Method of forming material film, integrated circuit device, and method of manufacturing the integrated circuit device

1. A method of forming a material film, the method comprising:

supplying a first precursor comprising a first central element and a first ligand having a first size onto a lower structure and forming a first chemisorbed layer of the first precursor on the lower structure;

supplying a second precursor comprising a second central element and a second ligand having a second size onto a resultant structure in which the first chemisorbed layer is formed, and forming a second chemisorbed layer of the second precursor on the lower structure, wherein the second size is less than the first size; and

forming a material film comprising the first central element and the second central element by supplying a reactive gas to the first chemisorbed layer and the second chemisorbed layer to remove the first ligand and the second ligand from the lower structure,

wherein each of the first central element and the second central element is a semiconductor element.

2. The method of claim 1 , wherein each of the first central element and the second central element is silicon (Si).

3. The method of claim 1 , wherein a first molecular weight of the first precursor is greater than a second molecular weight of the second precursor.

4. The method of claim 1 , wherein the first ligand comprises an aromatic functional group, an alkoxy functional group, a thiol functional group, or a —Si—(CH 2 ) n —Si— group, wherein n is an integer ranging from 1 to 5.

5. The method of claim 1 , wherein the reactive gas comprises an oxidizing gas or a reducing gas.

6. The method of claim 1 , further comprising treating the material film using hydrogen plasma.

7. The method of claim 1 , wherein the material film is part of an integrated circuit (IC) device, and the method is a method of forming the IC device, the IC device including a lower structure having a step structure defining a trench,

wherein the material film is formed inside the trench, and

wherein the forming of the material film comprises performing an atomic layer deposition (ALD) cycle at least once.

8. A method of manufacturing an integrated circuit (IC) device, the method comprising:

preparing a lower structure for the IC device, the lower structure having a step structure defining a trench; and

forming a material film inside the trench,

wherein the forming of the material film comprises performing an atomic layer deposition (ALD) cycle at least once, the ALD cycle comprising:

a first process of supplying a first precursor comprising a first central element and a first ligand having a first size into the trench and forming a first chemisorbed layer of the first precursor inside the trench;

a second process of supplying a second precursor comprising a second central element and a second ligand having a second size into the trench in which the first chemisorbed layer is formed, and forming a second chemisorbed layer of the second precursor inside the trench, wherein the second size is less than the first size; and

a third process of forming an atomic-level material film comprising the first central element and the second central element inside the trench by supplying a reactive gas to the first chemisorbed layer and the second chemisorbed layer.

9. The method of claim 8 , wherein the ALD cycle further comprises a fourth process of treating the atomic-level material film using hydrogen plasma after the third process is performed.

10. The method of claim 8 , wherein the forming of the material film further comprises treating the atomic-level material film using hydrogen plasma after the ALD cycle is performed plural times.

11. The method of claim 8 , wherein the material film is a silicon oxide film, and

each of the first central element and the second central element is a silicon (Si) atom.

12. The method of claim 8 , wherein the material film is a silicon oxide film,

the first ligand comprises an aromatic functional group, an alkoxy functional group, a thiol functional group, or a —Si—(CH 2 ) n —Si— group, and

the second ligand does not include the aromatic functional group, the alkoxy functional group, the thiol functional group, or the —Si—(CH 2 ) n —Si— group,

wherein n is an integer ranging from 1 to 5.

13. The method of claim 8 , wherein the material film is a silicon oxide film, and

the second precursor comprises silane (SiH 4 ), disilane (Si 2 H 6 ), silane substituted with halogen, organic silane, or organic aminosilane.

14. An integrated circuit (IC) device manufactured using the method of claim 8 ,

wherein the material film comprises a silicon oxide film,

wherein an upper portion of the silicon oxide film, which is relatively close to an entrance of the trench, comprises carbon atoms at a first content, and

a lower portion of the silicon oxide film, which is relatively close to a bottom surface of the trench, comprises carbon atoms at a second content lower than the first content.

15. A method of manufacturing an integrated circuit (IC) device, the method comprising:

forming a trench defining an active region in a substrate; and

forming a silicon oxide film inside the trench,

wherein the forming of the silicon oxide film comprises performing an atomic layer deposition (ALD) cycle at least once, the ALD cycle comprising:

a first process of supplying a first precursor comprising a first silicon central element and a first ligand having a first size into the trench and forming a first chemisorbed layer of the first precursor inside the trench;

a second process of supplying a second precursor comprising a second silicon central element and a second ligand having a second size into the trench in which the first chemisorbed layer is formed, and forming a second chemisorbed layer of the second precursor inside the trench, wherein the second size is less than the first size; and

a third process of forming an atomic-level silicon oxide film inside the trench by supplying an oxidizing gas to the first chemisorbed layer and the second chemisorbed layer.

16. The method of claim 15 , wherein the first ligand comprises an aromatic functional group, an alkoxy functional group, a thiol functional group, or a —Si—(CH 2 ) n —Si— group, and

wherein the second ligand does not comprise the aromatic functional group, the alkoxy functional group, the thiol functional group, or the —Si—(CH 2 ) n —Si— group,

wherein n is an integer ranging from 1 to 5.

17. The method of claim 15 , wherein a first molecular weight of the first precursor is greater than a second molecular weight of the second precursor.

18. The method of claim 15 , wherein the ALD cycle further comprises a fourth process of treating the atomic-level silicon oxide film using hydrogen plasma after the third process is performed.

19. The method of claim 15 , wherein the forming of the silicon oxide film further comprises treating the atomic-level silicon oxide film using hydrogen plasma after the ALD cycle is performed plural times.

20. An integrated circuit (IC) device manufactured using the method of claim 15 , wherein the silicon oxide film has a carbon atom content of less than 3 atomic percent (at %),

wherein an upper portion of the silicon oxide film, which is relatively close to an entrance of the trench, comprises carbon atoms at a first content that is selected in the range of more than 0 at % and less than 3 at %, and

wherein a lower portion of the silicon oxide film, which is relatively close to a bottom surface of the trench, comprises carbon atoms at a second content that is selected in the range of more than or equal to 0 at % and less than 3 at %, and the second content is lower than the first content.