Etching method

1. A method of etching comprising:

(a) providing a substrate including a silicon-containing film and a mask on the silicon-containing film in a chamber of a plasma treatment system; and

(b) etching the silicon-containing film with a chemical species in plasma generated from a process gas in the chamber, the process gas including a phosphorus gas component, a fluorine gas component, and a hydrogen fluoride gas component.

2. The method of claim 1 , further comprising forming a protective film containing phosphorous-oxygen bonds contained in the process gas on a side wall surface of a recess formed by the etching.

3. The method of claim 1 , further comprising, before step (b), setting the temperature of a substrate support that supports the substrate to 0° C. or less.

4. The method of claim 1 , wherein the silicon-containing film includes a silicon oxide film, a silicon oxide film and a silicon nitride film, or a silicon oxide film and a polycrystalline silicon film.

5. The method of claim 1 , wherein the phosphorus gas component includes a halogen component.

6. The method of claim 1 , wherein the phosphorus gas component includes the phosphorous component selected from the group consisting of PF 3 , PCl 3 , PF 5 , PCl 5 , POCl 3 , PH 3 , PBr 3 , and PBr 5 .

7. The method of claim 1 , wherein the process gas further includes an oxygen gas component.

8. The method of claim 1 , wherein the plasma treatment system is an inductively coupled plasma treatment system.

9. The method of claim 1 , wherein the process gas further includes a halogen gas component containing a halogen component other than fluorine component.

10. The method of claim 9 , wherein the halogen gas component is Cl 2 gas and/or HBr gas.

11. The method of claim 1 , wherein

a ratio of the flow rate of a second gas to the flow rate of a first gas in the process gas is above 0 and 0.5 or less,

the first gas is all gases included in the process gas excluding the phosphorus gas component, and

the second gas is the phosphorus gas component.

12. The method of claim 11 , wherein the ratio is 0.075 or more and 0.3 or less.

13. The method of claim 1 , wherein

step (b) includes periodically applying pulsed bias electric power to a bottom electrode of a substrate support that supports the substrate, when the plasma is present in the chamber, and

the bias electric power is radio-frequency bias electric power or pulsed DC voltage with negative polarity.

14. The method of claim 13 , wherein a frequency defining a period in which the pulsed bias electric power is applied to the bottom electrode is 5 Hz or higher and 100 kHz or lower.

15. The method of claim 1 , wherein the phosphorus gas component includes a fluorine component.

16. The method of claim 15 , wherein the phosphorus gas component includes PF 3 or PF 5 .

17. The method of claim 1 , wherein the fluorine gas component includes at least one gas selected from the group consisting of a fluorocarbon gas and a carbon-free fluorine gas.

18. The method of claim 17 , wherein the process gas further includes a hydrofluorocarbon gas.

19. The method of claim 17 , wherein the fluorocarbon gas includes at least one fluorocarbon gas selected from the group consisting of CF 4 , C 3 F 8 , C 4 F 6 , and C 4 F 8 .

20. The method of claim 19 , wherein the carbon-free fluorine gas is nitrogen trifluoride gas or sulfur hexafluoride gas.

21. The method of claim 1 , wherein the plasma treatment system is a capacitively coupled plasma treatment system.

22. The method of claim 21 , wherein

the plasma treatment system includes a substrate support in the chamber and an upper electrode disposed above the substrate support, and

in step (b), the plasma is generated by supplying a radio-frequency power to the upper electrode.

23. The method of claim 21 , wherein in step (b), the plasma is generated by supplying a radio-frequency power to a bottom electrode of a substrate support configured to support the substrate in the chamber.

24. The method of claim 23 , wherein a frequency of the radio-frequency power is a frequency within a frequency range from 27 MHz to 100 MHz.

25. A method of etching comprising:

(a) providing a substrate including a silicon-containing film and a mask on the silicon-containing film in a chamber of a plasma treatment system; and

(b) etching the silicon-containing film with a chemical species in plasma generated from a process gas in the chamber, the process gas including a phosphorus gas component, a hydrogen fluoride gas component, a hydrofluorocarbon gas component, and a halogen gas component containing a halogen component other than fluorine.

26. A method of etching comprising:

(a) providing a substrate having a silicon-containing film and a mask on the silicon-containing film in a chamber of a plasma treatment system; and

(b) generating plasma from a process gas in the chamber to etch the silicon-containing film and forming a recess in the silicon-containing film, the process gas including a hydrogen fluoride gas component, a phosphorus gas component, and a carbon gas component.

27. The method of claim 26 , wherein

the process gas further includes a rare gas, and

among the flow rates of all gases in the process gas excluding the rare gas, the flow rate of the hydrogen fluoride gas component is largest.

28. The method of claim 26 , wherein in step (b), a temperature of a substrate support that supports the substrate is set to a temperature of 0° C. or less or −40° C. or less.

29. The method of claim 26 , wherein the process gas further includes a fluorine-free halogen gas component.

30. The method of claim 26 , wherein the mask includes a carbon component.

31. The method of claim 26 , wherein a proportion of the flow rate of the phosphorous gas component to the flow rate of the process gas excluding a rare gas is 1% or more and 20% or less.

32. The method of claim 26 , wherein a flow rate of the hydrogen fluoride gas component is larger than a flow rate of the phosphorus gas component and a flow rate of the carbon gas component.

33. The method of claim 32 , wherein a proportion of the flow rate of the hydrogen fluoride gas component to the flow rate of the process gas excluding a rare gas is 50% or more and less than 99%.

34. The method of claim 26 , wherein the carbon gas component includes at least one gas selected from the group consisting of a fluorocarbon gas and a hydrofluorocarbon gas.

35. The method of claim 34 , wherein the carbon gas component includes at least two carbon atoms.

36. A plasma treatment system for etching a silicon-containing film of a substrate having the silicon-containing film and a mask, the plasma treatment system comprising:

a chamber;

a substrate support configured to support the substrate in the chamber;

a gas supply unit configured to supply a process gas containing a hydrogen fluoride gas component, a phosphorus gas component, and a carbon gas component in the chamber;

a plasma generator configured to generate plasma from the process gas; and

a controller configured to control the gas supply unit to supply the process gas into the chamber to etch the silicon-containing film of the substrate supported by the substrate support, and to control the plasma generator to generate plasma from the process gas in the chamber.