Microcontact printed thin film capacitors

• US 8,828,480 B2
• Filed: 03/12/2013
• Issued: 09/09/2014
• Est. Priority Date: 10/28/2005
• Status: Expired due to Fees

• Current Assignee: Penn State Research Foundation (Pennsylvania State University)
• Original Assignee: Penn State Research Foundation (Pennsylvania State University)
• Inventors: McKinstry, Susan Trolier, Randall, Clive A., Nagata, Hajime, Pinceloup, Pascal G., Skamser, Daniel J., Randall, Michael S., Tajuddin, Azizuddin, Baeson, James J.
• Primary Examiner(s): Empie, Nathan
• Assistant Examiner(s): ZHAO, XIAO SI
• Application Number:
  US13/795,179
• Publication Number:
  US 20130337153A1
• Time in Patent Office: 546 Days
• Field of Search: 427/58, 427/79, 427/97.3, 427/98.4, 101/327, 101/483, 101/492
• US Class Current: 427/97.3
• CPC Class Codes: H01G 4/1227 based on alkaline earth titanates
• CPC Class Codes: H01G 4/306 made by thin film techniques
• CPC Class Codes: H01G 4/33 Thin- or thick-film capacitors thin- or thick-film circuits H01L27/00; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor H01L28/40

Abstract

The invention relates to thin film single layers, electronic components such as multilayer capacitors which utilize thin film layers, and to their methods of manufacture. Chemical solution deposition and microcontact printing of dielectric and electrode layers are disclosed. High permittivity BaTiO3 multilayer thin film capacitors are prepared on Ni foil substrates by microcontact printing and by chemical solution deposition. Multilayer capacitors with BaTiO3 dielectric layers and LaNiO3 internal electrodes are prepared, enabling dielectric layer thicknesses of 1 μμm or less. Microcontact printing of precursor solutions of the dielectric and electrode layers is used.

Claims

1. A method of forming a microcontact printed layer of stoichiometric barium titanate on a Ni foil substrate comprising,

reacting a Ba precursor solution with a Ti precursor solution to produce a precursor solution suitable for producing stoichiometric barium titanate,

applying the precursor solution onto a stamp that has a predetermined pattern thereon to form a coated stamp,

compressing the coated stamp onto a Ni foil substrate to form a pattern of the precursor solution on the Ni foil substrate,

drying the pattern,

pyrolyzing the pattern and

firing the pattern to produce a micro contact printed layer of stoichiometric barium titanate on the Ni foil substrate.

2. The method of claim 1 wherein the Ni foil substrate is any of annealed Ni foil, virgin Ni foil and 99.99% pure Ni foil.

3. A method of manufacture of a multilayer capacitor by microcontact printing comprising,

forming a precursor solution of an electrode,

applying the precursor solution of the electrode onto a stamp having a predetermined pattern to form a coated stamp,

compressing the coated stamp onto a SiO₂/Si substrate to form a pattern of the precursor solution of the electrode on the substrate,

heat treating the precursor solution of the electrode to produce a crystallized layer of patterned electrode on the substrate,

forming a precursor solution of a dielectric material,

applying the precursor solution of the dielectric material onto a stamp having a predetermined pattern to form a dielectric precursor material coated stamp,

compressing the dielectric precursor material coated stamp onto the patterned electrode to form a pattern of the dielectric precursor solution on the patterned electrode,

applying the precursor solution of the electrode onto a stamp having a predetermined pattern to form a coated stamp,

compressing the coated stamp onto the patterned precursor solution of dielectric to form a multilayer monolith, and

heat treating the monolith to produce multilayer capacitor.

4. The method of claim 3 wherein the electrode is LaNiO₃ and the dielectric is BaTiO₃.

5. The method of claim 3 wherein the electrode is LaNiO₃ and the dielectric is Ba(Ti_1-xM_x)O₃ where M is any of Mn, Y, Ho, Dy, Er, Mg, Ca, Co, Sr, Zr or mixtures thereof.

