Precursor source mixtures

• US 6,984,591 B1
• Filed: 04/20/2000
• Issued: 01/10/2006
• Est. Priority Date: 04/20/2000
• Status: Expired due to Term

• Current Assignee: GlobalFoundries, Inc.
• Original Assignee: International Business Machines Corporation
• Inventors: Neumayer, Deborah Ann, Buchanan, Douglas A.
• Primary Examiner(s): Zarabian, Amir
• Assistant Examiner(s): BRYANT, KIESHA ROSE
• Application Number:
  US09/553,997
• Time in Patent Office: 2,091 Days
• Field of Search: 438/778, 438/680, 438/681, 438/643, 257/751, 257/295
• US Class Current: 438/778
• CPC Class Codes: C23C 16/16 from metal carbonyl compounds
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/401 containing silicon
• 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 16/42 Silicides
• CPC Class Codes: C23C 16/4485 by evaporation without using carrier gas in contact with the source material C23C16/4486 takes precedence
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• 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 21/02183 the material containing tantalum, e.g. Ta2O5
• CPC Class Codes: H01L 21/02186 the material containing titanium, e.g. TiO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• 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 21/0228 : deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/28194 : by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/28556 : by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/288 : from a liquid, e.g. electrolytic deposition
• CPC Class Codes: H01L 21/3141 : Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/3142 : of nano-laminates, e.g. alternating layers of Al203-Hf02
• CPC Class Codes: H01L 21/31616 : Deposition of Al2O3
• 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
• CPC Class Codes: H01L 21/823462 : with a particular manufacturing method of the gate insulating layers, e.g. different gate insulating layer thicknesses, particular gate insulator materials or particular gate insulator implants
• CPC Class Codes: H01L 21/823828 : with a particular manufacturing method of the gate conductors, e.g. particular materials, shapes
• CPC Class Codes: H01L 21/823857 : with a particular manufacturing method of the gate insulating layers, e.g. different gate insulating layer thicknesses, particular gate insulator materials or particular gate insulator implants
• CPC Class Codes: H01L 27/0805 : Capacitors only
• CPC Class Codes: H01L 28/65 : comprising a noble metal or a noble metal oxide, e.g. platinum (Pt), ruthenium (Ru), ruthenium dioxide (RuO2), iridium (Ir), iridium dioxide (IrO2)
• CPC Class Codes: H01L 29/495 : the conductor material next to the insulator being a simple metal, e.g. W, Mo H01L29/4908, H01L29/4983 take precedence
• CPC Class Codes: H01L 29/513 : the variation being perpendicular to the channel plane
• CPC Class Codes: H01L 29/517 : the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence
• CPC Class Codes: H01L 29/66181 : Conductor-insulator-semiconductor capacitors, e.g. trench capacitors
• CPC Class Codes: H01L 2924/00 : Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 : Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

A precursor source mixture useful for CVD or ALD of a film comprising: at least one precursor composed of an element selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ti, Zr, Hf, Sc, Y, La, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, P, Sb and Bi, to which is bound at least one ligand selected from the group consisting of hydride, alkyl, alkenyl, cycloalkenyl, aryl, alkyne, carbonyl, amido, imido, hydrazido, phosphido, nitrosyl, nitryl, nitrate, nitrile, halide, azide, alkoxy, siloxy, silyl, and halogenated, sulfonated or silyated derivatives thereof, which is dissolved, emulsified or suspended in an inert liquid selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ethers, aldehydes, ketones, acids, phenols, esters, amines, alkylnitrile, halogenated hydrocarbons, silyated hydrocarbons, thioethers, amines, cyanates, isocyanates, thiocyanates, silicone oils, nitroalkyl, alkylnitrate, and mixtures thereof. The precursor source mixture may be a solution, emulsion or suspension and may consist of a mixture of solid, liquid and gas phases which are distributed throughout the mixture.

