Multilayer multicomponent high-k films and methods for depositing the same

• US 20060264066A1
• Filed: 04/07/2006
• Published: 11/23/2006
• Est. Priority Date: 04/07/2005
• Status: Abandoned Application

• Current Assignee: Aviza Technology Inc (Sumitomo Corporation)
• Original Assignee: Aviza Technology Inc (Sumitomo Corporation)
• Inventors: Bartholomew, Larry D., Treichel, Helmuth, Owyang, Jon S.
• Application Number:
  US11/400,366
• Publication Number:
  US 20060264066A1
• Time in Patent Office: Days
• US Class Current: 438/785
• CPC Class Codes: C23C 16/308 Oxynitrides
• CPC Class Codes: C23C 16/45523 Pulsed gas flow or change of composition over time
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02145 the material containing aluminium, e.g. AlSiOx
• CPC Class Codes: H01L 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• CPC Class Codes: H01L 21/02153 the material containing titanium, e.g. TiSiOx
• CPC Class Codes: H01L 21/02161 the material containing more than one metal element
• 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 21/02183 the material containing tantalum, e.g. Ta2O5
• CPC Class Codes: H01L 21/02186 the material containing titanium, e.g. TiO2
• CPC Class Codes: H01L 21/02194 the material containing more than one metal element
• CPC Class Codes: H01L 21/02266 deposition by physical ablation of a target, e.g. sputtering, reactive sputtering, physical vapour deposition or pulsed laser deposition
• 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 21/28202 in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
• 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 21/31604 Deposition from a gas or vapour H01L21/31691, H01L21/31695 take precedence
• CPC Class Codes: H01L 21/31608 : Deposition of SiO2 H01L21/31625, H01L21/31629 and H01L21/31633 take precedence
• CPC Class Codes: H01L 21/31637 : Deposition of Tantalum oxides, e.g. Ta2O5
• CPC Class Codes: H01L 21/31645 : Deposition of Hafnium oxides, e.g. HfO2
• CPC Class Codes: H01L 28/40 : Capacitors
• 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 29/518 : the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material

Abstract

The present invention provides systems and methods for forming a multi-layer, multi-component high-k dielectric film. In some embodiments, the present invention provides systems and methods for forming high-k dielectric films that comprise hafnium, titanium, oxygen, nitrogen, and other components. In a further aspect of the present invention, the dielectric films are formed having composition gradients.

Claims

1. A dielectric film comprising a hafnium component and/or a titanium component and/or a silicon component and/or an oxygen component and/or a nitrogen component.

2. The dielectric film of claim 1 which comprises a hafnium component, a titanium component, a silicon component, an oxygen component, and a nitrogen component.

3. A dielectric film comprising a composition of HfTiSi_xO_yN_z wherein x, y, and z represent a number from 0 to 2, respectively.

4. A method of forming a film on a substrate, characterized in that two or more precursors, at least one of the precursors containing a titanium containing chemical component, are conveyed to a process chamber together or sequentially and form a mono-layer on a 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 is formed in the film.

5. The method of forming a film according to claim 4 wherein the film is formed by any one of ALD, energy assisted ALD, CVD, energy assisted CVD, PVD or reactive PVD.

6. The method of claim 5 wherein the film is formed at a temperature between 20°

C. to 800°

C. and a pressure between 0.001 mTorr to 600 Torr.

7. A semiconductor film stack comprising:

a substrate comprised of Si, SiO₂ or SOI;

a first layer atop the substrate and comprised of any one of HfSiO_x wherein the concentration of Si is greater than the concentration of Hf, TiSiO_x wherein the concentration of Si is greater than the concentration of Ti, AlSiO_x wherein the concentration of Si is greater than the concentration of Al, or HfSiTiO_x wherein the concentration of Si is greater than the total concentration of Hf plus Ti, and HfTiO_x;

a second layer atop the first layer and comprised of any one of HfO_x, HfTiO_x, HfAlO_x, TiO_x, HfTaTiO_x, TaO_x, HfTaO_x, TiTaO_x, TiAlO_x, or TiAlO_x;

a third layer atop the second layer and comprised of any one of HfON, TiON, SiON, HfTiON, HfSiON, TiSiON, or HfTiSiON;

a forth layer atop the third layer and comprised of any one of TiN, TaN, AlN, TiAlN, TaAlN, SiN_x, Ru, RuO₂, CoWP, or TaCN; and

a fifth layer atop the fourth layer and comprised of any one of W, WN, Ru, NiSi_x, or doped-Si.

