Dielectric material

• US 20050242330A1
• Filed: 04/30/2004
• Published: 11/03/2005
• Est. Priority Date: 04/30/2004
• Status: Active Grant

• Current Assignee: Hewlett-Packard Development Company, L.P. (HP Inc.), Oregon State University (Oregon University System)
• Original Assignee: Hewlett-Packard Development Company, L.P. (HP Inc.), Oregon State University (Oregon University System)
• Inventors: Anderson, Jeremy, Mardilovich, Peter, Herman, Gregory S., Keszler, Douglas
• Granted Patent: US 7,773,365 B2
• Time in Patent Office: Days
• US Class Current: 252/570
• CPC Class Codes: C01G 1/00 Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general electrolytic production of inorganic compounds C25B1/00
• CPC Class Codes: C01G 27/00 Compounds of hafnium
• CPC Class Codes: C01G 27/06 Sulfates
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01B 3/12 ceramics
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/31637 Deposition of Tantalum oxides, e.g. Ta2O5
• CPC Class Codes: H01L 21/31641 Deposition of Zirconium oxides, e.g. ZrO2
• CPC Class Codes: H01L 21/31645 Deposition of Hafnium oxides, e.g. HfO2
• CPC Class Codes: H01L 29/517 the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence

Abstract

One embodiment of a dielectric material may include a metal containing cation and a polyatomic anion.

Claims

1. A dielectric material, comprising:

a metal containing cation; and

a polyatomic anion.

2. A dielectric material according to claim 1 wherein said polyatomic anion includes one or more of sulfate (SO₄²⁻

), borate (BO₃³⁻

), phosphate (PO₄³⁻

), tungstate (WO₄²⁻

) and silicate (SiO₄⁴⁻

).

3. A dielectric material according to claim 1, wherein said dielectric material comprises a film in an electronic component, and wherein said electronic component includes one or more of a field effect transistor and a capacitor.

4. A dielectric material according to claim 1, wherein said dielectric material comprises a thin film on a plastic substrate.

5. A dielectric material according to claim 1 wherein said metal containing cation includes one or more of hafnium (Hf⁴⁺), titanium (Ti⁴⁺), zirconium (Zr⁴⁺), cerium (Ce⁴⁺), tin (Sn⁴⁺), tantalum (Ta⁵⁺), niobium (Nb⁴⁺), yttrium (Y³⁺), molybdenum (Mo⁴⁺), tungsten (W⁶⁺), aluminum (Al³⁺), gallium (Ga³⁺), zinc (Zn²⁺), chromium (Cr³⁺), iron (Fe³⁺), bismuth (Bi³⁺), lanthanides, hafnium suboxide (HfO²⁺), zirconium suboxide (ZrO²⁺), titanium suboxide (TiO²⁺), tantalum suboxide (TaO²⁺), yttrium suboxide (YO⁺), niobium suboxide (NbO²⁺), molybdenum suboxide (MoO²⁺), tungsten suboxide (WO⁴⁺), aluminum suboxide (AlO⁺), gallium suboxide (GaO⁺), suboxides of the lanthanide series, hafnium oxy-hydroxide (HfO_y(OH)_z^(4-2y-z)+), zirconium oxy-hydroxide (ZrO_y(OH)_z^(4-2y-z)+), titanium oxy-hydroxide (TiO_y(OH)_z^(4-2y-z)+), tantalum oxy-hydroxide (TaO_y(OH)_z^(5-2y-z)+), yttrium oxy-hydroxide (YO_y(OH)_z^(3-2y-z)+), niobium oxy-hydroxide (NbO_y(OH)_z^(4-2y-z)+), molybdenum oxy-hydroxide (MoO_y(OH)_z^(4-2y-z)+), tungsten oxy-hydroxide (WO_y(OH)_z^(6-2y-z)+), aluminum oxy-hydroxide (AlO_y(OH)_z^(3-2y-z)+), gallium oxy-hydroxide (GaO_y(OH)_z^(3-2y-z)+), zinc oxy-hydroxide (ZnO_y(OH)_z^(2-2y-z)+), chromium oxy-hydroxide (CrO_y(OH)_z^(3-2y-z)+), iron oxy-hydroxide (FeO_y(OH)_z^(3-2y-z)+), bismuth oxy-hydroxide (BiO_y(OH)_z^(3-2y-z)+), and oxy-hydroxides of the lanthanide series.

