;

(R_yOp)_x(R_tCp)_zM¹R′

_4-x-z

 

wherein;

M¹=Hf, Zr and/or Ti;

(R_yOp) represents one pentadienyl (Op) ligand, substituted or not, with y R substituents in any position on Op;

(R_tCp) represents one cyclopentadienyl (Cp) ligand, substituted or not, with t R substituents in any position on Cp;

Each R substituting the pentadienyl or R substituting the cyclopentadienyl is a substituent independently selected from the group consisting of Cl, C1-C4 linear or branched, alkyl, alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl, each R substituting the pentadienyl or each R substituting the cyclopentadienyl being similar to or different from other R substituting the pentadienyl or other R substituting the cyclopentadienyl, respectively;

Each R′

is a ligand independently selected from the group consisting of H, a halogen (F, Cl, Br, I), C1-C4 linear or branched, alkyl, alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl, each R′

being similar or different;

x is an integer representing the number of pentadienyl (Op) ligand, substituted or not;

z is an integer representing the number of cyclopentadienyl (Cp) ligand, substituted or not;

y is an integer representing the number of substituents on each Op, and is independently selected for each Op;

t is an integer representing the number of substituents on each Cp, and is independently selected for each Cp;

0≦

x≦

3, preferably x=0 or 1;

0≦

z≦

3, preferably z=2;

0≦

y≦

7, preferably y=2 and in this case each R is methyl;

0≦

t≦

5, preferably t=1 and R is a methyl group; and

Unspecified substituents to Op or Op ligands are H by default;

(c) optionally introducing at least one M² containing precursor, M² being selected from the group essentially consisting of Mg, Ca, Zn, B, Al, In, Lanthanides (Sc, Y, La and other rare earths), Si, Ge, Sn, Ti, Zr, Hf, V, Nb, 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., preferably between 150°

C. and 350°

C.,

provided that when a=0, b=2, c=0, x=0, z=2, at least one t on at least one Cp is different from zero.

23. :

The method of claim 22, wherein the oxygen containing fluids are selected from the group consisting of O₂, 03, H₂O, H₂O₂, oxygen-containing radicals such as O. or OH. and mixtures thereof.

24. :

The method of claim 22, wherein the nitrogen-containing fluids are selected from the group consisting of N₂, NH₃, hydrazine and its alkyl or aryl derivatives, nitrogen-containing radicals such as N., NH., NH₂. and mixtures thereof.

25. :

The method of claim 22, wherein the oxygen and nitrogen-containing fluids are selected from the group consisting of NO, NO₂, N₂O, N₂O₅, N₂O₄ and mixtures thereof.

26. :

The method of claim 22, wherein the pressure is comprised between 1 Pa and 100000 Pa, preferably 25 Pa and 1000 Pa.

27. :

The method of claim 22, wherein the various reactants can be introduced simultaneously (chemical vapor deposition), sequentially (atomic layer deposition) or combinations of continuous and pulse introduction of each precursor.

28. :

The method of claim 22, wherein further comprising the step of;

(g) 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.

29. :

The method of claim 22, wherein the at least one metal containing precursor introduced in step b) has a melting point below 50 C, preferably below 35°

C.

30. :

The method of claim 29, wherein the at least one metal containing precursor is liquid at room temperature.

31. :

The method of claim 22, further comprising the step of;

(h) mixing together at least two different metal containing precursors A and B to provide a precursor mixture, A being (R_yOp)_x(R_tCp)_zM¹R′

_4-x-z, and B being selected from the group consisting of (R_yOp)_x(R_tCp)_zM¹R′

_4-x-z M¹(NMe₂)₄, M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmp)₄, M¹(OtBu)₄, M¹(OtBu)₂(mmp)₂ and mixtures thereof; and

(i) providing said metal precursor mixture into said reactor.

32. :

The method of claim 31 wherein step (h) and (i) are carried out instead of step (b).

33. :

The method of claim 22, to form an M¹oxyde containing film wherein a=0, b being equal to about 2 and c=0, the metal containing precursor of steps (b) and/or (h) being selected from the group consisting of;

Hf(MeCp)₂Me₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂ and mixtures thereof.

34. :

The method of claim 22, to form an M¹oxynitride-containing dielectric film wherein a=0, 1.5≦

b≦

2.5 and 0<

c≦

0.5, the metal containing precursor of step (b) and/or (h) being selected from the group consisting of HfCp₂Me₂, Hf(MeCp)₂Me₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂.

35. :

The method of claim 22, to form an M¹M² oxide containing dielectric film wherein 0≦

a<

1 and c=0, the metal containing precursor of step (b) and/or (h) being selected from the group consisting of HfCp₂Me₂, Hf(MeCp)₂Me₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂ the M² containing precursor of step (c) being introduced into the reactor, said precursor being preferably selected from the group consisting of Si, Mg and/or Ta.