8. A dielectric film comprising a silicon-rich bottom layer;

a nitrogen-rich top layer; and

a hafnium titanate layer formed between said top and bottom layers wherein in the silicon-rich bottom layer, the concentration of silicon is greater than the concentration of hafnium, titanium or nitrogen, or combination thereof.

9. The dielectric film of claim 8 wherein the concentration of silicon decreases as a function of distance away from a substrate atop which the dielectric film is formed.

10. The dielectric film of claim 8 wherein the concentration of silicon in the silicon-rich bottom layer is up to 80 percent.

11. The dielectric film of claim 8 wherein in the hafnium-titanate layer, the concentration of silicon is smaller than the concentration of hafnium, titanium, nitrogen or combination thereof.

12. A semiconductor film stack comprising:

a substrate comprised of doped-Si, or metal;

a first layer atop the substrate and comprised of any one of TiN, TaN, AlN, TiAlN, TaAlN, SiN_x, Ru, RuO₂, CoWP, NiSi_x, or TaCN;

a second layer atop the first layer and comprised of any one of W, WN, Ru, NiSi_x, or doped-Si.

a third layer atop the second layer and comprised of any one of TiN, TaN, AlN, TiAlN, TaAlN, SiN_x, Ru, RuO₂, CoWP, NiSi_x, or TaCN;

a fourth layer atop the third layer and comprised of any one of HfO_x, HfTiO_x, HfAlO_x, TiO_x, HfTaTiO_x, TaO_x, HfTaO_x, TiTaO_x, TiAlO_x, TiAlO_x, HfSiO_x, TiSiO_x, TaSiO_x, AlSiO_x, or HfSiTiTaO_x;

a fifth layer atop the fourth layer and comprised of any one of TiN, TaN, AlN, TiAlN, TaAlN, SiN_x, Ru, RuO₂, CoWP, or TaCN; and

a sixth layer atop the fifth layer and comprised of any one of W, WN, Ru, NiSi_x, or doped-Si.

13. A method of forming a film on one or more substrates in a process chamber, comprising:

exposing the one or more substrates to one or more precursors to form a monolayer of the precursors on the substrate, and purging the process chamber of excess precursors;

exposing the one or more substrates to one or more reactants to react with the monolayer of the precursors on the substrate to form a compound, and purging the process chamber of excess reactants; and

repeating said exposing steps until the desired thickness of film is formed, wherein the concentration of each precursor is controlled during each repetition of the step so that a composition gradient of each precursor is established throughout the thickness of the film.

14. A semiconductor film comprising:

a substrate comprised of Si, SiO₂ or SOI; and

a first layer atop the substrate comprised of any one of HfO_x, HfTiO_x, HfAlO_x, TiO_x, HfTaTiO_x, TaO_x, HfTaO_x, TiTaO_x, TiAlO_x, or TiAlO_x.

15. The film of claim 14 further comprising:

an interlayer formed between said substrate and said first layer and comprised of any one of HfSiO_x wherein the concentration of Si is greater than the concentration of Hf, TiSiO_x wherein the concentration of Si is greater than the concentration of Ti, AlSiO_x wherein the concentration of Si is greater than the concentration of Al, or HfSiTiO_x wherein the concentration of Si is greater than the total concentration of Hf plus Ti and HfTiO_x.

16. The film of claim 15 further comprising a second layer formed atop the first layer and comprised of any one of HfON, TiON, SiON, HfTiON, HfSiON, TiSiON, or HfTiSiON.

17. The film of claim 16 further comprising a third layer atop the second layer and comprised of any one of TiN, TaN, AlN, TiAlN, TaAlN, SiN_x, Ru, RuO₂, CoWP, or TaCN.

18. The film of claim 17 further comprising a fourth layer atop the third layer and comprised of any one of W, WN, Ru, NiSi_x, or doped-Si.