6. A dielectric material according to claim 1 wherein said dielectric material comprises HfO_2-x-z/2(OH)_z(SO₄)_x, and wherein x ranges from 0.1 to 1.9.

7. A dielectric material according to claim 1 further comprising a dopant cation including one or more of titanium (Ti⁴⁺), zirconium (Zr⁴⁺), cerium (Ce⁴⁺), tin (Sn⁴⁺), tantalum (Ta⁵⁺), niobium (Nb⁴⁺), haffiium (Hf⁴⁺), yttrium (Y³⁺), molybdenum (Mo⁴⁺), tungsten (W⁶⁺), aluminum (Al³⁺), gallium (Ga³⁺), zinc (Zn²⁺), chromium (Cr³⁺), iron (Fe³⁺), bismuth (Bi³⁺), and lanthanides.

8. A dielectric material according to claim 1 wherein said dielectric material is amorphous up to a temperature of 740°

C.

9. A dielectric material according to claim 1 wherein said dielectric material is amorphous up to a temperature of 1200°

C.

10. A dielectric material according to claim 1 wherein said dielectric material is manufactured from a precursor, and wherein said precursor comprises a solution.

11. A dielectric material according to claim 10 wherein said solution comprises a clear solution having an absence of complexing organic materials.

12. A dielectric material according to claim 1 wherein said dielectric material has a breakdown electric field strength of at least 2.0 MV/cm.

13. A dielectric material according to claim 1 wherein said dielectric material has a dielectric constant of at least 10.

48. A dielectric material according to claim 1 wherein said metal containing cation includes one or more oxides, sub-oxides and sub-oxy-hydroxides.

49. A dielectric material according to claim 1 wherein said dielectric material comprises HfO_2-x-z/2(OH)_z(SO₄)_x, and wherein z ranges from 0.0 to 2.0.

14. A method of making a dielectric material, comprising:

providing a metal containing cation;

providing a polyatomic anion; and

reacting said polyatomic anion and said metal containing cation.

15. A method according to claim 14 wherein said providing a metal containing cation comprises providing an aqueous solution containing a metal containing cation including one or more of haffiium (Hf⁴⁺), titanium (Ti⁴⁺), zirconium (Zr⁴⁺), cerium (Ce⁴⁺), tin (Sn⁴⁺), tantalum (Ta⁵⁺), niobium (Nb⁴⁺), yttrium (Y³⁺), molybdenum (Mo⁴⁺), tungsten (W⁶⁺), aluminum (Al³⁺), gallium (Ga³⁺), zinc (Zn²⁺), chromium (Cr³⁺), iron (Fe³⁺), bismuth (Bi³⁺), lanthanides, hafnium suboxide (HfO²⁺), zirconium suboxide (ZrO²⁺), titanium suboxide (TiO²⁺), tantalum suboxide (TaO²⁺), yttrium suboxide (YO⁺), niobium suboxide (NbO²⁺), molybdenum suboxide (MoO²⁺), tungsten suboxide (WO⁴⁺), aluminum suboxide (AlO⁺), gallium suboxide (GaO⁺), suboxides of the lanthanide series hafnium oxy-hydroxide (HfO_y(OH)_z^(4-2y-z)+), zirconium oxy-hydroxide (ZrO_y(OH)_z^(4-2y-z)+), titanium oxy-hydroxide (TiO_y(OH)_z^(4-2y-z)+), tantalum oxy-hydroxide (TaO_y(OH)_z^(5-2y-z)+), yttrium oxy-hydroxide (YO_y(OH)_z^(3-2y-z)+), niobium oxy-hydroxide (NbO_y(OH)_z^(4-2y-z)+), molybdenum oxy-hydroxide (MoO_y(OH)_z^(4-2y-z)+), tungsten oxy-hydroxide (WO_y(OH)_z^(6-2y-z)+), aluminum oxy-hydroxide (AlO_y(OH)_z^(3-2y-z)+), gallium oxy-hydroxide (GaO_y(OH)_z^(3-2y-z)+), zinc oxy-hydroxide (ZnO_y(OH)_z^(2-2y-z)+), chromium oxy-hydroxide (CrO_y(OH)_z^(3-2y-z)+), iron oxy-hydroxide (FeO_y(OH)_z^(3-2y-z)+), bismuth oxy-hydroxide (BiO_y(OH)_z^(3-2y-z)+), and oxy-hydroxides of the lanthanide series.