36. :

The method of claim 35, wherein the M² containing precursor is selected from the group consisting of disiloxane, trisilylamine, disilane, trisilane, alkoxysilane SiH_x(OR¹)_4-x, silanol Si(OH)_x(OR¹)_4-x (preferably Si(OH)(OR¹)₃;

more preferably Si(OH)(OtBu)₃ aminosilane SiH_x(NR¹R²)_4-x (where x is comprised between 0 and 4;

R¹ and R² are independently selected from the group consisting of H or a C1-C6 carbon chain, either linear, branched or cyclic;

preferably TriDMAS SiH(NMe₂)₃;

BTBAS SiH₂(NHtBu)₂;

BDEAS SiH₂(NEt₂)₂), (or their germanium equivalent and mixtures thereof, trimethylaluminum, dimethylaluminum hydride, an alkoxyalane AlRⁱ_x(OR′

)_3-x (where x is comprised between 0 and 4;

R¹ and R² are independently H or a C1-C6 carbon chain, either linear, branched or cyclic;

preferably AlR¹R²(OR′

), most preferably AlMe₂(OiPr)), amidoalane AlRⁱ_x(NR′

R″

)_3-x (where x is comprised between 0 and 4;

R¹ and R² are independently H or a C1-C6 carbon chain, either linear, branched or cyclic), Ta(OMe)₅, Ta(OEt)₅, Ta(OR¹)₄(O—

C(R²)(R³)—

CH₂—

OR⁴) (each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic, preferably TAT-DMAE Ta(OEt)(OCMe₂CH₂—

OMe)), Ta(OR¹)₄(O—

C(R²)(R³)—

CH₂—

N(R⁴)(R⁵)) (each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic, Ta(NMe₂)₅, Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═

NR¹)(NR²R³)₃ (each R¹ and R² are independently H or a C1-C6 carbon chain, either linear, branched or cyclic and where the amino ligand can have different substituent) and each of their niobium counterparts, a lanthanide metal source (Sc, Y, La, Ce, Pr, Nd, Gd . . . ) source with at least one β

-diketonate ligand, such as of the form Ln(—

O—

C(R¹)—

C(R²)—

C(R³)—

O—

)(—

O—

C(R⁴)—

C(R⁵)—

C(R⁶)—

O—

)(—

O—

C(R⁷)—

C(R⁸)—

C(R⁹)—

O—

) where each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic), or of the form of a cyclopentadienyl lanthanide Ln(R¹Cp)(R²Cp)(R³Cp) (where each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic), Ln(NR¹R²)(NR³R⁴)(NR⁵R⁶) (where each Rⁱ is bonded to nitrogen and is independently H or a C1-C6 carbon chain, either linear, branched or cyclic or an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each Rⁱ is bonded to silicon and is independently H or a C1-C4 carbon chain, either linear, branched or cyclic), a IVA metal source with M² is similar or different from M¹ but in which the M² source is different from the M¹ metal source introduced in step b) in the reactor, said IVA metal source being selected from (R_yOp)_x(R_tCp)_zM¹R′

_4-x-z, M¹(OR¹)₄ or other alkoxide-containing metal sources, M(NR¹R²)₄, or adducts containing these species. a divalent metal A source (preferably Mg, Ca, Zn) of the form A(—

O—

C(R¹)—

C(R²)—

C(R³)—

O—

)(—

O—

C(R⁴)—

C(R⁵)—

C(R⁶)—

O—

) (where each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic) or of the form of a cyclopentadienyl lanthanide A(R¹Cp)(R²Cp) (where each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic).

37. :

The method of claim 22, to form an M¹M² oxynitride containing dielectric film wherein 0≦

a<

1 and 0<

c≦

0.5, the metal containing precursor of step (b) and/or (h) being selected from the group consisting of HfCp₂Me₂, Hf(MeCp)₂Me₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂, the M² containing precursor of step (c) being introduced into the reactor, said precursor being preferably selected from the group consisting of Si, Mg and/or Ta, and wherein in step (d) at least one oxygen containing precursor and at least one nitrogen containing precursor is introduced into the reactor.

38. :

The method of claim 37, wherein the M² containing precursor is selected from the group consisting of disiloxane, trisilylamine, disilane, trisilane, a alkoxysilane SiH_x(OR¹)_4-x, a silanol Si(OH)_x(OR¹)_4-x (preferably Si(OH)(OR¹)₃;

more preferably Si(OH)(OtBu)₃ an aminosilane SiH_x(NR¹R²)_4-x (where x is comprised between 0 and 4;

R¹ and R² are independently H or a C1-C6 carbon chain, either linear, branched or cyclic;

preferably TriDMAS SiH(NMe₂)₃;

BTBAS SiH₂(NHtBu)₂);

BDEAS SiH₂(NEt₂)₂) and mixtures thereof (or their germanium equivalent), trimethylaluminum, dimethylaluminum hydride, an alkoxyalane AlRⁱ_x(OR′

)_3-x (where x is comprised between 0 and 4;

