Method of fabricating semiconductor device

• US 9,349,583 B2
• Filed: 02/25/2013
• Issued: 05/24/2016
• Est. Priority Date: 03/14/2012
• Status: Active Grant

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Kim, Youn-Soo, Park, Min-Young, Kang, Sang-Yeol, Yoo, Cha-Young, Lim, Jae-Soon, Choi, Jae-Hyoung
• Primary Examiner(s): ISAAC, STANETTA D
• Application Number:
  US13/775,595
• Publication Number:
  US 20130244445A1
• Time in Patent Office: 1,184 Days
• Field of Search: 438/761
• US Class Current: 1/1
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45527 characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
• CPC Class Codes: H01L 21/02104 Forming layers deposition in general C23C; crystal growth in general C30B
• CPC Class Codes: H01L 28/40 Capacitors
• CPC Class Codes: H01L 29/40117 the electrodes comprising a charge-trapping insulator

Abstract

Methods of fabricating a semiconductor device include forming a deposited film on a semiconductor substrate in a process chamber by repeatedly forming unit layers on the semiconductor substrate. The unit layer is formed by forming a preliminary unit layer on the semiconductor substrate by supplying a process material including a precursor material and film-control material into the process chamber, purging the process chamber, forming a unit layer from the preliminary unit layer, and again purging the process chamber. The precursor material includes a central atom and a ligand bonded to the central atom, and the film-control material includes a hydride of the ligand.

Claims

1. A method of fabricating a semiconductor device, comprising:

forming a deposited film on a semiconductor substrate in a process chamber by repeatedly forming a unit layer on the semiconductor substrate;

wherein forming the unit layer comprises;

forming a preliminary unit layer on the semiconductor substrate by supplying a process material including a precursor material and a film-control material into the process chamber, wherein the precursor material includes a central atom and a ligand bonded to the central atom, and the film-control material comprises a hydride of the ligand of the precursor material;

firstly purging the process chamber in which the semiconductor substrate having the preliminary unit layer is located;

forming the unit layer from the preliminary unit layer in the firstly purged process chamber; and

secondly purging the process chamber in which the semiconductor substrate having the unit layer is located.

2. The method according to claim 1, wherein the precursor material is adsorbed onto the semiconductor substrate to form a precursor-adsorbed layer.

3. The method according to claim 2, wherein the film-control material is coordinated to the central atom of the precursor-adsorbed layer to form a more chemically stable material from the precursor-adsorbed layer than the precursor-adsorbed layer.

4. The method according to claim 1, wherein forming the preliminary unit layer comprises:

forming a precursor-adsorbed layer on the semiconductor substrate by supplying the precursor material into the process chamber, wherein the precursor-adsorbed layer includes a base part and an over-adsorbed part bonded to the base part; and

separating the over-adsorbed part from the base part by supplying the film-control material into the process chamber.

5. The method according to claim 4, wherein the film-control material breaks a bond between the over-adsorbed part and the base part while being bonded to the central atom of the over-adsorbed part.

6. The method according to claim 1, wherein the preliminary unit layer includes both of the precursor material and the film-control material.

7. The method according to claim 6, wherein the ligand of the precursor material and the film-control material that provide the preliminary unit layer are separated from the preliminary unit layer to form a residual product while forming the unit layer from the preliminary unit layer, and the residual product is removed while secondly purging the process chamber.

8. The method according to claim 1, wherein the ligand includes a first ligand and a second ligand which are bonded to the central atom of the precursor material and have different chemical formulas from each other, and wherein the film-control material is a hydride of the first ligand.

9. A method of fabricating a semiconductor device, comprising:

forming a deposited film on a semiconductor substrate in a process chamber by repeatedly forming a unit layer on the semiconductor substrate;

wherein forming the unit layer comprises;

forming a surface-control layer on the semiconductor substrate by supplying a first film-control material into the process chamber;

forming a precursor-adsorbing layer that is adsorbed onto the surface-control layer by supplying the precursor material into the process chamber, to form a preliminary unit layer including the surface-control layer and precursor-adsorbing layer, wherein the precursor material is a compound which includes a central atom and a ligand bonded to the central atom;

firstly purging the process chamber in which the semiconductor substrate having the preliminary unit layer is located;

forming a residual product by separating the surface-control layer and the ligand of the precursor-adsorbing layer from the precursor-adsorbing layer while forming the unit layer from the preliminary unit layer; and

secondly purging the process chamber in which the semiconductor substrate having the unit layer is located to remove the residual product.

10. The method according to claim 9, wherein a coordination number of a central atom of the preliminary unit layer is greater than a coordination number of the central atom of the precursor material.

11. The method according to claim 9, further comprising initiating supply of the precursor material while the first film-control material is in the process chamber.