16. A method according to claim 14 wherein said providing a polyatomic anion comprises providing an aqueous solution containing a polyatomic anion including one or more of sulfate (SO₄²⁻

), borate (BO₃³⁻

), phosphate (PO₄³⁻

), tungstate (WO₄²⁻

) and silicate (SiO₄⁴⁻

).

17. A method according to claim 14 wherein said reacting takes place at a temperature of at most 100°

C.

18. A method according to claim 14 wherein said reacting takes place at a temperature in a range of 60°

C. to 350°

C.

19. A method according to claim 14 wherein said reacting takes place at atmospheric pressure in ambient air.

20. A method according to claim 14 wherein said polyatomic anion and said metal cation comprise a solution, further comprising adding a cation dopant to said solution, wherein said cation dopant includes one or more of titanium (Ti⁴⁺), zirconium (Zr⁴⁺), cerium (Ce⁴⁺), tin (Sn⁴⁺), tantalum (Ta⁴⁺) and niobium (Nb⁴⁺), and wherein said cation dopant is added in a range of 1 cation atomic percent to 50 cation atomic percent of said solution.

21. A method according to claim 14 wherein said metal cation comprises an aqueous solution of hafnium oxy chloride (HfOCl₂), said polyatomic anion comprises an aqueous solution of sulfuric acid (H₂SO₄), said reacting said polyatomic anion with said metal cation forms a solution, and said method further comprises at least partially dehydrating said solution.

22. A method according to claim 21 wherein an excess of said metal containing cation is reacted with said polyatomic anion, and wherein said solution does not include precipitate.

23. A method according to claim 21 wherein an excess of said polyatomic anion is reacted with said metal containing cation, and wherein said solution does not include precipitate.

24. A dielectric material produced by a process comprising:

providing a metal containing cation;

providing a polyatomic anion; and

reacting said polyatomic anion and said metal containing cation.

25. A process of forming a dielectric film, comprising:

providing a metal containing cation;

providing a polyatomic anion;

reacting said polyatomic anion and said metal containing cation to form a precursor solution; and

printing said precursor solution on a substrate through an inkjet printhead.

26. A process according to claim 25 wherein said reacting takes place at atmospheric pressure.

27. A process according to claim 25 wherein said reacting takes place at a temperature less than 100°

C.

28. A process according to claim 25 wherein said printing comprises printing a predetermined pattern on said substrate with said precursor solution through an inkjet printhead and in the absence of a mask.

29. A process according to claim 25 wherein said printing on said substrate provides an amorphous thin film having an absence of organics, and wherein said amorphous thin film is adapted for deposition of a subsequent film thereon in the absence of an annealing step.

