IN SITU DEPOSITION OF DIFFERENT METAL-CONTAINING FILMS USING CYCLOPENTADIENYL METAL PRECURSORS

• US 20090035946A1
• Filed: 07/15/2008
• Published: 02/05/2009
• Est. Priority Date: 07/31/2007
• Status: Abandoned Application

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Zagwijn, Peter, Pierreux, Dieter, Jongbloed, Bert
• Application Number:
  US12/173,374
• Publication Number:
  US 20090035946A1
• Time in Patent Office: Days
• US Class Current: 438/763
• CPC Class Codes: C23C 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient compositions
• CPC Class Codes: C23C 16/45546 specially adapted for a substrate stack in the ALD reactor
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/022 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides adhesion layers or buffer layers H01L21/02304, H01L21/02362
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/3142 of nano-laminates, e.g. alternating layers of Al203-Hf02
• CPC Class Codes: H01L 21/31616 Deposition of Al2O3
• CPC Class Codes: H01L 21/31641 Deposition of Zirconium oxides, e.g. ZrO2
• CPC Class Codes: H01L 21/31645 Deposition of Hafnium oxides, e.g. HfO2

Abstract

A method is disclosed depositing multiple layers of different materials in a sequential process within a deposition chamber. A substrate is provided in a deposition chamber. A plurality of cycles of a first atomic layer deposition (ALD) process is sequentially conducted to deposit a layer of a first material on the substrate in the deposition chamber. These first cycles include pulsing a cyclopentadienyl metal precursor. A plurality of cycles of a second ALD process is sequentially conducted to deposit a layer of a second material on the layer of the first material in the deposition chamber. The second material comprises a metal different from the metal in the cyclopentadienyl metal precursor.

Claims

1. A method of depositing multiple layers of different materials in a sequential process within a deposition chamber, the method comprising:

providing a substrate in a deposition chamber;

sequentially conducting a plurality of cycles of a first atomic layer deposition (ALD) process to deposit a layer of a first material on the substrate in the deposition chamber, the first cycles including pulsing a cyclopentadienyl metal precursor; and

sequentially conducting a plurality of cycles of a second ALD process to deposit a layer of a second material on the layer of the first material in the deposition chamber, wherein the second material comprises a metal different from the metal in the cyclopentadienyl metal precursor.

2. The method of claim 1, wherein the first and second materials comprise metal oxide materials.

3. The method of claim 2, wherein the first material comprises zirconium oxide or hafnium oxide, and the second material comprises aluminum oxide.

4. The method of claim 1, further comprising conducting a further plurality of cycles of the first ALD process within the deposition chamber to deposit a second layer of the first material over the layer of the second material.

5. The method of claim 1, wherein the cycles of the first ALD process are conducted at a first average temperature and the cycles of the second ALD process are conducted at a second average temperature, the first and second temperatures being within about 25°

C. of one another.

6. The method of claim 5, wherein the first and second temperatures are within about 10°

C. of one another.

7. The method of claim 5, wherein the deposition chamber comprises a batch vertical furnace housing a plurality of substrates, wherein providing the substrate comprises loading a plurality of substrates into the deposition chamber, and sequentially conducting the pluralities of the first and second ALD processes comprises depositing the layers of the first and second materials on the plurality of substrates.

8. The method of claim 1, wherein the cyclopentadienyl metal precursor comprises a precursor selected from the group consisting of bis(cyclopentadienyl)bis(methoxy) hafnium (IV), bis(cyclopentadienyl)methyl methoxy hafnium (IV), bis(methylcyclopentadienyl)bis(methoxy) hafnium (IV), bis(methylcyclopentadienyl)methyl methoxy hafnium (IV), bis(cyclopentadienyl)bis(methoxy) zirconium (IV), bis(cyclopentadienyl)methyl methoxy zirconium (IV), bis(methylcyclopentadienyl)bis(methoxy) zirconium (IV), and bis(methylcyclopentadienyl)methyl methoxy zirconium (IV).

9. The method of claim 1, wherein the first material comprises zirconium oxide or hafnium oxide, and the second material comprises aluminum oxide, the method further comprising sequentially conducting another plurality of cycles of the first ALD process to deposit an additional layer of zirconium oxide or hafnium oxide over the layer of aluminum oxide within the deposition chamber

10. The method of claim 9, wherein sequentially conducting the plurality of cycles of the second ALD process comprises pulsing trimethyl aluminum.

