Method to selectively etch silicon nitride to silicon oxide using water crystallization

Patent metadata

Field	Value
Publication number	US-12424447-B2
Application number	US-202217967996-A
Country	US
Kind code	B2
Filing date	Oct 18, 2022
Priority date	Oct 18, 2022
Publication date	Sep 23, 2025
Grant date	Sep 23, 2025

Abstract

Embodiments of improved processes and methods that provide selective etching of silicon nitride are disclosed herein. More specifically, a cyclic, two-step dry etch process is provided to selectively etch silicon nitride layers formed on a substrate, while protecting oxide layers formed on the same substrate. The cyclic, two-step dry etch process sequentially exposes the substrate to: (1) a hydrogen plasma to modify exposed surfaces of the silicon nitride layer and the oxide layer to form a modified silicon nitride surface layer and a modified oxide surface layer, and (2) a halogen plasma to selectively etch silicon nitride by removing the modified silicon nitride surface layer without removing the modified oxide surface layer. The oxide layer is protected from etching during the removal step (i.e., step 2) by creating a crystallized water layer on the oxide layer during the surface modification step (i.e., step 1).

First claim

What is claimed is:

1. A method of selectively etching silicon nitride over oxide, comprising:
providing a substrate having a silicon nitride layer and an oxide layer exposed on a surface of the substrate;
exposing the surface of the substrate to a hydrogen plasma to: (a) modify an exposed surface of the silicon nitride layer to form a first modified layer, and (b) modify an exposed surface of the oxide layer to form a second modified layer, wherein a gas pressure used to generate the hydrogen plasma and a temperature of the substrate create a crystallized water layer, which bonds with the exposed surface of the oxide layer to form the second modified layer between the crystallized water layer and an unmodified portion of the oxide layer underlying the second modified layer;
exposing the surface of the substrate to a halogen plasma to selectively etch the silicon nitride layer over the oxide layer by removing the first modified layer without removing the second modified layer, wherein during said exposing the surface of the substrate to the halogen plasma, the crystallized water layer reduces etching of the oxide layer by preventing reactive species of the halogen plasma from reaching the second modified layer; and
repeating said exposing the surface of the substrate to the hydrogen plasma and said exposing the surface of the substrate to the halogen plasma one or more times until a predetermined amount of the silicon nitride layer is selectively etched.

2. The method of claim 1 , wherein the first modified layer is a silicon layer, wherein the second modified layer is a silicon dioxide layer, and wherein the reactive species of the halogen plasma selectively etch silicon over silicon dioxide to further reduce or eliminate etching of the oxide layer.

3. The method of claim 1 , wherein the gas pressure ranges between 10 mTorr and 1500 Torr and the temperature of the substrate ranges between 0° C. and −80° C.

4. The method of claim 1 , wherein during said exposing the surface of the substrate to the hydrogen plasma, the hydrogen plasma reacts with the exposed surface of the silicon nitride layer to form a first reaction byproduct, which is vaporized at the gas pressure and the temperature of the substrate to form the first modified layer.

5. The method of claim 4 , wherein the first reaction byproduct is ammonia (NH 3 ), and wherein the first modified layer is a silicon layer.

6. The method of claim 1 , wherein during said exposing the surface of the substrate to the hydrogen plasma, the hydrogen plasma reacts with the exposed surface of the oxide layer to produce a second reaction byproduct, which freezes at the gas pressure and the temperature of the substrate to create the crystallized water layer on the exposed surface of the oxide layer and form the second modified layer.

7. The method of claim 6 , wherein the second reaction byproduct is water (H 2 O), and wherein the second modified layer is a silicon dioxide layer.

8. The method of claim 1 , wherein the first modified layer is a silicon layer, wherein the second modified layer is a silicon dioxide layer, and wherein the method further comprises generating the halogen plasma from one or more process gases, which have an etch selectivity of silicon to silicon dioxide of 5:1 or greater.

9. The method of claim 8 , wherein the one or more processing gases comprise one or more of chlorine (Cl 2 ), hydrogen bromide (HBr), difluoride (F 2 ), xenon difluoride (XeF2), tetrafluoromethane (CF 4 ), nitrogen trifluoride (NF 3 ) and sulfur hexafluoride (SF 6 ).

