Multilayer encapsulation stacks by atomic layer deposition
Methods of depositing an encapsulation stack without damaging underlying layers are discussed. The encapsulation stacks are highly conformal, have low etch rates, low atomic oxygen concentrations, good hermeticity and good adhesion. These films may be used to protect chalcogen materials in PCRAM devices. Some embodiments utilize a two-step process comprising a first ALD process to form a protective layer and a second plasma ALD process to form an encapsulation layer.
1. A method of forming an encapsulation stack, the method comprising:
providing a substrate with a surface having at least one feature thereon, the surface comprising a film stack with a first exposed material and a second exposed material, the first exposed material comprising carbon and the second exposed material comprising a chalcogen, the feature having a height and width defining an aspect ratio;
forming a conformal dielectric protective layer directly on the first exposed material and the second exposed material by sequentially exposing the substrate to a first reactant and a second reactant, the protective layer comprising silicon nitride, and the first reactant comprising SiR a X b , where R is an organic group or H, X is a halogen, and a+b=4; and
forming a conformal hermetic encapsulation layer on the protective layer by sequentially exposing the substrate to a silicon precursor and a nitrogen precursor and a second plasma, the encapsulation layer comprising silicon nitride, wherein the substrate is maintained at a temperature less than or equal to about 250° C.,
wherein the protective layer is formed at a rate of greater than or equal to about 1 Å/min and the protective layer is formed without damaging the second exposed material.
2. The method of claim 1 , wherein the protective layer substantially adheres to the surface of the first exposed material and the second exposed material.
3. The method of claim 1 , wherein the aspect ratio is greater than or equal to 5:1.
4. The method of claim 1 , wherein forming the protective layer comprises exposing the substrate to a first plasma with a power less than or equal to about 200 W.
5. The method of claim 4 , wherein the surface of the substrate is nitridated to a depth of less than or equal to about 10 Å.
6. The method of claim 1 , wherein the substrate is maintained at a pressure greater than or equal to about 5 Torr during formation of the protective layer.
7. The method of claim 1 , wherein the second plasma has a power greater than or equal to about 50 W.
8. The method of claim 1 , wherein the substrate is maintained at a pressure less than or equal to about 20 Torr during formation of the encapsulation layer.
9. The method of claim 1 , wherein the encapsulation layer is formed by a plurality of exposure cycles, the cycles repeated at a rate of less than or equal to about 20 cycles/minute.
10. The method of claim 1 , wherein the encapsulation layer has a wet etch rate of less than or equal to about 8.5 Å/min in 100:1 DHF.
11. The method of claim 1 , wherein the encapsulation layer has a thickness of greater than or equal to about 10 Å.
12. The method of claim 1 , wherein oxidation of the encapsulation layer is less than or equal to about 3 Å under oxidative test conditions comprising one or more of PEALD of 60 Å of silicon oxide using BDEAS and 50 W of O 2 /Ar plasma or a steam anneal at 400° C. for 2 hours.
13. The method of claim 3 , wherein the aspect ratio is greater than or equal to about 10:1.
14. The method of claim 1 , wherein the first reactant consists essentially of one or more of SiCl 4 , SiBr 4 , SiI 4 , SiH 2 Cl 2 or SiH 2 I 2 .
15. The method of claim 14 , wherein the first reactant comprises chlorine.
16. The method of claim 14 , wherein the first reactant comprises bromine.
17. The method of claim 1 , wherein the first reactant comprises iodide.
18. The method of claim 1 , wherein forming the protective layer comprises substantially no plasma.