Monolayer-by-monolayer growth of MgO layers using Mg sublimation and oxidation

Patent metadata

Field	Value
Publication number	US-10648069-B2
Application number	US-201816161161-A
Country	US
Kind code	B2
Filing date	Oct 16, 2018
Priority date	Oct 16, 2018
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

A MgO layer is formed using a process flow wherein a Mg layer is deposited at a temperature <200° C. on a substrate, and then an anneal between 200° C. and 900° C., and preferably from 200° C. and 400° C., is performed so that a Mg vapor pressure >100.6 Torr is reached and a substantial portion of the Mg layer sublimes and leaves a Mg monolayer. After an oxidation between −223° C. and 900° C., a MgO monolayer is produced where the Mg:O ratio is exactly 1:1 thereby avoiding underoxidized or overoxidized states associated with film defects. The process flow may be repeated one or more times to yield a desired thickness and resistance x area value when the MgO is a tunnel barrier or Hk enhancing layer. Moreover, a doping element (M) may be added during Mg deposition to modify the conductivity and band structure in the resulting MgMO layer.

First claim

We claim:

1. A method of forming a MgO layer having a 1:1 Mg:O ratio, comprising:
(a) sputter depositing a first Mg layer on a substrate;
(b) performing a first anneal at a first temperature between 200° C. and 900° C. in a first chamber such that a Mg vapor pressure reaches at least 10 0.6 Torr and a substantial portion of the first Mg layer sublimes thereby leaving a first Mg monolayer on the substrate; and
(c) performing a first oxidation at a second temperature between −223° C. and 900° C. by exposing the first Mg monolayer to oxygen or an oxygen species and thereby forming a first MgO monolayer with a 1:1 Mg:O ratio.

2. The method of claim 1 wherein the first Mg layer is deposited at a third temperature less than 200° C., and the sputter deposition of the first Mg layer is performed in a chamber different from the first chamber.

3. The method of claim 1 wherein sputter depositing the first Mg layer is performed at essentially the first temperature so that sputter deposition of the first Mg layer and the first anneal are both accomplished in the first chamber.

4. The method of claim 1 further comprising:
(a) sputter depositing a second Mg layer on the first MgO monolayer;
(b) performing a second anneal at a temperature between 200° C. and 900° C. such that a Mg vapor pressure reaches at least 10 −6 Torr and a substantial portion of the second Mg layer sublimes thereby leaving a second Mg monolayer on the first MgO monolayer; and
(c) performing a second oxidation at a temperature between −223° C. and 900° C. by exposing the second Mg monolayer to oxygen or an oxygen species and thereby forming a second MgO monolayer with a 1:1 Mg:O ratio wherein the first and second MgO monolayers form a MgO layer that is essentially free of defects.

5. The method of claim 4 further comprised of repeating a process flow of Mg deposition, Mg sublimation at a temperature between 200° C. and 900° C., and Mg oxidation at a temperature between −223° C. and 900° C. one or more times to form the MgO layer comprised of a plurality of MgO monolayers on the first MgO monolayer, and having a desired resistance×area (RA) product.

6. The method of claim 4 wherein the substrate is a free layer or a reference layer, and the MgO layer is a tunnel barrier layer in a perpendicularly magnetized magnetic tunnel junction (p-MTJ).

7. The method of claim 4 wherein the substrate is a seed layer or a free layer and the MgO layer is a Hk enhancing layer in a p-MTJ.

8. The method of claim 1 wherein the substrate is a first MgO sub-layer formed by a natural oxidation or radical oxidation of a Mg layer, or by sputter deposition of MgO.

9. The method of claim 1 wherein the MgO layer is an insulating layer.

10. The method of claim 1 wherein the MgO layer is formed in a magnetic random access memory (MRAM), spin torque MRAM, sensor in a read head of a hard disk drive (HDD), biosensor, or in a spin-logic based device.