30. A process according to claim 25 wherein said providing a metal containing cation comprises providing an aqueous solution containing a metal containing cation including one or more of hafnium (Hf⁴⁺), titanium (Ti⁴⁺), zirconium (Zr⁴⁺), cerium (Ce⁴⁺), tin (Sn⁴⁺), tantalum (Ta⁵⁺), niobium (Nb⁴⁺), yttrium (Y³⁺), molybdenum (Mo⁴⁺), tungsten (W⁶⁺), aluminum (Al³⁺), gallium (Ga³⁺), zinc (Zn²⁺), chromium (Cr³⁺), iron (Fe³⁺), bismuth (Bi³⁺), lanthanides, hafnium suboxide (HfO²⁺), zirconium suboxide (ZrO²⁺), titanium suboxide (TiO²⁺), tantalum suboxide (TaO²⁺), yttrium suboxide (YO⁺), niobium suboxide (NbO²⁺), molybdenum suboxide (MoO²⁺), tungsten suboxide (WO⁴⁺), aluminum suboxide (AlO⁺), gallium suboxide (GaO⁺), suboxides of the lanthanide series, hafnium oxy-hydroxide (HfO_y(OH)_z^(4-2y-z)+), zirconium oxy-hydroxide (ZrO_y(OH)_z^(4-2y-z)+), titanium oxy-hydroxide (TiO_y(OH)_z^(4-2y-z)+), tantalum oxy-hydroxide (TaO_y(OH)_z^(5-2y-z)+), yttrium oxy-hydroxide (YO_y(OH)_z^(3-2y-z)+), niobium oxy-hydroxide (NbO_y(OH)_z^(4-2y-z)+), molybdenum oxy-hydroxide (MoO_y(OH)_z^(4-2y-z)+), tungsten oxy-hydroxide (WO_y(OH)_z^(6-2y-z)+), aluminum oxy-hydroxide (AlO_y(OH)_z^(3-2y-z)+), gallium oxy-hydroxide (GaO_y(OH)_z^(3-2y-z)+), zinc oxy-hydroxide (ZnO_y(OH)_z^(2-2y-z)+), chromium oxy-hydroxide (CrO_y(OH)_z^(3-2y-z)+), iron oxy-hydroxide (FeO_y(OH)_z^(3-2y-z)+), bismuth oxy-hydroxide (BiO_y(OH)_z^(3-2y-z)+), and oxy-hydroxides of the lanthanide series, and wherein said providing a polyatomic anion comprises providing an aqueous solution containing a polyatomic anion including one or more of sulfate (SO₄²⁻

), borate (BO₃³⁻

), phosphate (PO₄³⁻

), tungstate (WO₄²⁻

) and silicate (SiO₄⁴⁻

).

31. A process of depositing a dielectric film, comprising:

providing a metal containing cation;

providing a polyatomic anion;

reacting said polyatomic anion with said metal containing cation to form a precursor solution; and

applying said precursor solution on a substrate by an application chosen from the group including spin-coating, dip-coating, spray-coating, and inkjet printing.

32. An electronic device including a dielectric film, wherein said dielectric film is manufactured from components comprising:

a metal containing cation that includes one or more of hafnium suboxide (HfO²⁺), zirconium suboxide (ZrO²⁺), titanium suboxide (TiO²⁺), tantalum suboxide (TaO²⁺), yttrium suboxide (YO⁺), niobium suboxide (NbO²⁺), molybdenum suboxide (MoO²⁺), tungsten suboxide (WO⁴⁺), aluminum suboxide (AlO⁺), gallium suboxide (GaO⁺), and suboxides of the lanthanide series; and

a polyatomic anion including one or more of sulfate (SO₄²⁻

), borate (BO₃³⁻

), phosphate (PO₄³⁻

), tungstate (WO₄²⁻

) and silicate (SiO₄⁴⁻

).

33. A device according to claim 32 wherein said device includes one or more of a field effect transistor and a capacitor.

34. A device according to claim 32 wherein said dielectric film has a breakdown electric field strength of greater than 2.0 MV/cm.

35. A device according to claim 32 wherein said dielectric film has substantially no mass loss in a temperature range of approximately 200 to 740°

C.

