Additive for ALD deposition profile tuning in gap features

1. A method for performing atomic layer deposition (ALD) on a substrate, comprising:

exposing the substrate to a first reactant and an additive, such that exposure to the first reactant and exposure to the additive are initiated substantially simultaneously, the first reactant and the additive being configured to adsorb on exposed surfaces of the substrate, a partial pressure of the first reactant and a partial pressure of the additive being configured so that adsorption of the additive in a gap feature of the substrate decreases as depth increases in the gap feature, wherein the first reactant is a metal-containing precursor, and wherein the additive is an alcohol or an organoamine,

wherein, during the exposure to the first reactant and the additive that is initiated substantially simultaneously, the partial pressure of the additive is configured to prevent diffusion of the additive to a bottom of the gap feature and the partial pressure of the first reactant is configured to enable diffusion of the first reactant to the bottom of the gap feature,

wherein exposing the substrate to the first reactant and the additive includes, pulsing the first reactant and the additive into a carrier gas stream that is flowed into a process chamber in which the substrate is disposed, wherein pulsing the first reactant and the additive into the carrier gas stream includes simultaneously turning on a flow of the first reactant and a flow of the additive into the carrier gas stream;

after exposing the substrate to the first reactant and the additive, exposing the substrate to a second reactant, the second reactant configured to react with the adsorbed first reactant to form a thin film product, the thin film product being an oxide or a nitride, the second reactant configured to react with the adsorbed additive to remove the adsorbed additive from the substrate surface,

wherein exposing the substrate to the second reactant includes, pulsing the second reactant into the carrier gas stream.

2. The method of claim 1 , wherein the additive is configured to compete with the first reactant for available adsorption locations on the exposed surfaces of the substrate, the first reactant and the additive being configured to adsorb as a self-limiting monolayer, wherein adsorption of the additive prevents formation of the thin film product at locations where the additive adsorbed on the substrate surface.

3. The method of claim 2 , wherein the partial pressure of the additive is less than the partial pressure of the first reactant.

4. The method of claim 2 , wherein a temperature of the process chamber is controlled to provide for the partial pressures of the first reactant and the additive.

5. The method of claim 1 , further comprising:

repeating the operations of exposing the substrate to the first reactant and the additive simultaneously, and exposing the substrate to the second reactant, for a predefined number of cycles so as to deposit multiple layers of the thin film product, wherein a deposition amount of the thin film product along sidewalls of the gap feature increases with increasing depth in the gap feature.

6. The method of claim 1 ,

wherein after exposing the substrate to the first reactant and the additive simultaneously, a first purge operation is performed to remove unreacted quantities of the first reactant and the additive from the process chamber;

wherein after exposing the substrate to the second reactant, a second purge operation is performed to remove unreacted quantities of the second reactant, and quantities of the deposited additive that have been removed from the substrate surface, from the process chamber.

7. The method of claim 6 ,

wherein performing the first purge operation includes continuing the flow of the carrier gas stream through the process chamber and evacuating the process chamber so as to remove the unreacted quantities of the first reactant and the additive from the process chamber;

wherein performing the second purge operation includes continuing the flow of the carrier gas stream through the process chamber and evacuating the process chamber so as to remove the unreacted quantities of the second reactant, and the quantities of the deposited additive that have been removed from the substrate surface, from the process chamber.

8. The method of claim 1 ,

wherein the thin film product is an oxide of silicon; and

wherein the first reactant is a silicon-containing precursor.

9. The method of claim 8 , wherein the first reactant is diisopropylaminosilane (DIPAS), bis(diethylamine)silane (BDEAS) or bis(tertiarybuthylamine)silane (BTBAS).

10. A method for performing atomic layer deposition (ALD) on a substrate, comprising:

exposing the substrate to a first reactant and an additive, such that exposure to the first reactant and exposure to the additive are initiated substantially simultaneously, the first reactant and the additive being configured to adsorb on exposed surfaces of the substrate, a partial pressure of the first reactant and a partial pressure of the additive being configured so that adsorption of the additive in a gap feature of the substrate decreases as depth increases in the gap feature, wherein the first reactant is diisopropylaminosilane (DIPAS) or bis(diethylamine)silane (BDEAS), and wherein the additive is an alcohol or an organoamine,

wherein, during the exposure to the first reactant and the additive that is initiated substantially simultaneously, the partial pressure of the additive is configured to prevent diffusion of the additive to a bottom of the gap feature and the partial pressure of the first reactant is configured to enable diffusion of the first reactant to the bottom of the gap feature,

wherein exposing the substrate to the first reactant and the additive includes, pulsing the first reactant and the additive into a carrier gas stream that is flowed into a process chamber in which the substrate is disposed, wherein pulsing the first reactant and the additive into the carrier gas stream includes simultaneously turning on a flow of the first reactant and a flow of the additive into the carrier gas stream;

performing a first purge operation;

after exposing the substrate to the first reactant and the additive, exposing the substrate to a second reactant, the second reactant configured to react with the adsorbed first reactant to form a thin film product, the thin film product being silicon dioxide, the second reactant configured to react with the adsorbed additive to remove the adsorbed additive from the substrate surface,

wherein exposing the substrate to the second reactant includes, pulsing the second reactant into the carrier gas stream;

performing a second purge operation;

repeating the operations of exposing the substrate to the first reactant and the additive substantially simultaneously, performing the first purge operation, exposing the substrate to the second reactant, and performing the second purge operation, for a predefined number of cycles so as to deposit multiple layers of the thin film product, wherein a deposition amount of the thin film product along sidewalls of the gap feature increases with increasing depth in the gap feature.

11. The method of claim 10 , wherein the additive is configured to compete with the first reactant for available adsorption locations on the exposed surfaces of the substrate, the first reactant and the additive being configured to adsorb as a self-limiting monolayer, wherein adsorption of the additive prevents formation of the thin film product at locations where the additive adsorbed on the substrate surface.

12. The method of claim 11 , wherein the partial pressure of the additive is in the range of approximately 0.1 to 25 Torr, and wherein the partial pressure of the first reactant is in the range of approximately 0.001 to 15 Torr.