10. A method of selectively etching silicon nitride over oxide, comprising:
providing a substrate having a silicon nitride layer and an oxide layer exposed on a surface of the substrate;
generating a hydrogen plasma at a gas pressure less than 1500 Torr and a temperature of the substrate less than or equal to 0° C.;
exposing the surface of the substrate to the hydrogen plasma, wherein the hydrogen plasma:
reacts with an exposed surface of the silicon nitride layer to form a first reaction byproduct, which is vaporized at the gas pressure and the temperature of the substrate to form a first modified layer on the silicon nitride layer; and
reacts with an exposed surface of the oxide layer to produce a second reaction byproduct, which freezes at the gas pressure and the temperature of the substrate to create a crystallized water layer and form a second modified layer on the oxide layer; and

exposing the surface of the substrate to a halogen plasma to selectively etch the silicon nitride layer by removing the first modified layer without removing the second modified layer.

11. The method of claim 10 , further comprising repeating said exposing the surface of the substrate to the hydrogen plasma and said exposing the surface of the substrate to the halogen plasma a number of cycles to selectively etch a predetermined amount of the silicon nitride layer.

12. The method of claim 10 , wherein the gas pressure ranges between 10 mTorr and 1500 Torr and the temperature of the substrate ranges between 0° C. and −80° C.

13. The method of claim 10 , wherein during said exposing the surface of the substrate to the halogen plasma, the crystallized water layer reduces etching of the oxide layer by preventing reactive species of the halogen plasma from reaching the second modified layer.

14. The method of claim 13 , wherein the first modified layer is a silicon layer, wherein the second modified layer is a silicon dioxide layer, and wherein the reactive species of the halogen plasma selectively etch silicon over silicon dioxide to further reduce or eliminate etching of the oxide layer.

15. The method of claim 10 , wherein the halogen plasma is generated from one or more process gases, which have an etch selectivity of silicon to silicon dioxide of 5:1 or greater.

16. The method of claim 10 , wherein the hydrogen plasma is generated from one or more process gases comprising hydrogen (H 2 ), hydrogen bromide (HBr), methane (CH 4 ) and hydrogen sulfide (H 2 S), and wherein the halogen plasma is generated from one or more process gases comprising chlorine (Cl 2 ), hydrogen bromide (HBr), difluoride (F 2 ), xenon difluoride (XeF2), tetrafluoromethane (CF 4 ), nitrogen trifluoride (NF 3 ) and sulfur hexafluoride (SF 6 ).

17. The method of claim 10 , wherein the first reaction byproduct is ammonia (NH 3 ) and the first modified layer is a silicon layer, and wherein the second reaction byproduct is water (H 2 O) and the second modified layer is a silicon dioxide layer.

18. The method of claim 17 , wherein when the surface of the substrate is exposed to the hydrogen plasma, the gas pressure used to generate the hydrogen plasma and the temperature of the substrate:
vaporize the ammonia (NH 3 ) from the exposed surface of the silicon nitride layer to form the silicon layer; and
freeze the water (H 2 O) on the exposed surface of the oxide layer to create the crystallized water layer, which bonds with the exposed surface of the oxide layer to form the silicon dioxide layer.

19. The method of claim 18 , wherein the gas pressure used to generate the hydrogen plasma and the temperature of the substrate is selected from a pressure-temperature window comprising a pressure range between 10 mTorr and 1500 Torr and a temperature range between 0° C. and −80° C.

Assignees

• Tokyo Electron Ltd

Inventors

• Tsai Yu-Hao
• Wang Mingmei
• Zhang Du

Classifications

• H10P50/695

  characterised by the process involved to create the mask, e.g. lift-off masks or sidewalls or to modify the mask · CPC title

• H10P50/692 Primary

  characterised by their composition, e.g. multilayer masks or materials · CPC title

• H10P95/00

  Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass · CPC title

• H10P50/283 Primary

  by chemical means · CPC title

• H01L21/3086

  Electricity · mapped topic