Method for forming a gate insulating film

1. A method for forming a gate insulating film of a high dielectric constant metal silicate on a semiconductor substrate, comprising the steps of:

(a) with the semiconductor substrate being held at 500° C. or less and a predetermined pressure, exposing the semiconductor substrate to a first precursor containing a metal element of the high dielectric constant metal silicate to form a first adsorption layer of the first precursor on the semiconductor substrate;

(b) purging the first precursor;

(c) exposing the first adsorption layer to an oxidizing agent and thus oxidizing the first adsorption layer to form a metal oxide film from the first adsorption layer;

(d) purging the oxidizing agent;

(e) after the step (d), exposing the metal oxide film to a second precursor containing silicon to form a second adsorption layer of the second precursor on the metal oxide film;

(f) purging the second precursor;

(g) exposing the second adsorption layer to the oxidizing agent and thus oxidizing the second adsorption layer to form a silicon oxide film from the second adsorption layer; and

(h) purging the oxidizing agent, wherein

a cycle comprised of the steps (a), (b), (c), and (d) is performed at least once to form at least one layer of an atomic layer level of the metal oxide film, and a cycle comprised of the steps (e), (f), (g), and (h) is performed at least once to form at least one layer of an atomic layer level of the silicon oxide film, whereby the high dielectric constant metal silicate is formed,

in the step (a), exposure time of the semiconductor substrate to the first precursor is determined by saturation time of a thickness of the one layer of the metal oxide film deposited by the cycle,

in the step (c), exposure time of the first adsorption layer to the oxidizing agent is determined by time required for an oxygen content in the metal oxide film to reach 97% or more of a composition that is determined by stoichiometry,

in the step (e), exposure time of the metal oxide film to the second precursor is determined by saturation time of a thickness of the one layer of the silicon oxide film deposited in the cycle, and

in the step (g), exposure time of the second adsorption layer to the oxidizing agent is determined by time required for an oxygen content in the silicon oxide film to reach 97% or more of a composition that is determined by stoichiometry.

2. The method according to claim 1 , wherein the exposure time to the oxidizing agent in each of the steps (c) and (g) is 5 seconds or more per semiconductor substrate, and is set to either the exposure time in the step (c) or the exposure time in the step (g) which has a longer duration of the step.

3. The method according to claim 1 , wherein the high dielectric constant metal silicate is a hafnium silicate (HfSiO) or a hafnium lanthanum silicate (HfLaSiO).

4. The method according to claim 1 , wherein the oxidizing agent is ozone (O 3 ), water vapor (H 2 O), heavy water (D 2 O), or dinitrogen monoxide (N 2 O), or an oxygen radical.

5. The method according to claim 1 , wherein the first precursor is hafnium tetrachloride (HfCl 4 ), tetrakis-ethyl-methyl-amino-hafnium (TEMAH), or tetrakis-di-methyl-amino-hafnium (TDMAH), and the second precursor is silicon tetrachloride (SiCl 4 ), tris-di-methyl-amino-silicon (TDMAS), or tetraethyl orthosilicate (TEOS).

6. The method according to claim 1 , wherein in the step (c) of exposing the first adsorption layer to the oxidizing agent, a heating temperature of the semiconductor substrate is a temperature of an atomic layer deposition (ALD) reaction or up to a temperature at which a reaction mode transitions from the atomic layer deposition (ALD) reaction to a chemical vapor deposition (CVD) reaction, and the predetermined pressure is a pressure up to right before in-plane uniformity of the semiconductor substrate is degraded.

7. The method according to claim 1 , wherein in the step (c) of exposing the first adsorption layer to the oxidizing agent, a heating temperature of the semiconductor substrate is 300° C. or higher and is such a temperature that a chemical vapor deposition (CVD) reaction does not become dominant, and the predetermined pressure is 1.33×10 2 Pa to 3.99×10 2 Pa.

8. A method for forming a gate insulating film of a high dielectric constant metal silicate on a semiconductor substrate, comprising the steps of:

(a) with the semiconductor substrate being held at 500° C. or less and a predetermined pressure, exposing the semiconductor substrate to a first precursor containing a metal element of the high dielectric constant metal silicate and a second precursor containing silicon of the high dielectric constant metal silicate at mixing ratio corresponding to a composition ratio of the dielectric constant metal silicate, thereby forming on the semiconductor subtrate and absorption layer made of the first precursor and the second precursor and having a composition ratio corresponding to the composition ratio of high dielectric constant metal silisate;

(b) purging the first precursor and the second precursor;

(c) exposing the adsorption layer to an oxidizing agent and thus oxidizing the adsorption layer to form a metal silicate film from the adsorption layer; and

(d) purging the oxidizing agent, wherein

a cycle comprised of the steps (a), (b), (c), and (d) is performed at least once to form at least one layer of an atomic layer level of the metal silicate film, whereby the high dielectric constant metal oxide is formed,

in the step (a), exposure time of the semiconductor substrate to the precursor and the second precursor is set to a longer one of respective saturation times of thickness of the one layer deposited by the cycle which are obtained when an oxide film of a metal of the high dielectric constant metal silicate and an oxide film of silicon of the high dielectric constant metal silicate are independently deposited, and

in the (c), exposure time of the absorption layer to the oxidizing agent is set to a longer of respective time required for an oxegen content in the oxide film of the metal and oxegen content in the oxide film of silicon to reach 97% or more of a composition that is determined by stoichiometry when the oxide film of the metal of the high dielectric constant metal silicate and the oxide film of silicon of the dielectric constant metal silicate are independently deposited.

9. The method according to claim 8 , wherein the high dielectric constant metal silicate is a hafnium silicate (HfSiO) or a hafnium lanthanum silicate (HfLaSiO).

10. The method according to claim 8 , wherein the oxidizing agent is ozone (O 3 ), water vapor (H 2 O), heavy water (D 2 O), or dinitrogen monoxide (N 2 O), or an oxygen radical.

11. The method according to claim 8 , wherein the first precursor is hafnium tetrachloride (HfCl 4 ), tetrakis-ethyl-methyl-amino-hafnium (TEMAH), or tetrakis-di-methyl-amino-hafnium (TDMAH), and the second precursor is silicon tetrachloride (SiCl 4 ), tris-di-methyl-amino-silicon (TDMAS), or tetraethyl orthosilicate (TEOS).

12. The method according to claim 8 , wherein the first precursor and the second precursor contain oxygen.

13. The method according to claim 8 , wherein in the step (c) of exposing the adsorption layer to the oxidizing agent, a heating temperature of the semiconductor substrate is a temperature of an atomic layer deposition (ALD) reaction or up to a temperature at which a reaction mode transitions from the atomic layer deposition (ALD) reaction to a chemical vapor deposition (CVD) reaction, and the predetermined pressure is a pressure up to right before in-plane uniformity of the semiconductor substrate is degraded.

14. The method according to claim 8 , wherein in the step (c) of exposing the adsorption layer to the oxidizing agent, a heating temperature of the semiconductor substrate is 300° C. or higher and such a temperature that a chemical vapor deposition (CVD) reaction does not become dominant, and the predetermined pressure is 1.33×10 2 Pa to 3.99×10 2 Pa.