METHODS OF FORMING THIN FILMS AND METHODS OF FABRICATING INTEGRATED CIRCUIT DEVICES USING THE SAME

• US 20170062205A1
• Filed: 06/15/2016
• Published: 03/02/2017
• Est. Priority Date: 08/24/2015
• Status: Active Grant

• Current Assignee: Adeka Corporation, Samsung Electronics Co. Ltd.
• Original Assignee: Adeka Corporation, Samsung Electronics Co. Ltd.
• Inventors: Chang, Jae wan, Kim, Youn soo, Shiratori, Tsubasa
• Granted Patent: US 9,960,032 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/30604 Chemical etching
• CPC Class Codes: H01L 21/31 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques encapsulating layers H01L21/56; After treatment of these layers; Selection of materials for these layers
• CPC Class Codes: H01L 29/66795 with a horizontal current flow in a vertical sidewall of a semiconductor body, e.g. FinFET, MuGFET

Abstract

Provided herein are methods of forming thin films. In some embodiments, to form a thin film, a precursor adsorption layer including an organic ligand is formed by supplying a precursor including a metal or silicon central atom, and the organic ligand onto a lower structure. An intermediate result layer is formed by supplying a non-oxidant onto the precursor adsorption layer. In forming the intermediate result layer, the organic ligand included in the precursor adsorption layer is substituted with a substituent. An oxide film including the central atom is formed from the intermediate result layer by supplying an oxidant onto the intermediate result layer.

Claims

1. A method of forming a thin film, comprising:

forming a precursor adsorption layer comprising an organic ligand by supplying a precursor and the organic ligand onto a lower structure, wherein the precursor comprises a metal or silicon central atom;

forming an intermediate result layer by supplying a non-oxidant onto the precursor adsorption layer, wherein the organic ligand of the precursor adsorption layer is substituted with a substituent; and

forming an oxide film comprising the central atom from the precursor adsorption layer by supplying an oxidant onto the intermediate result layer.

2. The method of claim 1, wherein the non-oxidant comprises a nitrogen-containing material and the substituent is amidogen (—

NH₂).

3. The method of claim 1, wherein the precursor comprises an amido ligand.

4. The method of claim 1, wherein the precursor comprises a first ligand comprising an amido ligand, and at least one second ligand selected from a C1 to C5 aliphatic organic ligand and a C4 to C20 aromatic organic ligand.

5. The method of claim 1, wherein the precursor is represented by the following formula:

M(NR¹R²)_mR³_n,

wherein M is the central atom;

N is a nitrogen atom;

R¹ and R² are each independently a C1 to C5 alkyl group;

R³ is one selected from NR¹R², a C1 to C5 aliphatic organic ligand, and a substituted or unsubstituted C4 to C20 aromatic organic ligand;

m and n are each independently an integer of 0 or more; and

m+n is an integer of 2 to 8.

6-15. -15. (canceled)

16. A method of fabricating an integrated circuit device, comprising:

forming a lower structure having a step height on a substrate; and

forming an oxide film on the lower structure,

wherein the forming of the oxide film comprises;

forming a precursor adsorption layer on an upper surface and sidewalls of the lower structure, the precursor adsorption layer comprising metal or silicon central atoms and organic ligands bonded to the central atoms;

substituting at least a portion of the organic ligands with a substituent by supplying a non-oxidant onto the precursor adsorption layer; and

forming an oxide film that comprises the central atoms by supplying an oxidant onto the precursor adsorption layer comprising the substituent, thereby forming the oxide film.

17. The method of claim 16, wherein in the step of forming the precursor adsorption layer, the organic ligands comprise an amido ligand, and

in the step of substituting at least the portion of the organic ligands with the substituent, the non-oxidant is a nitrogen-containing material.

18. The method of claim 16, wherein forming the precursor adsorption layer further comprises supplying a precursor onto the lower structure, where the precursor is represented by the following formula:

M(NR¹R²)_mR³_n,

wherein M is the central atom;

N is a nitrogen atom;

R¹ and R² are each independently a C1 to C5 alkyl group;

R³ is one selected from NR¹R², a C1 to C5 aliphatic organic ligand, and a substituted or unsubstituted C4 to C20 aromatic organic ligand;

m and n are each independently an integer of 0 or more; and

m+n is an integer of 2 to 8.

19. The method of claim 16, wherein in the step of substituting at least the portion of the organic ligands with the substituent, the non-oxidant is NH₃, NH₂A¹, or NHA¹A², wherein A¹ and A² are the same or different and are each independently a C1 to C5 linear or branched alkyl group or a substituted or unsubstituted C4 to C20 aromatic group.

21. The method of claim 16, wherein the step of forming the lower structure comprises:

forming a mold pattern on the substrate, the mold pattern comprising a hole exposing a conductive region of a substrate;

forming an electrode having a sidewall extending along an inner wall of the hole; and

exposing the sidewall of the electrode by removing the mold pattern to provide an exposed surface comprising the sidewall of the electrode, and

the step of forming the oxide film comprises forming a ZrO₂ film covering the exposed surface.

22. The method of claim 16, wherein the step of forming the lower structure comprises forming a fin-type active region protruding upwards from the substrate by partially etching the substrate, and

the step of forming the oxide film comprises forming a ZrO₂ film covering the fin-type active region.

20. (canceled)

23. A method of forming a thin film, comprising:

supplying a precursor and an organic ligand onto a lower structure to form a precursor adsorption layer, wherein the precursor comprises a metal or silicon central atom;

supplying a non-oxidant onto the precursor adsorption layer to form an intermediate result layer, wherein supplying the non-oxidant onto the precursor adsorption layer comprises substituting the organic ligand of the precursor adsorption layer with a substituent; and

supplying an oxidant onto the intermediate result layer to form the thin film, the thin film comprising the metal or silicon central atom from the precursor adsorption layer.

24. The method of claim 23, wherein the non-oxidant comprises a nitrogen-containing material and the substituent is amidogen (—

NH₂).

25. The method of claim 23, wherein the precursor comprises an amido ligand.

32. The method of claim 23, wherein the precursor is (cyclopentadienyl)tris(dimethylamino)zirconium and the non-oxidant is NH₃.

33. The method of claim 23, wherein the oxidant comprises O₃, H₂O, O₂, NO₂, NO, N₂O, H₂O, alcohol, a metal alkoxide, plasma O₂, remote plasma O₂, plasma N₂O, and/or plasma H₂O.

34. The method of claim 23, further comprising:

performing a first purge after the forming of the precursor adsorption layer;

performing a second purge after the forming of the intermediate result layer; and

performing a third purge after the forming of the oxide film.

35. The method of claim 23, wherein the precursor comprises zirconium (Zr) and an amido ligand,

the non-oxidant comprises a nitrogen-containing material, and

the oxide film comprises ZrO₂.

36. The method of claim 23, wherein the lower structure comprises an electrode layer, and the oxide film is a dielectric film on the electrode layer.

37. The method of claim 23, wherein the lower structure comprises a fin-type active region comprising a semiconductor, and

the oxide film is a dielectric film covering an upper surface and sidewalls of the fin-type active region.

26-31. -31. (canceled)