Claims

1. A precursor source mixture utilized for chemical vapor deposition or atomic layer deposition comprising at least one precursor compound which is dissolved, emulsified or suspended in an inert organic liquid, where

said precursor compound is a precursor metal atom bound to a ligand selected from the group consisting of hydride, carbonyl, imido, hydrazido, phosphido, nitrosyl, nitryl, nitrate, nitrite, halide, azide, siloxy, and silyl, with the proviso that the precursor compound is not an alkylamine alane, MeAu(PMe₃), or (Me₃P)Cu(tertbutoxy), tantalum cyclopentadienyl hydride, copper bound to a β

-diketonate, β

-diiminate, β

-diketiminate, and the proviso that the precursor compound is not bound to a diketoamido (RC(O)NC(O)CR), imidoylamidinato (RC(NH)NC(NH)CR), ketimidoylamidinato RC(O)NC(NH)CR, or hydrocarbyl C(R₂)C(CH₃)₂C(R₂)N(R₂) ligand, wherein R is a hydrocarbon and the proviso that the precursor metal atom is not Pt and with the proviso that when the precursor metal atom is Ru and said ligand is a carbonyl, then the precursor is selected from the group consisting of Ru₃CO₁₂ and Ru₃(CO)₁₂.

2. The precursor source mixture of claim 1 wherein said inert organic liquid is an aliphatic hydrocarbon, aromatic hydrocarbon, alcohol, ether, aldehyde, ketone, acid, phenol, ester, alkylnitrile, halogenated hydrocarbon, silyated hydrocarbon, thioether, amine, cyanate, isocyanate, thiocyanate, silicone oil, nitroalkyl, alkylnitrate, or mixtures thereof.

3. The precursor source mixture of claim 1 wherein said inert organic liquid vaporizes at a higher temperature than said at least one precursor compound.

4. The precursor source mixture of claim 2 wherein said inert organic liquid is a C_5-12 alkane.

5. The precursor source mixture of claim 1 wherein said inert organic liquid contains an additive of no more than 30% by volume of the inert organic liquid.

6. The precursor source mixture of claim 5 wherein said additive is an additional precursor ligand, an additional precursor adduct, or other coordinating compound selected from the group consisting of phosphines, phosphites, aryls, amines, arsines, stibenes, ethers, sulfides, nitrites, isonitriles, alkenes, pyridines, heterocycles, tetrahydrofuran, dimethylformamide, marcrocycles, schiff bases, cycloalkenes, alcohols, phosphine oxides and alkynes.

7. The precursor source mixture of claim 5 wherein the additive is selected from the group consisting of methanol, ethanol, isopropanol, neopentanol, trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, dimethylamine, diethylamine, bistrimethylsilylamine, ammonia, ethylenediamine, propylenediamine, trimethylethylethylenediamine, triphenylphosphine, triethylphosphine, trimethylphosphine, allyl, cyclopentadiene, benzene, ethylbenzene, toluene, cyclohexadiene, cyclooctadiene, cycloheptatriene, cyclooctatetraene, mesitylene, tertrahydrofuran, dimethylformamide, dimethylsulfoxide, butyl acetate, acetic acid, ethylhexanoic acid, methane, ethane, pyridine, and PF₃.

8. The precursor source mixture of claim 1 wherein the inert organic liquid is composed of two or more components selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ethers, aldehydes, ketones, acids, phenols, esters, amines, alkylnitrile, halgonated hydrocarbons, silyated hydrocarbons, thioethers, amines, cyanates, isocyanates, thiocyanates, silicone oils, nitroalkyl, alkylnitrate, and/or mixtures of one or more of the above and an additive of no more than 30% by volume of the inert organic liquid wherein the additive is selected from the group consisting of additional precursor ligand, additional precursor adduct, and other coordinating compound selected from the group consisting of phosphines, phosphites, aryls, amines, arsines, stibenes, ethers, sulfides, nitriles, isonitriles, alkenes, pyridines, heterocycles, tetrahydrofuran, dimethylformamide, marcrocycles, schiff bases, cycloalkenes, alcohols, phosphine oxides, and alkynes.

9. The precursor source mixture of claim 8 wherein the additive is selected from the group consisting of methanol, ethanol, isopropanol, neopentanol, trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, dimethylamine, diethylamine, bistrimethylsilylamine, ammonia, ethylenediamine, propylenediamine, trimethylethylethylenediamine, triphenylphosphine, triethylphosphine, trimethylphosphine, allyl, cyclopentadiene, benzene, ethylbenzene, toluene, cyclohexadiene, cyclooctadiene, cycloheptatriene, cyclooctatetraene, mesitylene, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, butyl acetate, acetic acid, ethylhexanoic acid, methane, ethane, pyridine, and PF₃.