6. A method of manufacture of a multilayer capacitor comprising,

forming a precursor solution of a dielectric material,

applying the precursor solution of the dielectric on to a sapphire single crystal substrate and spin casting the substrate having the precursor solution of dielectric thereon,

heat treating the precursor solution to produce crystallized dielectric,

forming a precursor solution of an electrode material,

applying the precursor solution of electrode material onto the crystallized dielectric and spin casting,

heat treating the precursor solution of electrode material to produce a layer of crystallized electrode material on the crystallized layer of dielectric material,

applying the precursor solution of the dielectric on to the crystallized electrode material and spin casting, and

heat treating to produce a multilayer capacitor.

7. The method of claim 6 wherein the electrode is LaNiO₃ and the dielectric is BaTiO₃.

8. The method of claim 6 wherein the electrode is LaNiO₃ and the dielectric is Ba(Ti_1-xM_x)O₃ where M is any of Mn, Y, Ho, Dy, Er, Mg, Ca, Co, Sr, Zr or mixtures thereof.

9. A method of manufacture of a multilayer capacitor comprising,

forming a precursor solution of a dielectric material,

applying the precursor solution of the dielectric on to a Ni foil substrate and spin casting the substrate having the precursor solution of dielectric thereon,

heat treating the precursor solution to produce crystallized dielectric,

forming a precursor solution of an electrode material,

applying the precursor solution of electrode material onto the crystallized dielectric and spin casting,

heat treating the precursor solution of electrode material to produce a layer of crystallized electrode material on the crystallized layer of dielectric material,

applying the precursor solution of the dielectric on to the crystallized electrode material and spin casting, and

heat treating to produce a multilayer capacitor.

10. The method of claim 9 wherein the electrode is LaNiO₃ and the dielectric is BaTiO₃.

11. The method of claim 9 wherein the electrode is LaNiO₃ and the dielectric is Ba(Ti_1-xM_x)O₃ where M is any of Mn, Y, Ho, Dy, Er, Mg, Ca, Co, Sr, Zr or mixtures thereof.

12. A method of manufacture of a multilayer capacitor comprising,

forming a precursor solution of an electrode material,

applying the precursor solution of the electrode material on to a stamp to form a stamp coated with the precursor solution of electrode,

compressing the coated stamp onto a SiO₂/Si substrate to produce a patterned layer of electrode precursor solution,

heat treating the electrode precursor solution to produce a patterned electrode,

forming a precursor solution of dielectric and spin casting the precursor solution of dielectric onto the patterned electrode,

heat treating the precursor solution of dielectric to produce crystallized dielectric,

applying a layer of the precursor solution of electrode on to a second stamp to form a stamp coated with the precursor solution of electrode material,

compressing the second stamp coated with the precursor solution of electrode material onto the crystallized dielectric to form a patterned layer of electrode precursor solution on the crystallized dielectric, and

heat treating to produce a multilayer capacitor.

13. The method of claim 12 wherein the electrode is LaNiO₃ and the dielectric is BaTiO₃.

14. The method of claim 12 wherein the electrode is LaNiO₃ and the dielectric is Ba(Ti_1-xMn_x)O₃ where x=0.01.

15. A method of manufacture of a multilayer capacitor comprising,

forming a precursor solution of an electrode material,

applying the precursor solution of the electrode material on to a stamp to form a stamp coated with the precursor solution of electrode,

compressing the coated stamp onto a Ni foil substrate to produce a patterned layer of electrode precursor solution,

heat treating the electrode precursor solution to produce a patterned electrode,

forming a precursor solution of dielectric and spin casting the precursor solution of dielectric onto the patterned electrode,

heat treating the precursor solution of dielectric to produce crystallized dielectric,

applying a layer of the precursor solution of electrode on to a second stamp to form a stamp coated with the precursor solution of electrode material,

compressing the second stamp coated with the precursor solution of electrode material onto the crystallized dielectric to form a patterned layer of electrode precursor solution on the crystallized dielectric, and

heat treating to produce a multilayer capacitor.