11. The method of claim 9, wherein sequentially conducting pluralities of each of the first and second ALD processes comprises maintaining the substrate at a temperature between about 300°

C. and 500°

C.

12. An apparatus comprising:

a processing chamber configured to contain a plurality of substrates;

a cyclopentadienyl metal precursor source connected to the chamber to deliver a vapor of the cyclopentadienyl metal precursor into the chamber;

an oxygen precursor source connected to the chamber to deliver a vapor of the oxygen precursor into the chamber;

an aluminum precursor source connected to the chamber to deliver a vapor of the aluminum precursor into the chamber; and

a deposition control system configured to conduct ALD in the chamber of a metal oxide from the cyclopentadienyl metal precursor and the oxygen precursor, the deposition control system also configured to conduct ALD in the chamber of aluminum oxide from the aluminum precursor and the oxygen precursor.

13. The apparatus of claim 12, wherein the cyclopentadienyl metal precursor comprises a precursor selected from the group consisting of bis(cyclopentadienyl)bis(methoxy)hafiiium (IV), bis(cyclopentadienyl)methyl methoxy hafnium (IV), bis(methylcyclopentadienyl)bis(methoxy)hafiium (IV), bis(methylcyclopentadienyl)methyl methoxy hafnium (IV), bis(cyclopentadienyl)bis(methoxy) zirconium (IV), bis(cyclopentadienyl)methyl methoxy zirconium (IV), bis(methylcyclopentadienyl)bis(methoxy) zirconium (IV), and bis(methylcyclopentadienyl)methyl methoxy zirconium (IV).

14. The apparatus of claim 12, wherein the oxygen precursor comprises ozone (O₃), H₂O, or O₂.

15. The apparatus of claim 12, wherein the aluminum precursor comprises trimethyl aluminum (TMA).

16. The apparatus of claim 12, wherein the deposition control system is programmed to control the chamber temperature and to conduct the ALD of the metal oxide and the aluminum oxide at chamber temperatures within about 25°

C. of one another.

17. The apparatus of claim 12, wherein the deposition control system is programmed to control the chamber temperature and to conduct the ALD of the metal oxide and the aluminum oxide at chamber temperatures within about 300-500°

C.

18. The apparatus of claim 17, wherein the deposition control system is programmed to conduct the ALD of the metal oxide and the aluminum oxide at temperatures within about 300-350°

C.

19. An apparatus comprising:

a processing chamber configured to contain a plurality of substrates;

a first reactant source connected to the chamber to deliver a vapor of the first reactant into the chamber, the first reactant comprising a cyclopentadienyl metal precursor;

a second reactant source connected to the chamber to deliver a vapor of the second reactant into the chamber, the second reactant comprising a metal different from the metal in the cyclopentadienyl metal precursor; and

a deposition control system configured to conduct a first ALD process in the chamber of a first metallic layer from the cyclopentadienyl metal precursor, the deposition control system also configured to conduct a second ALD process in the chamber of a second metallic layer from the second reactant, the deposition control system configured to conduct the first and second ALD processes at temperatures within about 25°

C. of one another.

20. The apparatus of claim 19, wherein the deposition control system is configured to conduct the first and second ALD processes at temperatures within about 10°

C. of one another.

21. The apparatus of claim 19, wherein the deposition control system is configured to conduct the first and second ALD processes at temperatures within about 5°

C. of one another.

22. The apparatus of claim 19, wherein the cyclopentadienyl metal precursor comprises a precursor selected from the group consisting of bis(cyclopentadienyl)bis(methoxy) hafnium (IV), bis(cyclopentadienyl)methyl methoxy hafnium (IV), bis(methylcyclopentadienyl)bis(methoxy) hafnium (IV), bis(methylcyclopentadienyl)methyl methoxy hafnium (IV), bis(cyclopentadienyl)bis(methoxy) zirconium (IV), bis(cyclopentadienyl)methyl methoxy zirconium (IV), bis(methylcyclopentadienyl)bis(methoxy) zirconium (IV), and bis(methylcyclopentadienyl)methyl methoxy zirconium (IV).