10. The precursor source mixture of claim 1 wherein the inert organic liquid is composed of C₅–

C₁₂ alkane and contains an additive of no more than 30% by volume of the inert organic liquid wherein the additive is selected from the group consisting of an additional precursor ligand, an additional precursor adduct, or other coordinating compound selected from the group consisting of phosphines, phosphites, aryls, amines, arsines, stibenes, ethers, sulfides, nitriles, isonitriles, alkenes, pyridines, heterocycles, tetrahydrofuran, dimethylformamide, macrocycles, schiff bases, cycloalkenes, alcohols, phosphine oxides, and alkynes.

11. The precursor source mixture of claim 10 wherein the additive is methanol, ethanol, isopropanol, neopentanol, trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, dimethylamine, diethylamine, bistrimethylsilylamine, ammonia, ethylenediamine, propylenediamine, trimethylethylethylenediamine, triphenylphosphine, triethylphosphine, trimethylphosphine, allyl, cyclopentadiene, benzene, ethylbenzene, toluene, cyclohexadiene, cyclooctadiene, cycloheptatriene, cyclooctatetraene, mesitylene, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, butyl acetate, acetic acid, ethylhexanoic acid, methane, ethane, pyridine, or PF₃.

12. A method for chemical vapor deposition or atomic layer deposition comprising:

vaporizing the precursor compound in the precursor source mixture of claim 1, introducing the vaporized precursor into a chemical vapor deposition or atomic layer deposition reactor with optional addition of other co-reactant(s), and depositing a constituent of the vaporized precursor on a substrate to form a film.

13. The method of claim 12 wherein said film is a component in an electronic device.

14. The method of claim 12 wherein said co-reactant(s) is introduced separately from said vaporized precursor.

15. The method of claim 12 comprising vaporizing the precursor in the precursor source mixture, and introducing the vaporized precursor into an atomic layer deposition reactor with separate addition of other co-reactant(s) and inert purge gas and depositing a film on a substrate by sequential introduction of alternating pulses of vaporized precursor(s), purge gas, co-reactant(s) and purge gas.

16. The method of claim 12 wherein the co-reactant is a reducing agent, an oxidizing agent, a nitriding agent or a silyating agent.

17. The method of claim 16 wherein said co-reactant is a reducing agent selected from the group consisting of hydrogen, forming gas, silane, and combinations thereof.

18. The method of claim 16 wherein said co-reactant is an oxidizing agent selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, nitrous oxide, and combinations thereof.

19. The method of claim 16 wherein said co-reactant is a nitriding agent selected from the group consisting of ammonia, hydrazine, hydrogen azide, tertbutylamine, isopropylamine, and combinations thereof.

20. The method of claim 16 wherein said co-reactant is a silyating agent selected from the group consisting of silane, dislanes, chlorosilanes, silylamines, silazanes, and combinations thereof.

21. The method of claim 12 comprising subjecting said substrate to a sequence of alternating pulses of three or more different gases wherein one of said gases comprises vaporized precursor of said precursor source mixture, another of said gases is a purge gas and another of said gases is a reducing agent.

22. The method of claim 12 comprising subjecting said substrate to a sequence of alternating pulses of three or more different gases wherein one of said gases comprising said vaporized precursor of said precursor source mixture, another of said gases is a purge gas and another of said gases is an nitriding agent.

23. The method of claim 12 comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises said vaporized precursor of said precursor source mixture, another of said gases is a purge gas, another of said gases is an oxidizing agent and another of said gases is selected from the group consisting of any vaporized precursor and a vaporized precursor of said precursor source mixture.

24. The method of claim 12 comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises vaporized precursor of said precursor source mixture, another of said gases is a purge gas, another of said gases is an nitriding agent and another of said gases is selected from the group consisting of any vaporized precursor and a vaporized precursor of said precursor source mixture.

25. The method of claim 12 comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises vaporized precursor of said precursor source mixture, another of said gases is a purge gas, another of said gases is a reducing agent and another of said gases is selected from the group consisting of any vaporized precursor and a vaporized precursor of said precursor source mixture.

