Etching method, semiconductor manufacturing apparatus, and method of manufacturing semiconductor device

1. An etching method comprising

alternately switching a first step and a second step,

the first step introducing a first gas containing a fluorine atom without supplying a radiofrequency voltage to form a surface layer on a surface of a target cooled at a temperature equal to or lower than the liquefaction temperature of the first gas; and

the second step introducing a second gas gaseous at the temperature and different from the first gas with halting the introduction of the first gas, and supplying the radiofrequency voltage to generate plasma from the second gas and thus etch the target by sputtering using the plasma,

wherein the introduction of the second gas is halted before the introduction of the first gas in the first step, and

the first step is performed without the introduction of the second gas,

wherein the etching method further comprises

alternately switching a third step and a fourth step,

the third step introducing the first gas without supplying the radiofrequency voltage, and

the fourth step introducing a third gas containing a hydrogen atom and supplying the radiofrequency voltage to modify the surface layer.

2. The etching method according to claim 1 , further comprising

vaporizing a residue of the surface layer after the alternate switch between the first and second steps by irradiating light toward the target,

wherein the light is infrared light, visible light, or ultraviolet light.

3. The etching method according to claim 1 ,

wherein the first gas containing a fluorine atom is represented by a composition formula C x H y F z ,

where C denotes carbon, H denotes hydrogen, F denotes fluorine, x denotes an integer equal to or larger than 1, y denotes an integer equal to or larger than 0, and z denotes an integer equal to or larger than 2.

4. The etching method according to claim 1 , further comprising:

a fifth step of introducing a fourth gas different from the third gas and supplying the radiofrequency voltage to remove a modified part of the surface layer.

5. The method according to claim 1 ,

wherein the target has an opening on the surface, and

the surface layer is formed on a bottom surface of the opening in the first step.

6. The method according to claim 1 ,

wherein the introduction of the first gas in the first step and the introduction of the second gas in the second step are alternately switched while the non-supply of the radiofrequency voltage in the first step and the supply of the radiofrequency voltage in the second step are alternately switched.

7. The method according to claim 1 ,

wherein the surface layer is liquid or solid.

8. An etching method comprising

alternately switching a first step and a second step,

the first step introducing a first gas containing a fluorine atom without supplying a radiofrequency voltage to form a surface layer on a surface of a target cooled at a temperature equal to or lower than the liquefaction temperature of the first gas; and

the second step introducing a second gas gaseous at the temperature and different from the first gas with halting the introduction of the first gas, and supplying the radiofrequency voltage to generate plasma from the second gas and thus etch the target by sputtering using the plasma,

wherein the introduction of the second gas is halted before the introduction of the first gas in the first step,

wherein the first step is performed without the introduction of the second gas,

wherein the first step includes:

a first sub-step of introducing the first gas at a first temperature and a first pressure in a gas phase region of the first gas, without supplying the radiofrequency voltage;

a second sub-step of cooling the target at a second temperature lower than the first temperature and a second pressure in a liquid phase region of the first gas, without supplying the radiofrequency voltage, to form the surface layer in liquid phase;

a third sub-step of cooling the target at a third temperature lower than the second temperature and a third pressure in a solid phase region of the first gas, without supplying the radiofrequency voltage to form the surface layer in solid phase;

a fourth sub-step of cooling the target at a fourth temperature and a fourth pressure lower than the third pressure in the solid phase region, without supplying the radiofrequency voltage, and

wherein the second step introduces the second gas and supplies the radiofrequency voltage to generate plasma from the second gas at the fourth temperature and the fourth pressure in the solid phase region and thus etch the target by sputtering using the plasma.

9. The etching method according to claim 8 ,

wherein the second pressure is higher than a pressure at a triple point of the first gas.

10. A method of manufacturing a semiconductor device, comprising:

preparing a target including a film above a semiconductor substrate; and

alternately switching a first step and a second step,

the first step introducing a first gas containing a fluorine atom without supplying radiofrequency voltage to form a surface layer on the target cooled at a temperature equal to or lower than the liquefaction temperature of the first gas, and

the second step introducing a second gas gaseous at the temperature and different from the first gas with halting the introduction of the first gas, and supplying the radiofrequency voltage to generate plasma from the second gas and thus etch the target by sputtering using the plasma,

wherein the introduction of the second gas is halted before the introduction of the first gas in the first step, and

the first step is performed without the introduction of the second gas,

wherein the method further comprises

alternately switching a third step and a fourth step,

the third step introducing the first gas without supplying the radiofrequency voltage,

the fourth step introducing a third gas containing a hydrogen atom and supplying the radiofrequency voltage to modify the surface layer.

11. The method according to claim 10 , further comprising

irradiating light toward the target to vaporize a residue of the surface layer after the alternate switch between the first and second steps.

12. The method according to claim 10 ,

wherein the first gas containing a fluorine atom is represented by a composition formula C x H y F z

where C denotes carbon, H denotes hydrogen, F denotes fluorine, x denotes an integer equal to or larger than 1, y denotes an integer equal to or larger than 0, and z denotes an integer equal to or larger than 2.

13. The method according to claim 10 , further comprising:

a fifth step of introducing a fourth gas different from the third gas and supplying the radiofrequency voltage to remove a modified part of the surface layer.

14. The method according to claim 10 ,

wherein the surface layer is liquid or solid.