System and method for forming multi-component dielectric films

• US 20050064207A1
• Filed: 04/21/2004
• Published: 03/24/2005
• Est. Priority Date: 04/21/2003
• Status: Active Grant

• Current Assignee: Avid Technology Incorporated
• Original Assignee: Avid Technology Incorporated
• Inventors: Senzaki, Yoshihide, Park, Seung Gyun
• Granted Patent: US 7,470,470 B2
• Time in Patent Office: Days
• US Class Current: 428/446
• CPC Class Codes: C23C 16/029 Graded interfaces
• CPC Class Codes: C23C 16/308 Oxynitrides
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• 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 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02337 treatment by exposure to a gas or vapour
• 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 21/3143 composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
• CPC Class Codes: H01L 21/3145 formed by deposition from a gas or vapour
• CPC Class Codes: H01L 21/31608 Deposition of SiO2 H01L21/31625, H01L21/31629 and H01L21/31633 take precedence
• CPC Class Codes: H01L 21/31612 on a silicon body
• CPC Class Codes: H01L 21/31645 Deposition of Hafnium oxides, e.g. HfO2

Abstract

The present invention provides systems and methods for mixing precursors such that a mixture of precursors are present together in a chamber during a single pulse step in an atomic layer deposition (ALD) process to form a multi-component film. The precursors are comprised of at least one different chemical component, and such different components will form a mono-layer to produce a multi-component film. In a further aspect of the present invention, a dielectric film having a composition gradient is provided.

Claims

1. A method of forming a film on a surface of a substrate, characterized in that:

two or more precursors, each of the precursors containing at least one different chemical component, are conveyed to a process chamber together and form a mono-layer on the surface of the substrate, said mono-layer containing each of the separate chemical components.

2. The method of claim 1 wherein said substrate surface is selected from the group consisting of silicon, plastics, polymers, metals, alloys, organics, inorganics, or mixtures thereof.

3. The method of claim 1 where the precursors have the formula:

M(L)x

where M is a metal selected from the group of;

Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Th, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge or mixtures thereof;

where L is a ligand selected from the group consisting of amine, amides, alkoxides, halogens, hydrides, alkyls, asides, nitrates, nitrites, cyclopentadienyls, carbonyl, carboxylates, diketonates, alkenes, alkynes, or a substituted analogs thereof, and combinations thereof; and

where x is an integer less than or equal to the valence number for M.

4. The method of claim 1 further comprising supplying at least one reactant that reacts with said monolayer.

5. The method of claim 4, wherein said at least one reactant is delivered sequentially or simultaneously with the precursors.

6. The method of claim 4, wherein said at least one reactant is a nitridating reactant, reducing reactant, oxidizing reactant, or a mixture thereof.

7. The method of claim 6, wherein said nitridating reactant is selected from the group consisting of ammonia, deuterated ammonia, 15N-ammonia, amines or amides, hydrazines, alkyl hydrazines, nitrogen gas, nitric oxide, nitrous oxide, nitrogen radicals, N-oxides, or mixtures thereof.

8. The method of claim 6, wherein said oxidizing reactant is selected from the group consisting of ozone, oxygen, singlet oxygen, triplet oxygen, atomic oxygen, water, peroxides, air, nitrous oxide, nitric oxide, H₂O₂, and mixtures thereof.

24. The method of claim 1 wherein said monolayer is selected from the group consisting of metals and metal, metal alloy or mix metal oxides, silicates, nitrides and oxynitrides.

25. The method of claim 1 wherein each said monolayer is compositionally variable and electrically and physically compatible with the adjacent said monolayers.

9. A method for forming a multi-component film on a surface of a substrate comprising the steps of:

vaporizing two or more precursors, each of the precursors containing at least one metal or metalloid component;

conveying the two or more precursors into a process chamber wherein the precursors are present together in the process chamber;

forming a mono-layer on the surface of the substrate, said mono-layer containing each of the metal or metalloid components; and

purging said process chamber.

10. The method of claim 9 wherein said forming step is carried out at a temperature in the range of approximately 20 to 800 C.

11. The method of claim 9 wherein said process chamber is at a pressure in the range of approximately 0.001 mTorr to 600 Torr.

12. The method of claim 9 wherein the step of conveying further includes mixing the two or more precursors and conveying the mixture of precursors into the process chamber.

13. The method of claim 9, wherein said purging step further comprises introducing a carrier gas to evacuate the precursors from the chamber.

14. The method of claim 9 further comprising conveying a reactant gas to the process chamber, wherein the reactant gas contacts the mono-layer formed on the surface of the substrate.

15. The method of claim 14 wherein the gas flow rate to the process chamber is in the range of approximately 0 to 20,000 sccm.

16. The method of claim 9 where the precursors have the formula:

M(L)x

where M is a metal selected from the group of;

Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Th, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge or mixtures thereof;

where L is a ligand selected from the group consisting of amine, amides, alkoxides, halogens, hydrides, alkyls, asides, nitrates, nitrites, cyclopentadienyls, carbonyl, carboxylates, diketonates, alkenes, alkynes, or a substituted analogs thereof, and combinations thereof; and

where x is an integer less than or equal to the valence number for M.

17. A dielectric film having a composition gradient comprising:

a silicon-rich bottom layer;

a nitrogen-rich top layer; and

a hafnium-rich layer formed between said top and bottom layers.

18. The dielectric film of claim 17, wherein each said silicon-rich bottom layer, said hafnium-intermediate layer and said nitrogen-rich top layer comprise at least one common compositional element.

19. The dielectric film of claim 18, wherein said at least one common compositional element is selected from the group consisting of oxygen, nitrogen and metal.

20. The dielectric film of claim 19, wherein said metal is selected from the group consisting of Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Th, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge and mixtures thereof.

21. The dielectric film of claim 19 wherein said metal further comprises metal, metal alloy or mixed metal oxides, silicates, nitrides, oxynitrides, or mixtures thereof.

22. A system for atomic layer deposition comprising:

at least a first vaporizer containing a first deposition precursor for deposition;

a least a second vaporizer containing a second deposition precursor for deposition;

a process chamber adapted to carry out an atomic layer deposition process; and

a manifold, said manifold being coupled to said first and second vaporizers and to said process chamber, said manifold being adapted to mix and convey the first and second deposition precursors to said process chamber.

23. The system of claim 22, wherein said process chamber further comprises:

a gas inlet coupled to said manifold; and

an inlet for supplying at least one reactant gas, wherein said inlet provides said at least one reactant in said process chamber in-situ in either sequential or simultaneous manner.

26. A method of forming a film on the surface of a substrate, characterized in that:

two or more precursors, each of the precursors containing at least one different chemical component, are conveyed to a process chamber together and form a mono-layer on the surface of the substrate, wherein the amount of each of the precursors conveyed to the process chamber is selectively controlled such that a desired composition gradient of one of more of the chemical components is formed in the film.