Systems and methods for thin-film deposition of metal oxides using excited nitrogen—oxygen species

1. A method for depositing a film on a substrate that is within a reaction chamber, the method comprising applying an atomic layer deposition cycle to the substrate, the cycle comprising:

exposing the substrate to a precursor gas for a precursor pulse interval then removing the precursor gas thereafter;

forming active N x O y species;

introducing the active N x O y species to a reaction chamber;

exposing the substrate to an oxidizer comprising an oxidant gas and the active N x O y species for an oxidation pulse interval then removing the oxidizer thereafter to thereby increase a film deposition rate and a film deposition uniformity; and

prior to introducing the active N x O y species to the reaction chamber, monitoring the active N x O y species using a sensor and adjusting one or more process parameters based on the monitoring.

2. The method of claim 1 wherein the precursor gas comprises a rare earth metal selected from the group consisting of Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu, and combinations thereof.

3. The method of claim 1 wherein the precursor gas comprises at least one of an organo-metallic and a metal halide compound.

4. The method of claim 1 wherein the precursor gas comprises at least one of:

hafnium tetrachloride (HfCl 4 );

titanium tetrachloride (TiCl 4 );

tantalum pentachloride (TaCl 5 );

tantalum pentafluoride (TaF 5 );

zirkonium tetrachloride (ZrCl 4 );

rare earth betadiketonate compounds including (La(THD) 3 ) and (Y(THD) 3 );

rare earth cyclopentadienyl (Cp) compounds including La(iPrCp) 3 ;

rare earth amidinate compounds including lanthanum tris-formamidinate La(FAMD) 3 ;

cyclooctadienyl compounds including rare earth metals;

alkylamido compounds including:

tetrakis-ethyl-methylamino hafnium (TEMAHf);

tetrakis (diethylamino) hafnium ((Et2N)4Hf or TDEAH); and

tetrakis (dimethylamino) hafnium ((Me2N)4Hf or TDMAH);

alkoxides;

halide compounds of silicon;

silicon tetrachloride;

silicon tetrafluoride; and

silicon tetraiodide.

5. The method of claim 1 wherein the oxidant gas is a nitrogen-containing species gas.

6. The method of claim 1 wherein the active N x O y species comprise activated ionic or radical species including at least one of NO*, N 2 O*, NO 2 *, NO 3 *, and N 2 O 5 *.

7. The method of claim 1 wherein the oxidant gas comprises ozone and one or more gasses selected from the group consisting of O, O 2 , NO, N 2 O, NO 2 , NO 3 , N 2 O 5 , an N x O y radical species, an N x O y ionic species, and combinations thereof.

8. The method of claim 7 wherein the oxidant gas comprises approximately 5 atomic percent to 25 atomic percent O 3 .

9. The method of claim 7 wherein O 3 is produced from O 2 and a nitrogen source gas wherein a mixture of the O 2 and nitrogen source gas is subjected to a plasma discharge.

10. The method of claim 9 wherein the nitrogen source gas is at least one of N 2 , NO, N 2 O, NO 2 , NO 3 , and N 2 O 5 .

11. The method of claim 10 wherein flow ratio of N 2 /O 2 is >0.001.

12. The method of claim 10 wherein the ratio of the O 2 and the nitrogen source gas determine at least one of:

an amount of the active N x O y species comprising activated ionic or radical species including at least one of NO*, N 2 O*, NO 2 *, NO 3 *, and N 2 O 5 *;

a concentration of the active N x O y species comprising activated ionic or radical species including at least one of NO*, N 2 O*, NO 2 *, NO 3 *, and N 2 O 5 *;

a growth rate of the deposited film;

a film uniformity across the substrate;

a dielectric constant of the deposited film;

an index of refraction of the deposited film; and

a molecular composition of the deposited film.

13. The method of claim 10 wherein a power input controls the plasma, and an amount of power delivered to the plasma determine at least one of:

an amount of the active N x O y species comprising activated ionic or radical species including at least one of NO*, N 2 O*, NO 2 *, NO 3 *, and N 2 O 5 *;

a concentration of the active N x O y species comprising activated ionic or radical species including at least one of NO*, N 2 O*, NO 2 *, NO 3 *, and N 2 O 5 *;

a growth rate of the deposited film;

a film uniformity across the substrate;

a dielectric constant of the deposited film;

an index of refraction of the deposited film; and

a molecular composition of the deposited film.

14. The method of claim 10 further comprising:

generating the oxidizer by exposing O 2 and a nitrogen source gas to a plasma discharge;

monitoring a ratio of O 3 and the active N x O y species generated by the plasma discharge; and

adjusting at least one of a power input to the plasma discharge, a temperature of a housing; a flow rate of the O 2 , and a flow rate of the nitrogen source gas to achieve a predetermined criterion.

15. The method of claim 14 wherein the predetermined criterion includes at least one of:

an oxidizer flow rate;

an oxidant/N x O y concentration ratio;

an active N x O y species concentration;

a ratio of the active N x O y species, wherein the active N x O y species gas contains a plurality of excited nitrogen-oxygen compounds; and

a concentration of a particular active nitrogen-oxygen compound.

16. The method of claim 1 wherein the active N x O y species comprises an excited N x O y radical species, an excited N x O y ionic species, and combinations thereof.

17. The method of claim 1 wherein oxidant gas comprises a mixture of two or more of O, O 2 , NO, N 2 O, NO 2 , NO 3 , N 2 O 5 , NO x , N x O y , radicals thereof, and O 3 , and wherein the mixture comprises approximately 5 atomic percent to 25 atomic percent O 3 .

18. The method of claim 1 further comprising:

exposing the substrate to a second precursor gas for a second precursor pulse interval then removing the second precursor gas thereafter; and

after removing the second precursor gas, exposing the substrate to an oxidizer comprising an oxidant gas and a nitrogen-containing species gas for a oxidation pulse interval then removing the oxidizer thereafter.

19. A method comprising depositing a metal oxide in any film stack using a metal halide precursor and an oxidant comprising ozone and excited nitrogen-oxygen species;

wherein the ozone and the excited nitrogen-oxygen species are formed using a remote plasma,

wherein, prior to introducing the excited nitrogen-oxygen species to a reaction chamber, the excited nitrogen-oxygen species are monitored using a sensor and one or more process parameters are adjusted based on the monitored excited nitrogen-oxygen species, and

wherein a deposition rate and a deposition uniformity increase as a result of the excited nitrogen-oxygen species.

20. The method of claim 19 wherein the metal oxide comprises at least one of Al 2 O 3 , HfO 2 , ZrO 2 , La 2 O 3 and Ta 2 O 5 .

21. The method of claim 19 wherein the metal halide comprises any metal in compound combination with any halide element.

22. A method for depositing a film on a substrate comprising controlling uniformity of deposition of the deposited film by monitoring active nitrogen-oxygen species using a sensor prior to introducing the active nitrogen-oxygen species to a reaction chamber and adjusting an amount of the active nitrogen-oxygen species provided to the reaction chamber based on the monitoring.