26. The method of claim 12 comprising subjecting said substrate to a sequence of alternating pulses of five or more different gases, wherein one of said gases comprises vaporized precursor of said precursor source mixture, another of said gases is a purge gas, another of said gases is a reducing agent and another of said gases is selected from the group consisting of any Si containing vaporized precursor and a Si containing vaporized precursor of said precursor source mixture.

27. The method of claim 12 wherein the substrate is selected from the group consisting of semiconductor substrates, dielectrics, metals, organic substrates, glasses, metal oxides, and plastic polymeric substrates, Si-containing semiconductor substrates, ceramics, silicon-on-insulator substrates, Ge substrates, SiGe substrates, GaAs substrates, and mixtures or multilayers thereof.

28. The method of claim 13 wherein said electronic device is a transistor, capacitor, diode, resistor, switch, light emitting diode, laser, wiring structure, or interconnect structure.

29. A method of fabricating a stack or trench capacitor structure composed of a bottom electrode, a dielectric layer, a top electrode layer and an optional dielectric buffer layer over said capacitor which is connected to underlying circuitry via a plug and optional barrier wherein at least one component of the capacitor structure is deposited according to claim 12.

30. The method of claim 29 wherein the optional dielectric barrier is selected from the group consisting of SiO₂, SiO_xN_y, Si₃N₄, TiON, AlN, SiN, TiN, Ta₂O₅, TiO₂, ZrO₂, HfO₂, Al₂O₃, La₂O₃, Y₂O₃, alloys, mixtures or layers thereof, and multicomponent metal oxides.

31. The method of claim 29 wherein the dielectric is a ferroelectric material.

32. The method of claim 29 wherein the plug material is selected from the group consisting of polysilicon, W, Mo, Ti, Cr, Cu, and doped or undoped alloys, mixtures and multilayers thereof.

33. The method of claim 29 wherein the conductive barrier is selected from the group consisting of TaN, TaSiN, TiAlN, TiSiN, TaWN, TiWN, NbN, ZrN, TaTiN, IrOx, Os, OsOx, MoSi, TiSi, ReO₂, and doped or undoped alloys, mixtures and multilayers thereof.

34. The method of claim 29 wherein the bottom electrode is selected from the group consisting of conductive materials, polysilicon, Ni, Pd, Pt, Cu, Ag, Au, Ru, Ir, Rh, OrOx, TaN, TaSiN, Ta, SrRuO₃, LaSrCO₃, and doped or undoped alloys, mixtures and multilayers thereof.

35. The method of claim 29 wherein the dielectric material is selected from the group consisting of SiO₂, SiO_xN_y, Si₃N₄, Ta₂O₅, TiO₂, ZrO₂, HfO₂, Al₂O₃, La₂O₃, Y₂O₃, multicomponent metal oxides, pervoskite type oxide having the formula ABO₃ wherein B is at least one acid oxide containing a metal selected from the group consisting of Al, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and Cu, and A is at least one additional cation having a positive formal charge of from about 1 to about 3, barium strontium titanate, barium strontium zirconate, barium strontium hafnate, lead titanate, yttrium alumnate, lanthanum alumnate, lead zirconium titanate, strontium bismuth tantalate, strontium bismuth niobate, bismuth titanate, lanthanum silicate, yttrium silicate, hafnium silicate, zirconium silicate, rate earth doped silicates and doped or undoped alloys, mixtures and multilayers thereof.

36. The method of claim 29 wherein the top electrode is selected from the group consisting of polysilicon, Ni, Pd, Pt, Cu, Ag, Au, Ru, Ir, Rh, IrOx, TaN, TaSiN, Ta, SrRuO₃, LaSrCoO₃, and doped or undoped alloys, mixtures and multilayers thereof.

37. A method of fabricating a wiring structure composed of etched trenches and vias into a dielectric layer, optional barrier material between dielectric and wiring material, and wiring material wherein at least one component of the wiring structure is deposited according to claim 12.

38. The method of claim 37 wherein the dielectric layer is selected from the group consisting of SiO₂, SiO_xN_y, Si₃N₄, phosphosilicate glass, metal oxides, Al₂O₃ and doped or undoped alloys, mixtures and multilayers thereof.