12. The method according to claim 9, further comprising stopping supplying the first film-control material into the process chamber, and supplying the precursor material into the process chamber after the supply of the first film-control material into the process chamber has stopped.

13. The method according to claim 9, further comprising starting the supply of the precursor material while the first film-control material is being supplied into the process chamber.

14. The method according to claim 9, further comprising starting the supply of the precursor material while the first film-control material is being supplied into the process chamber, and stopping the supply of the precursor material before the supply of the first film-control material stops.

15. The method according to claim 9, further comprising:

supplying a second film-control material into the process chamber before the process chamber is firstly purged after the supply of the precursor material into the process chamber stops.

16. The method according to claim 15, wherein the second film-control material is a material coordinated to the central atom of the precursor material.

17. A method of fabricating a semiconductor device, comprising:

forming a structure on a semiconductor substrate, wherein the structure has vertical side parts;

forming a deposited film on the semiconductor substrate having the structure in a process chamber, wherein forming the deposited film includes repeatedly forming a unit layer on the semiconductor substrate having the structure;

wherein forming the unit layer comprises;

forming a first preliminary unit layer by adsorbing a first precursor material onto the semiconductor substrate having the structure by supplying the first precursor material into the process chamber, wherein the first preliminary unit layer includes a base part and an over-adsorbed part that is physically bonded to the base part;

forming a second preliminary unit layer from the first preliminary unit layer by supplying a film-control material into the process chamber, wherein a portion of the film-control material reacts with the first preliminary unit layer to separate the over-adsorbed part from the base part and thereby form a second precursor material;

purging the process chamber in which the semiconductor substrate having the second preliminary unit layer is located;

forming a unit layer from the second preliminary unit layer; and

purging the process chamber in which the semiconductor substrate having the unit layer is located.

18. The method according to claim 17, wherein the first precursor material is a first compound including a central atom and a ligand bonded to the central atom, and a portion of the film-control material forms a second precursor material while being bonded to a central atom of the over-adsorbed part to separate the over-adsorbed part from the base part.

19. The method according to claim 18, wherein a portion of the film-control material is bonded to a central atom of the base part to increase the coordination number of the central atom of the base part.

20. The method according to claim 18, wherein the semiconductor substrate having the first preliminary unit layer includes an empty region on which the precursor material is not adsorbed.

21. The method according to claim 20, wherein forming the second preliminary unit layer includes adsorbing the second precursor material onto the empty region of the semiconductor substrate.

22. The method according to claim 20, wherein the over-adsorbed part is formed in an upper part of the structure, and the empty region is formed in a lower part of the structure located at a lower level than the over-adsorbed region.

23. A method of fabricating a semiconductor device, comprising:

forming a deposited film on a semiconductor substrate in a process chamber by repeatedly forming unit layers on the semiconductor substrate;

wherein forming the unit layer comprises;

forming a preliminary unit layer by supplying a first process material including a film-control material and precursor material into the process chamber, wherein the precursor material is a first compound including a central atom and a ligand bonded to the central atom, and the preliminary unit layer includes a second compound formed by the precursor material being bonded to the film-control material;

firstly purging the process chamber in which the semiconductor substrate having the preliminary unit layer is located;

forming a unit layer from the preliminary unit layer in the purged process chamber, wherein a residual product is formed by the film-control material of the second compound and the ligand of the precursor material of the second compound being separated from the preliminary unit layer while forming the unit layer from the preliminary unit layer; and

secondly purging the process chamber in which the semiconductor substrate having the unit layer is located and removing the residual product.

24. The method according to claim 23, wherein when the preliminary unit layer is formed, precursor molecules of the precursor material bond together in the process chamber to form a precursor cluster, and the film-control material forms the second compound by breaking bonds between molecules of the precursor cluster to be bonded to the molecules of the precursor cluster.

25. The method according to claim 23, wherein forming the preliminary unit layer is performed in a process atmosphere in which the first compound, the film-control material, and the second compound co-exist.

26. A method of fabricating a semiconductor device, comprising:

supplying a first precursor material into a process chamber in which a substrate is positioned, wherein the first precursor material is adsorbed onto the substrate to form a first preliminary unit layer including a base layer and an over-adsorbed layer;

supplying a film-control material into the process chamber, wherein the film-control layer reacts with the precursor material in the over-adsorbed layer to form a second precursor material, the second precursor material becoming adsorbed onto vacant portions of the substrate on which the first precursor material was not adsorbed;

supplying a process material into the process chamber, wherein the process material reacts with the film-control material to form a residual product; and

purging the residual product from the process chamber.

27. The method of claim 26, wherein the precursor material comprises a central atom and a ligand bonded to the central atom, and the film-control material comprises a hydride of the ligand of the precursor material.

28. The method of claim 27, wherein the process material comprises an oxygen-containing gas, a nitrogen-containing gas, or a reductant.