Energy conversion and storage films and devices by physical vapor deposition of titanium and titanium oxides and sub-oxides

• US 8,076,005 B2
• Filed: 03/22/2007
• Issued: 12/13/2011
• Est. Priority Date: 05/23/2003
• Status: Expired due to Fees

• Current Assignee: Demaray LLC
• Original Assignee: Springworks, LLC (Petters Group Worldwide LLC)
• Inventors: Demaray, Richard E., Zhang, Hong Mei, Narasimhan, Mukundan, Milonopoulou, Vassiliki
• Primary Examiner(s): Roman, Angel
• Application Number:
  US11/726,972
• Publication Number:
  US 20070172681A1
• Time in Patent Office: 1,727 Days
• Field of Search: 428/469, 428/472, 428/701, 428/702
• US Class Current: 428/469
• CPC Class Codes: C23C 14/0036 Reactive sputtering
• CPC Class Codes: C23C 14/083 of refractory metals or yttrium
• CPC Class Codes: C23C 14/345 using substrate bias
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02183 the material containing tantalum, e.g. Ta2O5
• CPC Class Codes: H01L 21/02186 the material containing titanium, e.g. TiO2
• CPC Class Codes: H01L 21/02192 the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
• CPC Class Codes: H01L 21/02194 the material containing more than one metal element
• CPC Class Codes: H01L 21/02197 the material having a perovskite structure, e.g. BaTiO3
• CPC Class Codes: H01L 21/022 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides adhesion layers or buffer layers H01L21/02304, H01L21/02362
• CPC Class Codes: H01L 21/02244 of a metallic layer
• CPC Class Codes: H01L 21/02266 deposition by physical ablation of a target, e.g. sputtering, reactive sputtering, physical vapour deposition or pulsed laser deposition
• CPC Class Codes: H01L 21/2855 by physical means, e.g. sputtering, evaporation H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/31604 Deposition from a gas or vapour H01L21/31691, H01L21/31695 take precedence
• CPC Class Codes: H01L 21/7687 Thin films associated with contacts of capacitors

Abstract

High density oxide films are deposited by a pulsed-DC, biased, reactive sputtering process from a titanium containing target to form high quality titanium containing oxide films. A method of forming a titanium based layer or film according to the present invention includes depositing a layer of titanium containing oxide by pulsed-DC, biased reactive sputtering process on a substrate. In some embodiments, the layer is TiO₂. In some embodiments, the layer is a sub-oxide of Titanium. In some embodiments, the layer is Ti_xO_y wherein x is between about 1 and about 4 and y is between about 1 and about 7. In some embodiments, the layer can be doped with one or more rare-earth ions. Such layers are useful in energy and charge storage, and energy conversion technologies.

Claims

1. A titanium-based layer, comprising:

titanium, the amount of titanium in the layer being represented by Ti_x, where x is between about 1 and about 4; and

oxygen, the amount of oxygen in the layer being represented by O_y, where y is between about 1 and about 7, wherein;

the titanium-based layer is densified, has a uniform thickness, is substantially free from columnar structures, and has a figure of merit, defined as the product of a dielectric constant of the titanium-based layer and a breakdown voltage of the titanium based layer, greater than 200 through a deposition process using a pulsed-DC power supply, an RF-bias to the substrate, and reactive ion sputtering on a substrate, wherein the pulsed-DC power supply is applied to a conductive ceramic target through a narrow-band rejection filter centered to remove power from the RF-bias such that the target voltage oscillates between positive and negative voltages.

2. The layer of claim 1, wherein the layer is TiO₂.

3. The layer of claim 2, wherein the layer is deposited between conducting layers to form a capacitor.

4. The layer of claim 2, wherein the layer includes at least one rare earth ion.

5. The layer of claim 4, wherein the layer is deposited between conducting layers to form a capacitor.

6. The layer of claim 4, wherein the at least one rare-earth ion includes erbium.

7. The layer of claim 4, wherein the layer is deposited between conducting layers to form a light-emitting device.

8. The layer of claim 4, wherein the layer is an optically active layer deposited on a light-emitting device.

9. The layer of claim 4, wherein the layer is an optically active layer applied to a light-emitting device.

10. The layer of claim 1, wherein the layer is sub-oxide of Titanium.

11. The layer of claim 10, wherein the layer is deposited between conducting layers to form a capacitor.

12. The layer of claim 10, wherein the layer includes at least one rare earth ion.

13. The layer of claim 12, wherein the layer is deposited between conducting layers to form a capacitor.

14. The layer of claim 12, wherein the at least one rare-earth ion includes erbium.

15. The layer of claim 12, wherein the layer is deposited between conducting layers to form a light-emitting device.

16. The layer of claim 12, wherein the layer is an optically active layer deposited on a light-emitting device.

17. The layer of claim 12, wherein the layer is an optically active layer applied to a light-emitting device.

18. The layer of claim 2, wherein the layer is a protective layer.

19. The layer of claim 18, wherein the protective layer is a catalytic layer.

20. The layer of claim 18, wherein the protective layer includes at least one rare-earth ion.

21. The layer of claim 1, further including depositing an TiO₂ layer on the layer wherein the layer and the TiO₂ layers are deposited between conducting layers to form a capacitor with decreased roll-off characteristics with decreasing thickness of the TiO₂ layer.

22. The layer of claim 1, wherein the layer includes at least one rare earth ion.

23. The layer of claim 22, wherein the at least one rare-earth ion includes erbium.

24. The layer of claim 22, wherein the layer is deposited between conducting layers to form a light-emitting device.

25. The layer of claim 22, wherein the layer is an optically active layer deposited on a light-emitting device.

26. The layer of claim 22, wherein the layer is an optically active layer applied to a light-emitting device.

27. The layer of claim 1, wherein the layer is a conducting oxide.

28. The layer of claim 27, wherein the substrate is a conducting electrode and the layer is a protective layer.

29. The layer of claim 28, wherein the protective layer is a catalytic layer.

30. The layer of claim 28, wherein the protective layer includes at least one rare-earth ion.

31. The layer of claim 27, wherein the substrate is a dielectric and the layer is a protective layer.

32. The layer of claim 31, wherein the protective layer is a catalytic layer.

33. The layer of claim 1, a temperature of the substrate is controlled during deposition.

34. The layer of claim 33, wherein the temperature is controlled using active temperature control.

35. The layer of claim 1, wherein the substrate includes a transistor structure.

36. The layer of claim 1, wherein the layer is an amorphous layer.