METHOD FOR HAFNIUM NITRIDE DEPOSITION

• US 20060208215A1
• Filed: 05/30/2006
• Published: 09/21/2006
• Est. Priority Date: 04/04/2003
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Rocklein, M. Noel, Kher, Shreyas, Metzner, Craig, George, Steven M., Kim, Yeong Kwan
• Granted Patent: US 7,547,952 B2
• Time in Patent Office: Days
• US Class Current: 252/62.3BT
• 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 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.

2. The composition of claim 1 formed by performing a method sequentially comprising:

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

b) purging the chamber with a purge gas;

c) exposing the substrate to atomic nitrogen or a radical nitrogen compound;

d) purging the chamber with the purge gas;

e) exposing the substrate to an alkylamidosilane precursor;

f) purging the chamber with the purge gas;

g) exposing the substrate to an oxygen precursor; and

h) purging the chamber with the purge gas.

3. The composition of claim 1, wherein the method further comprises repeating a)-h) to deposit HfSi_xO_yN_z at a thickness from about 2 Å

to about 1,000 Å

.

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

to about 50 Å

.

5. The composition of claim 2, wherein the alkylamido hafnium precursor is selected from the group consisting of (Et₂N)₄Hf, (Me₂N)₄Hf, and (EtMeN)₄Hf.

6. The composition of claim 5, wherein the alkylamidosilane precursor is selected from the group consisting of (Et₂N)₄Si, (Me₂N)₄Si, (Et₂N)₃SiH and (Me₂N)₃SiH.

7. The composition of claim 6, wherein the oxygen precursor is selected from the group consisting of H₂O, H₂O₂, organic peroxides, O, O₂, O₃ and radical oxygen compounds.

8. The composition of claim 2, wherein the method for forming further comprises:

i) exposing the substrate to an aluminum precursor; and

j) purging the chamber with the purge gas.

9. The composition of claim 8, wherein the aluminum precursor is selected from the group consisting of Me₃Al, Me₂AlH, AlCl₃, Me₂AlCl and (PrO)₃Al.

10. The composition of claim 1 formed by performing a method sequentially comprising:

exposing a substrate to a first process gas comprising an alkylamido hafnium precursor;

exposing the substrate to a second process gas comprising an oxygen precursor;

exposing the substrate to a third process gas comprising atomic nitrogen or a radical nitrogen compound; and

exposing the substrate to a fourth process gas comprising an alkylamidosilane precursor.

11. The composition of claim 10, wherein the alkylamido hafnium precursor is selected from the group consisting of (Et₂N)₄Hf, (Me₂N)₄Hf, and (EtMeN)₄Hf.

12. The composition of claim 10, wherein the alkylamidosilane precursor is selected from the group consisting of (Et₂N)₄Si, (Me₂N)₄Si, (Et₂N)₃SiH and (Me₂N)₃SiH.

13. The composition of claim 12, wherein the oxygen precursor is selected from the group consisting of H₂O, H₂O₂, organic peroxides, O, O₂, O₃ and radical oxygen compounds.

14. The composition of claim 13, wherein the method for forming further comprises:

exposing the substrate to a fifth process gas comprising an aluminum precursor selected from the group consisting of Me₃Al, Me₂AlH, AlCl₃, Me₂AlCl and (PrO)₃Al.

15. The composition of claim 1 formed by performing a method sequentially comprising:

exposing a substrate sequentially to an alkylamino hafnium precursor, an alkylamino silane precursor, and an oxygen precursor during a silicate cycle; and

exposing the substrate to atomic nitrogen or a radical nitrogen compound during a nitridization cycle.

16. The composition of claim 15, wherein the sequence of forming further comprises repeating the silicate cycle before the nitrogen cycle.

17. The composition of claim 15, wherein the silicate cycle is performed about 2 times for each nitrogen cycle performed.

18. The composition of claim 15, wherein the silicates cycle is repeated multiple times before the nitrogen cycle such that a higher concentration of nitrogen forms near the layer surface.

19. The composition of claim 15, wherein the alkylamido hafnium precursor is selected from the group consisting of (Et₂N)₄Hf, (Me₂N)₄Hf, and (EtMeN)₄Hf.