36. A device according to claim 32 wherein said dielectric film is substantially impervious to acidic solutions.

37. A device according to claim 32 wherein said dielectric film is substantially impervious to basic solutions.

38. A device according to claim 32 wherein said dielectric film has a dielectric constant of at least 5.

39. A device according to claim 32 wherein said dielectric film has a current density of up to 1.0 microamp/cm² for an applied field of up to 2.2 MV/cm.

40. A device according to claim 32 wherein said dielectric film has a breakdown electric field strength of at least 3.5 MV/cm.

41. A device according to claim 32 wherein said dielectric film has a dielectric constant of at least 13.

42. A device according to claim 32 wherein said dielectric film has a breakdown electric field strength of at least 4.0 MV/cm.

43. A method of depositing a dielectric film, comprising:

reacting a polyatomic anion with a metal containing cation to form a liquid solution; and

printing said liquid solution on a substrate through a nozzle.

44. A device for creating a dielectric film, comprising:

means for mixing first and second reactants to form a dielectric precursor solution; and

means for applying said precursor solution to a substrate, wherein said applications means is chosen from the group including a spin-coater, a dip-coater, a spray-coater, and an inkjet printer.

45. A method of making a dielectric material, comprising:

step for providing a metal containing cation;

step for providing a polyatomic anion; and

step for reacting said polyatomic anion and said metal containing cation.

46. A method according to claim 45 wherein said step for providing a metal containing cation comprises providing an aqueous solution containing a metal containing cation that includes one or more of hafnium (Hf⁴⁺), titanium (Ti⁴⁺), zirconium (Zr⁴⁺), cerium (Ce⁴⁺), tin (Sn⁴⁺), tantalum (Ta⁵⁺), niobium (Nb⁴⁺), yttrium (Y³⁺), molybdenum (Mo⁴⁺), tungsten (W⁶⁺), aluminum (Al³⁺), gallium (Ga³⁺), zinc (Zn²⁺), chromium (Cr³⁺), iron (Fe³⁺), bismuth (Bi³⁺), lanthanides, hafnium suboxide (HfO²⁺), zirconium suboxide (ZrO²⁺), titanium suboxide (TiO²⁺), tantalum suboxide (TaO²⁺), yttrium suboxide (YO⁺), niobium suboxide (NbO²⁺), molybdenum suboxide (MoO²⁺), tungsten suboxide (WO⁴⁺), aluminum suboxide (AlO⁺), gallium suboxide (GaO⁺), suboxides of the lanthanide series, hafnium oxy-hydroxide (HfO_yOH)_z^(4-2y-z)+), zirconium oxy-hydroxide (ZrO_y(OH)_z^(4-2y-z)+), titanium oxy-hydroxide (TiO_y(OH)_z^(4-2y-z)+), tantalum oxy-hydroxide (TaO_y(OH)_z^(5-2y-z)+), yttrium oxy-hydroxide (YO_y(OH)_z^(3-2y-z)+), niobium oxy-hydroxide (NbO_y(OH)_z^(4-2y-z)+), molybdenum oxy-hydroxide (MoO_y(OH)_z^(4-2y-z)+), tungsten oxy-hydroxide (WO_y(OH)_z^(6-2y-z)+), aluminum oxy-hydroxide (AlO_y(OH)_z^(3-2y-z)+), gallium oxy-hydroxide (GaO_y(OH)_z^(3-2y-z)+), zinc oxy-hydroxide (ZnO_y(OH)_z^(2-2y-z)+), chromium oxy-hydroxide (CrO_y(OH)_z^(3-2y-z)+), iron oxy-hydroxide (FeO_y(OH)_z^(3-2y-z)+), bismuth oxy-hydroxide (BiO_y(OH)_z^(3-2y-z)+), and oxy-hydroxides of the lanthanide series.

47. A method according to claim 45 wherein said step for providing a polyatomic anion comprises providing an aqueous solution containing a polyatomic anion including one or more of sulfate (SO₄²⁻

), borate (BO₃³⁻

), phosphate (PO₄³⁻

), tungstate (WO₄²⁻

) and silicate (SiO₄⁴⁻

).