39. The method of claim 37 wherein the optional barrier material is selected from the group consisting of WN, TiN, TaN, SiO₂, SiO_xN_y, Si₃N₄, phosphosilicate glass, metal oxides, Al₂O₃, and doped or undoped alloys, mixtures and multilayers thereof.

40. The method of claim 37 wherein the wiring material is selected from the group consisting of polysilicon, Al, W, Mo, Ti, Cr, Cu and doped or undoped alloys, mixtures and multilayers thereof.

41. A method of fabricating an electronic device composed of a substrate having source and drain regions and a channel region between said source and drain regions, a gate dielectric, aligned to and on top of said channel region, and a gate electrode aligned to and on top of said gate dielectric wherein at least one component of the electronic device is deposited according to claim 12.

42. A method of claim 41 wherein the gate dielectric selected from the group consisting of SiO₂, SiO_xN_y, Si₃N₄, Ta₂O₅, TiO₂, ZrO₂, HfO₂, Al₂O₃, La₂O₃, Y₂O₃, multicomponent metal oxides, pervoskite type oxide having the formula ABO₃ wherein B is at least one acid oxide containing a metal selected from the group consisting of Al, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and Cu, and A is at least one additional cation having a positive formal charge of from about 1 to about 3, barium strontium titantate, barium strontium zirconate, barium strontium hafnate, lead titanate, yttrium alumnate, lanthanum alumnate, lead zirconium titanate, strontium bismuth tantalate, strontium bismuth niobate, bismuth titanate, lanthanum silicate, yttrium silicate, hafnium silicate, zirconium silicate, rare earth doped silicates and doped or undoped alloys, mixtures and multilayers thereof.

43. The method of claim 41 wherein gate dielectric is composed of more than one layer.

44. The method of claim 41 wherein the gate electrode is selected from the group consisting of polysilicon, Al, Ag, Bi, Cd, Fe, Ga, Hf, In, Mn, Nb, Y, Zr, Ni, Pt, Be, Ir, Te, Re, Rh, W, Mo, Cr, Fe, Pd, Au, Rh, Ti, Cr, Cu, and doped or undoped alloys, mixtures and multilayers thereof.

45. The precursor source mixture of claim 1 wherein the at least one precursor compound is B, Al, Ga, In, As or Sb, hydride, chloride, fluoride, bromide, iodide, Cp or azide;

Mo(CO)₃;

Fe(CO)₅;

CO₂(CO)₈;

Os₃CO₁₂;

Cr(CO)₆;

Mn₂(CO)₁₀;

Mo(CO)₆;

Ni(CO)₄;

Re₂(CO)₁₀;

Ru₃(CO)₁₂;

W(CO)₆;

CF₃Co(CO)₄;

(CO)₄Fe[P(OCH₃)₃];

(CO)₄Fe[N(CH₃)₃];

CoNO(CO)₃;

OSi(CH₃)₃ Li, Na, K, Rb, Cs, Fr, Cu, Ag, Au, Hg, or Tl;

tetra-OSi(CH₃)₃ Si, Ge, Sn, Pb, Ti, Zr, or Hf;

tri-OSi(CH₃)₃, B, Al, Ga, In, P, As, or Sb;

diethylaminoarsine dichloride;

bisdimethylaminoasine chloride;

(CO)₄Fe[N(CH₃)₃], Li, Na, or K N(SiMe₃), CpCu(PEt₃);

CpCu(triphenylphosphine);

Ni(PF₃)₄;

Cr(PF₃)₆;

(Et₃P)₃Mo(CO)₃;

Ir(PF₃)₄;

Ti(NO₃)₄;

Zr(NO₃)₄;

Hf(NO₃)₄;

Si(CH₃)₃(NO₃);

RuNO(NO₃)₃;

gallium nitrate;

Sn(NO₃)₄;

Co(NO₃)₃;

VO(NO₃)₃;

CrO₂(NO₃)₂;

TiCl₄;

ZnCl₂;

ZrCl₄;

HfCl₄;

AlCl₃;

SiCl₄;

GaCl₃;

SnCl₄;

CoCl₃;

N(SiMe₃)Li, Na, or K;

B(CH₂SiMe₃)₃;

(Me₃SiCH₂)₄ Ti, Zr or Hf.