Method for selectivity enhancement during dry plasma etching

1. A method of etching a layer on a substrate, comprising:

disposing a substrate having a heterogeneous layer composed of a first material and a second material in a processing space of a plasma processing system, wherein the heterogeneous layer has an initial upper surface exposing the first material and the second material to a plasma environment in the processing space, and

performing a modulated plasma etching process to selectively remove the first material at a rate greater than removing the second material by applying radio frequency (RF) power pulses to a substrate holder that supports the substrate, the modulated plasma etching process including a modulation cycle that:

(i) preferentially reacts an etchant with the first material during a first phase of the modulation cycle, and

(ii) differentially adheres a passivant on the second material relative to the first material during a second phase of the modulation cycle,

wherein pulsing the RF power further includes:

(i) pulsing the RF power at a first RF power level for a first time duration; and

(ii) pulsing the RF power at a second RF power level for a second time duration,

wherein the second RF power level is less than the first RF power level, and the second time duration follows the first time duration.

2. The method of claim 1 , wherein an exposed surface of the first material is coplanar with an exposed surface of the second material.

3. The method of claim 1 , wherein the first material and the second material are silicon-containing materials of differing composition.

4. The method of claim 1 , wherein the first material and the second material are organic-containing materials of differing composition.

5. The method of claim 1 , wherein the first material is a first domain of a self-assembled block copolymer layer and the second material is a second domain of the self-assembled block copolymer layer.

6. The method of claim 5 , wherein the first domain of the self-assembled block copolymer is poly (meth methacrylate), and the second domain of the self-assembled block copolymer is polystyrene.

7. The method of claim 1 , wherein the passivant is introduced as a pulsed flow that is in phase with the RF pulses.

8. The method of claim 1 , wherein the passivant is introduced as a pulsed flow that is out of phase with respect to the RF pulses.

9. The method of claim 1 , wherein the passivant includes a C x H y R z -containing gas, wherein R represents a halogen element, x and y represent a real number greater than 0, and z represents a real number greater than or equal to 0.

10. A method of etching a layer on a substrate, comprising:

disposing a substrate having a heterogeneous layer composed of a first material and a second material in a processing space of a plasma processing system, wherein the heterogeneous layer has an initial upper surface exposing the first material and the second material to a plasma environment in the processing space, and

performing a modulated plasma etching process to selectively remove the first material at a rate greater than removing the second material, the modulated plasma etching process including a modulation cycle that:

preferentially reacts an etchant with the first material during a first phase of the modulation cycle, and

differentially adheres a passivant on the second material relative to the first material during a second phase of the modulation cycle,

wherein the modulated plasma etching process includes:

introducing a process gas composition to the plasma processing system, the process composition including a C x H y R z -containing gas, wherein R represents a halogen element, x and y represent a real number greater than 0, and z represents a real number greater than or equal to 0,

igniting plasma using a plasma source,

electrically biasing a substrate holder that supports the substrate with radio frequency (RF) power, and

modulating the RF power for the electrical biasing between a first power state during the first phase of the modulation cycle and a second power state during a second phase of the modulation cycle.

11. The method of claim 10 , further comprising:

selecting a process condition for the modulated plasma etching process and controlling a profile of the pattern formed within the heterogeneous layer, the process condition including setting a pulse amplitude, a pulse frequency, a pulse duty cycle, or a pulse waveform, or any combination thereof.

12. The method of claim 11 , wherein the process composition is continuously flowed into the plasma processing system during the pulsing.

13. The method of claim 10 , wherein the modulating of RF power for the electrical biasing comprises pulsing the RF power between an off-state and an on-state.

14. The method of claim 13 , further comprising:

achieving an etch rate of the first domain that is at least 4 times greater than the etch rate of the second domain.

15. The method of claim 10 , wherein the C x H y R z -containing gas has a hydrogen-to-carbon ratio (H/C) greater than unity, and a hydrogen-to-halogen ratio (H/R) greater than or equal to unity.

16. The method of claim 10 , wherein at least one constituent of the process composition is pulsed into the plasma processing system during the pulsing.

17. The method of claim 16 , wherein the pulsed flow of the at least one constituent of the process composition is in-phase or out-of-phase with the pulsing the RF power.

18. The method of claim 10 , wherein the modulating the RF power for the electrical biasing further comprises:

pulsing the RF power at a first RF power level for a first time duration; and

pulsing the RF power at a second RF power level for a second time duration, wherein the second RF power level is less than the first RF power level, and the second time duration follows the first time duration.

19. The method of claim 18 , wherein the pulsing the RF power for the electrical biasing further comprises:

pulsing the RF power at a third RF power level for a third time duration, wherein the third RF power level is less than the second RF power level, and the third time duration follows the second time duration.

20. The method of claim 18 , wherein the pulsing the RF power for the electrical biasing further comprises:

decreasing a RF power level for the pulsing the RF power.

21. The method of claim 18 , wherein the pulsing the RF power for the electrical biasing further comprises:

pulsing the RF power at a first RF power level for a first time duration;

pulsing the RF power at a second RF power level for a second time duration, wherein the second RF power level is less than the first RF power level, and the second time duration follows the first time duration; and

terminating the pulsing the RF power for a third time duration, the third time duration following the second time duration.

22. A method of patterning etching a layer on a substrate, comprising:

disposing a substrate having a phase-separated block copolymer layer thereon in a plasma processing system; and

selectively removing a first phase of the phase-separated block copolymer layer while retaining a second phase of the phase-separated block copolymer layer to form a pattern on the substrate by performing a pulsed etching process, the pulsed etching process comprising:

introducing a process gas composition to the plasma processing system, the process composition including a C x H y R z -containing gas, wherein R represents a halogen element, x and y represent a real number greater than 0, and z represents a real number greater than or equal to 0,

igniting plasma using a plasma source,

electrically biasing a substrate holder that supports the substrate with radio frequency (RF) power, and

pulsing the RF power for the electrical biasing.

23. The method of claim 22 , wherein the C x H y R z -containing gas has a hydrogen-to-carbon ratio (H/C) greater than unity, and a hydrogen-to-halogen ration (H/R) greater than or equal to unity.