R¹ and R² are independently H or a C1-C6 carbon chain, either linear, branched or cyclic;

preferably AlR¹R²(OR′

), most preferably AlMe₂(OiPr)), an amidoalane AlRⁱ_x(NR′

R″

)_3-x (where x is comprised between 0 and 4;

R¹ and R² are independently H or a C1-C6 carbon chain, either linear, branched or cyclic), Ta(OMe)₅, Ta(OEt)₅, Ta(OR¹)₄(O—

C(R²)(R³)—

CH₂—

OR⁴) (each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic, preferably TAT-DMAE Ta(OEt)(OCMe₂CH₂—

OMe)), Ta(OR¹)₄(O—

C(R²)(R³)—

CH₂—

N(R⁴)(R⁵)) (each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic, Ta(NMe₂)₅, Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═

NR¹)(NR²R³)₃ (each R¹ and R² are independently H or a C1-C6 carbon chain, either linear, branched or cyclic and where the amino ligand can have different substituent), and each of their niobium counterparts, a lanthanide metal source (Sc, Y, La, Ce, Pr, Nd, Gd . . . ) source with at least one β

-diketonate ligand, such as of the form Ln(—

O—

C(R¹)—

C(R²)—

C(R³)—

O—

)(—

O—

C(R⁴)—

C(R⁵)—

C(R⁶)—

O—

)(—

O—

C(R⁷)—

C(R⁸)—

C(R⁹)—

O—

) where each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic), or of the form of a cyclopentadienyl lanthanide Ln(R¹Cp)(R²Cp)(R³Cp) (where each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic), Ln(NR¹R²)(NR³R⁴)(NR⁵R³) (where each Rⁱ is bonded to nitrogen and is independently H or a C1-C6 carbon chain, either linear, branched or cyclic or an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each Rⁱ is bonded to silicon and is independently H or a C1-C4 carbon chain, either linear, branched or cyclic), a IVA metal source with M² is similar or different from M¹ but in which the M² source is different from the M¹ metal source introduced in step b) in the reactor, said IVA metal source being selected from (R_yOp)_x(R_tCp)_zM¹R′

_4-x-z, M¹(OR¹)₄ or other alkoxide-containing metal sources, M(NR¹R²)₄, or adducts containing these species. a divalent metal A source (preferably Mg, Ca, Zn) of the form A(—

O—

C(R¹)—

C(R²)—

C(R³)—

O—

)(—

O—

C(R⁴)—

C(R⁵)—

C(R⁶)—

O—

) (where each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic) or of the form of a cyclopentadienyl lanthanide A(R¹Cp)(R²Cp) (where each Rⁱ is independently H or a C1-C6 carbon chain, either linear, branched or cyclic).

39. :

A new precursor comprising composition for semi-conductor or RAM manufacture, said precursor having the formula;

(R_yOp)_x(R_tCp)_zM¹R′

_4-x-z

wherein;

M¹=Hf, Zr and/or Ti;

(R_yOp) represents one pentadienyl (Op) ligand, substituted or not, with y R in any position on Op;

(R_tCp) represents one cyclopentadienyl (Cp) ligand, substituted or not, with t R in any position on Cp;

Each R substituting the pentadienyl or R substituting the cyclopentadienyl are substituents independently selected from the group consisting of C1-C4 linear or branched, alkyl, alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl, each R substituting the pentadienyl or each R substituting the cyclopentadienyl being similar to or different from other R substituting the pentadienyl or other R substituting the cyclopentadienyl, respectively;

Each R′

is a ligand independently selected from the group consisting of C1-C4 linear or branched, alkyl, alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl, each R′

being similar or different;

x is an integer representing the number of pentadienyl ligand, substituted or not;

z is an integer representing the number of cyclopentadienyl ligand, substituted or not;

y is an integer representing the number of substituents on each Op, and is independent by selected for each Op;

t is an integer representing the number of substituents on each Cp, and is independent selected for each Cp;

0≦

x≦

3, preferably x=0 or 1;

0≦

z≦

3, preferably z=2;

0≦

y≦

7, preferably y=2 and in this case each R is methyl;

0≦

t≦

5, preferably t=1 and R is a methyl group;

Unspecified substituents to Cp or Op ligands are H by default; and

All R′

are not simultaneously equal to H when x=0,

provided that when a=0, b=2, c=0, x=0, z=2, at least one t on at least one Cp is different from zero.

40. :

The new precursor comprising composition of claim 39, wherein it further comprises a second metal containing precursor, different from the first metal precursor, said second metal containing precursor being selected from the group consisting of (R_yOp)_x(R_tCp)_zM¹R′

_4-x-z, M¹(NMe₂)₄, M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmp)₄, M¹ (OtBu)₄, M¹ (OtBu)₂(mmp)₂ and mixtures thereof.

41. :

The new precursor composition of claim 39, wherein the precursor melting point is lower than or equal to 50°

C.