Method of Manufacturing Vanadium Oxide Thin Film

• US 20090011145A1
• Filed: 08/23/2006
• Published: 01/08/2009
• Est. Priority Date: 08/24/2005
• Status: Abandoned Application

• Current Assignee: Electronics and Telecommunications Research Institute
• Original Assignee: Electronics and Telecommunications Research Institute
• Inventors: Lim, Jung Wook, Kim, Bong Jun, Yun, Sun-Jin, Kim, Hyun Tak, Chae, Byung Gyu, Kang, Kwang Yong
• Application Number:
  US12/064,807
• Publication Number:
  US 20090011145A1
• Time in Patent Office: Days
• US Class Current: 427/569
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45542 Plasma being used non-continuously during the ALD reactions
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/50 using electric discharges generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34

Abstract

Provided is a method of manufacturing a large-sized vanadium oxide thin film having a uniform surface, uniform film thickness and stable composition. According to the method, a vanadium-organometallic compound gas is injected into a chamber to form adsorption layer where molecules of the vanadium-organometallic compound are adsorbed on the surface of a substrate. After that, an oxygen precursor is injected into the chamber and thus allowed to accomplish surface-saturation reaction with the adsorbed materials to fabricate a vanadium oxide thin film.

Claims

1. A method of manufacturing a vanadium oxide thin film, the method comprising:

loading a substrate in a chamber;

(1) injecting a vanadium-organometallic compound vapor into the chamber to uniformly form adsorption layer of vanadium precursors on the substrate using surface saturation absorption;

(2) injecting an inert gas into the chamber in order to purge a vanadium-organometallic compound gas that has not been adsorbed; and

(3) injecting an oxygen precursor into the chamber to allow the oxygen precursor to accomplish surface-saturation reaction with the adsorbed materials to form a vanadium oxide thin film; and

(4) injecting an inert gas into the chamber in order to purge by-products of surface reaction in step (3) and residual oxidants; and

5) repeating the above-described processes (1)-(4) until vanadium oxide film of desired thickness is obtained.

2. The method of claim 1, wherein the substrate is formed of at least one selected from the group consisting of Si, glass, quartz and SiO₂-coated Si.

3. The method of claim 1, wherein the substrate has a diameter of 2-12 inch.

4. The method of claim 1, wherein a valence of the vanadium ion contained in the vanadium-organometallic compound precursors is one of +3, +4, and +5.

5. The method of claim 4, wherein the vanadium-organometallic compound gas containing the vanadium whose valence is +4 is one selected from the group consisting of V(NEt₂)₄, V{N(EtMe)}₄, and V(NMe₂)₄, where Me is ═

CH₃ and Et is ═

C₂H₅.

6. The method of claim 4, wherein the vanadium-organometallic compound gas containing the vanadium whose valence is +5 is one selected from the group consisting of VO{N(EtMe)}₃, VO(NMe₂)₃, VO(OMe)₃, VO(OEt)₃, VO(OC₃H₇)₃, and VOX₃, where X=Cl, F, Br, or I, and Me is CH₃ and Et is C₂H₅.

7. The method of claim 1, wherein the vanadium-organometallic compound gas is one selected from the group consisting of VX₃, where X==Cl, F, Br, or I, VX₄, where X=Cl, F, Br, or I, vanadium hexacarbonyl, vanadium 2,4-pentadionate, vanadium acetone acetonate, and cyclopentadienyl vanadium tetracarbonyl.

8. The method of claim 1, wherein a temperature of the reaction is maintained such that a vapor pressure of the vanadium-organometallic compound vapor is in a range of 0.01-10 torr.

9. The method of claim 1, wherein a temperature of the reaction is in a range of 100-350°

C.

10. The method of claim 1, wherein a temperature of the reaction is in a range of 350-500°

C.

11. The method of claim 10, wherein the vanadium-organometallic compound gas is vanadium halogenide.

12. The method of claim 1, wherein the oxygen precursor is one selected from the group consisting of ozone, H₂O, and an oxygen plasma.

13. The method of claim 1, further comprising, before the injecting of the vanadium-organometallic compound vapor, forming a buffer layer having a lattice constant similar to that of the vanadium oxide compound gas on the substrate.

