Method for hafnium nitride deposition

• US 20040198069A1
• Filed: 04/04/2003
• Published: 10/07/2004
• Est. Priority Date: 04/04/2003
• Status: Abandoned Application

• Current Assignee: Applied Materials Incorporated, The Board of Regents of the University of Colorado (University of Colorado System)
• Original Assignee: Applied Materials Incorporated
• Inventors: Rocklein, M. Noel, Kher, Shreyas, Metzner, Craig, George, Steven M., Kim, Yeong Kwan
• Application Number:
  US10/407,930
• Publication Number:
  US 20040198069A1
• Time in Patent Office: Days
• US Class Current: 438/785
• 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 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: H01L 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/02208 the precursor containing a compound comprising Si
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/28167 on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
• CPC Class Codes: H01L 21/28185 with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
• 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 21/318 composed of nitrides
• 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 generally is a method for forming a high-k dielectric layer, comprising depositing a hafnium compound by atomic layer deposition to a substrate, comprising, delivering a hafnium precursor to a surface of the substrate, reacting the hafnium precursor and forming a hafnium containing layer to the surface, delivering a nitrogen precursor to the hafnium containing layer, forming at least one hafnium nitrogen bond and depositing the hafnium compound to the surface.

Claims

1. A method for forming a layer comprising hafnium on a substrate surface, sequentially comprising:

a) exposing the substrate surface to a hafnium precursor to form a hafnium containing layer on the substrate surface;

b) purging the chamber with a purge gas;

c) reacting a second precursor with the hafnium containing layer;

d) purging the chamber with the purge gas;

e) reacting a third precursor with the hafnium containing layer;

f) purging the chamber with the purge gas;

g) reacting a fourth precursor with the hafnium containing layer; and

h) purging the chamber with the purge gas.

2. The method of claim 1, wherein the layer comprising hafnium is hafnium silicon oxynitride.

3. The method of claim 1, further comprising repeating steps a-h to deposit the layer comprising hafnium at a thickness from about 2 Å

to about 1,000 Å

.

4. The method of claim 3, wherein the thickness is from about 10 Å

to about 50 Å

.

5. The method of claim 1, wherein the hafnium precursor is selected from the group consisting of (Et₂N)₄Hf, (Me₂N)₄Hf, (EtMeN)₄Hf and Cl₄Hf.

6. The method of claim 5, wherein the second precursor is selected from the group consisting of ammonia, hydrazines, azides and radical nitrogen compounds.

7. The method of claim 6, wherein the third precursor is selected from the group consisting of SiH₄, Si₂H₆, Si₃H₈, Si₂Cl₆, (Et₂N)₄Si, (Me₂N)₄Si, (Et₂N)₃SiH and (Me₂N)₃SiH.

8. The method of claim 7, wherein the fourth precursor is selected from the group consisting of H₂O, H₂O₂, organic peroxides, O, O₂, O₃ and radical oxygen compounds.

9. The method of claim 1, further comprising:

i) reacting a fifth precursor with the hafnium containing layer; and

j) purging the chamber with the purge gas.

10. The method of claim 9, wherein the fifth precursor is selected from the group consisting of Me₃Al, Me₂AlH, AlCl₃, Me₂AlCl and (PrO)₃Al.

11. A method for growing a layer comprising hafnium, comprising:

exposing a substrate sequentially to at least four precursors during an ALD cycle to deposit a compound film comprising hafnium and at least three elements selected from the group consisting of silicon, aluminum, oxygen and nitrogen.

12. The method of claim 11, wherein the at least four precursors include a hafnium precursor selected from the group consisting of (Et₂N)₄Hf, (Me₂N)₄Hf, (EtMeN)₄Hf and Cl₄Hf.

13. The method of claim 11, wherein the at least four precursors include a silicon precursor selected from the group consisting of SiH₄, Si₂H₆, Si₃H₈, Si₂Cl₆, (Et₂N)₄Si, (Me₂N)₄Si, (Et₂N)₃SiH and (Me₂N)₃SiH.

14. The method of claim 11, wherein the at least four precursors include a nitrogen precursor selected from the group consisting of ammonia, hydrazines, azides and radical nitrogen compounds.

15. The method of claim 11, wherein the at least four precursors include an oxygen precursor selected from the group consisting of H₂O, H₂O₂, organic peroxides, O, O₂, O₃ and radical oxygen compounds.

16. The method of claim 11, wherein the at least four precursors include an aluminum precursor selected from the group consisting of Me₃Al, Me₂AlH, AlCl₃, Me₂AlCl and (PrO)₃Al.

17. The method of claim 11, wherein the layer comprising hafnium is deposited to a thickness from about 2 Å

to about 1,000 Å

.

18. The method of claim 17, wherein the thickness is from about 10 Å

to about 50 Å

.

19. A method for depositing a hafnium compound on a substrate in a chamber during an atomic layer deposition process, comprising:

conducting a first half reaction comprising a hafnium precursor;

conducting a second half reaction comprising an oxygen precursor;

conducting a third half reaction comprising a nitrogen precursor; and

conducting a fourth half reaction comprising a silicon precursor.

20. The method of claim 19, wherein the hafnium precursor is selected from the group consisting of (Et₂N)₄Hf, (Me₂N)₄Hf, (EtMeN)₄Hf and Cl₄Hf.

21. The method of claim 20, wherein the silicon precursor is selected from the group consisting of SiH₄, Si₂H₆, Si₃H₈, Si₂Cl₆, (Et₂N)₄Si, (Me₂N)₄Si, (Et₂N)₃SiH and (Me₂N)₃SiH.

22. The method of claim 21, wherein the nitrogen precursor is selected from the group consisting of ammonia, hydrazines, azides and radical nitrogen compounds.

23. The method of claim 22, wherein the oxygen precursor is selected from the group consisting of H₂O, H₂O₂, organic peroxides, O, O₂, O₃ and radical oxygen compounds.

24. The method of claim 19, further comprising conducting a fifth half reaction comprising an aluminum precursor selected from the group consisting of Me₃Al, Me₂AlH, AlCl₃, Me₂AlCl and (PrO)₃Al.

25. A composition of a semiconductor material, comprising HfSi_xO_yN_z,

wherein x is at least about 0.2 and less than about 4;

y is at least about 0.5 and less than about 4; and

z is at least about 0.05 and less than about 2.