16. The method of claim 15 wherein the electrode is LaNiO₃ and the dielectric is BaTiO₃.

17. The method of claim 15 wherein the electrode is LaNiO₃ and the dielectric is Ba(Ti_1-xMn_x)O₃ where x=0.01.

18. A method of forming a microcontact printed layer of Ba(Ti_1-xM_x)O₃ where M is a dopant thereof on to a substrate comprising,

forming an M precursor solution where M is any of Mn, Y, Ho, Dy, Er, Mg, Ca, Co or mixtures thereof,

forming a Ba precursor solution,

mixing the M precursor solution with the Ba precursor solution to produce a blended solution,

reacting the blended solution with a Ti precursor solution to produce a Ba(Ti_1-xM_x)O₃ precursor solution where 0.005≦

x≦

0.02,

applying the Ba(Ti_1-xM_x)O₃ precursor solution onto a stamp that has a predetermined pattern thereon to form a coated stamp,

compressing the coated stamp onto a substrate selected from the group consisting of Cu foil, alumina, cordierite, cordierite containing glass-ceramics alumina containing glass-ceramics, and Si/SiO₂ to form a pattern of the Ba(Ti_1-xM_x)O₃ precursor solution on the substrate,

drying the pattern,

pyrolyzing the pattern and

firing the pattern to produce a micro contact printed layer of Ba(Ti_1-xM_x)O₃ on the substrate.

19. A method of manufacture of a multilayer capacitor by microcontact printing comprising,

forming a precursor solution of an electrode,

applying the precursor solution of the electrode onto a stamp having a predetermined pattern to form a coated stamp,

compressing the coated stamp onto a substrate selected from the group consisting of Cu foil, alumina, cordierite, cordierite containing glass-ceramics alumina containing glass-ceramics, and Si/SiO₂ to form a pattern of the precursor solution of the electrode on the substrate,

heat treating the precursor solution of the electrode to produce a crystallized layer of patterned electrode on the substrate,

forming a precursor solution of a dielectric material,

applying the precursor solution of the electrode onto a stamp having a predetermined pattern to form a dielectric precursor material coated stamp,

compressing the dielectric precursor material coated stamp onto the patterned electrode to form a pattern of the dielectric precursor solution on the patterned electrode wherein the dielectric precursor material is a precursor for stoichiometric barium titanate,

applying the precursor solution of the electrode onto a stamp having a predetermined pattern to form a coated stamp,

compressing the coated stamp onto the patterned precursor solution of dielectric to form a multilayer monolith comprising a precursor solution of dielectric on crystallized electrode and precursor solution of electrode on the precursor solution of the dielectric, and

heat treating the monolith to produce a multilayer capacitor.

20. A method of manufacture of a multilayer capacitor comprising,

forming a precursor solution of a dielectric material for stoichiometric barium titanate,

applying the precursor solution of the dielectric on to a substrate selected from the group consisting of Cu foil, alumina, cordierite, cordierite containing glass-ceramics alumina containing glass-ceramics, and Si/SiO₂ and spin casting the substrate having the precursor solution of dielectric thereon,

heat treating the precursor solution to produce crystallized dielectric,

forming a precursor solution of an electrode material,

applying the precursor solution of electrode material onto the crystallized dielectric and spin casting,

heat treating the precursor solution of electrode material to produce a layer of crystallized electrode material on the crystallized layer of dielectric material,

applying the precursor solution of the dielectric on to the substrate and spin casting, and

heat treating to produce a multilayer capacitor.

21. A method of manufacture of a multilayer capacitor comprising,

forming a precursor solution of a dielectric material wherein the dielectric precursor material is a precursor for stoichiometric barium titanate,

applying the precursor solution of the dielectric on to a substrate selected from the group consisting of Cu foil, alumina, cordierite, cordierite containing glass-ceramics alumina containing glass-ceramics, and Si/SiO₂ and spin casting the substrate having the precursor solution of dielectric thereon,

heat treating the precursor solution to produce crystallized dielectric,

forming a precursor solution of an electrode material,

applying the precursor solution of electrode material onto the crystallized dielectric and spin casting,

heat treating the precursor solution of electrode material to produce a layer of crystallized electrode material on the crystallized layer of dielectric material,

applying the precursor solution of the dielectric on to the crystallized electrode material and spin casting, and

heat treating to produce a multilayer capacitor.