14. The method of claim 13, wherein the buffer layer is at least one selected from the group consisting of an aluminum oxide layer, a silicon oxide layer, an MgO layer, an insulation layer having a high dielectric constant, and a crystalline metal layer.

15. The method of claim 1, further comprising, after forming vanadium oxide film of desired thickness, in situ heat-treatment of the vanadium oxide thin film.

16. The method of claim 15, wherein the heat treating is performed in the chamber, or in an adjacent chamber having a similar atmosphere to that of the chamber, and the atmosphere in the adjacent chamber is a vacuum atmosphere or an inert gas atmosphere.

17. The method of claim 1, wherein the oxidant is oxygen plasma and the plasma is maintained for a predetermined period of time in the PEALD cycles.

18. The method of claim 17, wherein the time for which the plasma is maintained is the same as or shorter than a time for which the oxygen precursor is injected in the PEALD cycles.

19. The method of claim 17, wherein the plasma is directly applied to the surface of the substrate within the chamber or reactive particles generated due to a plasma in an adjacent chamber are injected to the chamber.

31. The method of claim 2.5, further comprising, after forming vanadium oxide film of desired thickness, in situ heat-treatment of the vanadium oxide thin film.

20. A method of manufacturing a vanadium oxide thin film, the method comprising:

loading a substrate in a chamber;

(1) injecting a TEMAV (tetra ethyl methyl amino vanadium;

V{N(C₂H₅CH₃)}₄) vapor into the chamber to form an adsorption layer containing vanadium ion on the surface by surface saturation adsorption;

(2) injecting an inert gas into the chamber in order to purge a TEMAV vapor that has not been adsorbed;

(3) injecting H₂O into the chamber to allow the H₂O to accomplish surface-saturation reaction with the adsorbed materials to form a vanadium oxide thin film; and

(4) injecting an inert gas into the chamber in order to purge a reaction by-product remaining in the chamber,

wherein the steps (1)-(4) are repeated a predetermined number of times.

21. The method of claim 20, wherein the substrate has a diameter of 2-12 inch.

22. The method of claim 20, wherein a temperature of the reaction under which the TEMAV gas is adsorbed on the substrate and the thin film is formed by the surface saturation reaction is in a range of 100-170°

C.

23. The method of claim 20, further comprising, before the injection of the TEMAV gas, forming a buffer layer having a lattice constant similar to that of the vanadium oxide compound gas on the substrate.

24. The method of claim 20, further comprising, after forming vanadium oxide film, of desired thickness, in situ heat-treatment of the vanadium oxide thin film.

25. A method of manufacturing a vanadium oxide thin film, the method comprising:

loading a substrate in a chamber;

(1) injecting a TEMAV (tetra ethyl methyl amino vanadium;

V{N(C₂H₅CH₃)}₄) vapor in the chamber to form adsorption layer containing vanadium ion on the surface of the substrate by surface saturation adsorption;

(2) injecting an inert gas into the chamber in order to purge a TEMAV vapor that has not been absorbed;

(3) injecting the oxygen gas into the chamber and generating an oxygen plasma for a predetermined period of time to allow the energetic particles in oxygen plasma to accomplish surface-saturation reaction with the adsorbed materials to form a vanadium oxide thin film; and

(4) injecting an inert gas to the chamber in order to purge a reaction by-product remaining in the chamber,

wherein the steps (1)-(4) are repeated a predetermined number of times.

26. The method of claim 25, wherein the substrate has a diameter of 2-12 inch.

27. The method of claim 25, wherein a temperature of the reaction under which the TEMAV vapor is adsorbed on the substrate and the thin film is formed by the surface saturation reaction is in a range of 100-1700°

C.

28. The method of claim 25, wherein the time for which the plasma is maintained is the same as or shorter than a time for which the oxygen gas is injected.

29. The method of claim 25, wherein the plasma is directly applied to the surface of the substrate within the chamber or reactive particles generated due to a plasma in an adjacent chamber are injected to the chamber.

30. The method of claim 25, further comprising, before the injection of the TEMAV gas, forming a buffer layer having a lattice constant similar to that of the vanadium oxide compound gas on the substrate.