11. The method of claim 2 wherein the first, second and third temperatures are essentially equivalent to enable sputter depositing the first Mg layer, the first anneal, and the first oxidation to be performed in the first chamber.

12. The method of claim 2 wherein the performing the first anneal also includes heating the substrate from the third temperature to the first temperature, and maintaining the first temperature for 5 to 300 seconds.

13. The method of claim 1 wherein the substrate is comprised of one or more of Mg, O, Al, Ti, V, Cr, Mn, Fe, Co, B, Ni, Zr, Mo, Nb, Hf, Ta, W, Ir, Pt, and Pd.

14. The method of claim 1 wherein exposing the first Mg monolayer to oxygen or an oxygen species comprises a natural oxidation or radical oxidation process, or exposure to ozone.

15. A method of forming a MgMO layer on a substrate, comprising:
(a) co-depositing Mg and M with a sputter deposition method at a first temperature to form a first MgM layer on a substrate wherein M is one or more of Ti, V, Cr, Mn, Fe, Ga, In, Al, Si, Ge, Sn, Zr, Mo, Nb, Hf, Ta, and N;
(b) performing a first anneal at a second temperature between 200° C. and 900° C. in a first chamber such that a Mg vapor pressure reaches at least 10 −6 Torr and a substantial portion of Mg atoms in the first MgM layer sublimes thereby leaving a first MgM monolayer on the substrate; and
(c) performing a first oxidation at a third temperature between −223° C. and 900° C. by exposing the first MgM monolayer to oxygen or an oxygen species and thereby forming a first MgMO monolayer wherein at least all of the Mg atoms are oxidized, and M serves to create a crystal structure or substitutional defect that provides a different band structure or conductivity compared with a MgO film.

16. The method of claim 15 further comprising:
(a) sputter depositing a second MgM layer on the first MgMO monolayer;
(b) performing a second anneal at a temperature between 200° C. and 900° C. such that a Mg vapor pressure reaches at least 10 0.6 Torr and a substantial number of Mg atoms in the second MgM layer sublimes thereby leaving a second MgM monolayer on the first MgMO monolayer; and
(c) performing a second oxidation at a temperature between −223° C. and 900° C. by exposing the second MgM monolayer to oxygen or an oxygen species and thereby forming a second MgMO monolayer wherein the first and second MgMO monolayers form a MgMO layer that is essentially free of defects.

17. The method of claim 16 wherein the MgMO layer serves as a tunnel barrier layer, Hk enhancing layer, or an insulation layer.

18. The method of claim 16 wherein the MgMO layer is formed in a magnetic random access memory (MRAM), spin torque MRAM, sensor in a read head of a HDD, biosensor, or in a spin-logic based device.

19. The method of claim 15 wherein depositing the first MgM layer and performing the first anneal are carried out in a first chamber.

20. The method of claim 15 wherein the third temperature is essentially equivalent to the second temperature, and the first oxidation is performed in the first chamber.

21. The method of claim 15 wherein the substrate is comprised of one or more of Mg, O, Al, Ti, V, Cr, Mn, Fe, Co, B, Ni, Zr, Mo, Nb, Hf, Ta, W, Ir, Pt, and Pd.

22. The method of claim 15 wherein exposing the first MgM monolayer to oxygen or an oxygen species comprises a natural oxidation or radical oxidation process, or exposure to ozone.

23. The method of claim 15 wherein a M content in the first MgM layer is from a plurality of parts per million (ppm) to about 75 atomic %.

Assignees

• Taiwan Semiconductor Mfg Co Ltd

Inventors

• Patel Sahil
• Jan Guenole
• Wang Yu-Jen

Classifications

• C23C14/0073

  by exposing the substrates to reactive gases intermittently · CPC title

• C01F5/04

  by oxidation of metallic magnesium · CPC title

• C23C14/185

  by cathodic sputtering · CPC title

• C23C14/5806

  Thermal treatment · CPC title

• C23C14/5873

  Removal of material · CPC title