Aqueous solutions, methods of manufacturing the same and uses thereof

Patent metadata

Field	Value
Publication number	US-2025333324-A1
Application number	US-202318879819-A
Country	US
Kind code	A1
Filing date	Jun 28, 2023
Priority date	Jun 30, 2022
Publication date	Oct 30, 2025
Grant date	—

Abstract

The present invention relates to aqueous solutions, methods of manufacturing the same and uses thereof. The aqueous solution comprises an alkaline earth metal added in the form of a water-soluble salt, manganese at least mainly present as a citrate complex of manganese having an oxidation state of +3 or +4, and optionally a lanthanide present in the form of a water soluble complex. The aqueous precursor solutions contain metals at appropriate stoichiometric ratios for producing films of complex inorganic metal oxides by Chemical Solution Deposition (CSD). The complex inorganic metal oxides can be used as memristor materials, and generally in microelectronic, magnetic, and spintronic devices, in solid oxide fuel cells, in magnetic refrigeration, and in the fields of biomedicine, and as catalysts.

First claim

1 . An aqueous solution comprising:
an alkaline earth metal in the form of a water-soluble salt, manganese, at least mainly present as a citrate complex of manganese having an oxidation state of +3 and/or +4, and exhibiting a molality of 0.1 to 5 with respect to the alkaline earth metal; and formulated into a precursor solution for chemical solution deposition of a thin film of a material having Formula I;

wherein:
R stands for a lanthanide,
A stands for an alkaline earth metal, and
x has a value in the range from 0.5 to 1.0,
said material being crystalline.

2 . The aqueous solution according to claim 1 , further comprising a lanthanide present in the form of a water soluble complex.

3 . The aqueous solution according to claim 1 , comprising, based on the total weight of the solution:
0.5 to 40% by weight of the water-soluble alkaline earth metal salt, 0.5 to 20%, by weight of the manganese, calculated as MnO 2 , and 0.1 to 15%, by weight of a lanthanide, calculated as an oxide of the lanthanide.

4 . The aqueous solution according to claim 1 , wherein the alkaline earth metal is selected from the group consisting of calcium, barium, strontium, and combinations thereof, and wherein the alkaline earth metal is in the form of a nitrate or an acetate.

5 . The aqueous solution according to claim 1 , comprising an Mn(III) or Mn(IV) citrato complex with, on average, one citrato ligand per Mn cation.

6 . The aqueous solution according to claim 1 , further comprising a lanthanide, in the form of a citrate complex.

7 . The aqueous solution according to claim 1 , comprising a water content of 40 to 80% by mass for chemical solution deposition of a thin film having a thickness of about 10 to 200 nm.

8 . The aqueous solution according to claim 1 , having a pH of 7 or more.

9 . The aqueous solution according to claim 1 , exhibiting a molality of 0.5 to 3 with respect to the alkaline earth metal.

10 . The aqueous solution according to claim 1 , wherein in Formula I:
R stands for Eu, Gd, Tb, Sm, Pr, La or Nd; and x has a value in the range of 0.55-1.0, 0.6-1.0, 0.65-1.0, 0.7-1.0, 0.75-1.0, 0.5 to 0.99, 0.55-0.99, 0.6-0.99, 0.65-0.99, 0.7-0.99, 0.75-0.99, 0.5 to 0.95, 0.55-0.95, 0.6-0.95, 0.65-0.95, 0.7-0.95, 0.75 to 0.95, or 0.75 to 0.9.

11 . The aqueous solution according to claim 1 , which is essentially free from free citrato ligands.

12 . A method of preparing an aqueous solution comprising:
providing a first aqueous solution of a water-soluble salt of an alkaline earth metal; providing at least one of the following:
a second aqueous solution of a citrate complex of manganese having an oxidation state of +3 and/or +4, or
a third aqueous solution containing a citrate complex of manganese having an oxidation state of +3 and/or +4 and a water-soluble complex of a lanthanide; and
mixing the first and at least one of the second or third aqueous solutions at a predetermined ratio to provide said aqueous solution.

13 . The method according to claim 12 , further comprising mixing the first aqueous solution with the second aqueous solution and of the third aqueous solution.

14 . The method according to claim 12 , further comprising:
dissolving citric acid in water to form an aqueous solution of citric acid; and adding lanthanide oxide into the aqueous solution of the citric acid to form a water-soluble complex of the lanthanide.

15 . The method according to claim 12 , further comprising:
providing a lanthanide oxide; dissolving a molar excess of citric acid, compared to the lanthanide oxide into an aqueous solution; contacting the lanthanide oxide with citric acid until at least essentially all lanthanide oxide has dissolved; and increasing the pH of the aqueous solution in order to form a stable citrato complex of the lanthanide.

16 . The method according to claim 12 , further comprising:
adding MnO 2 into an aqueous solution of citric acid; reducing Mn into Mn(II) in the aqueous citric acid solution; and raising the pH of the aqueous citric acid solution to at least 8 to form Mn(III) or Mn(IV) citrate or a combination thereof.

17 . The method according to claim 16 , further comprising reducing Mn(IV) and/or Mn(III) into Mn(II) by using hydrogen peroxide, incorporated into the aqueous citric acid solution.

18 . The method according to claim 16 , further comprising adding ammonia to the aqueous solution containing Mn(II) citrate to deprotonate citric acid and to oxidize manganese to Mn(III) or Mn(IV) or a combination thereof.

19 . (canceled)

20 . The method according to claim 16 , comprising adding MnO 2 to an aqueous solution containing lanthanide citrate.

21 . The method according to claim 20 , wherein the lanthanide is selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and combinations thereof.

22 . (canceled)

23 . The method according to claim 12 , further comprising preparing an aqueous precursor solution from the aqueous solution of claim 12 suitable for the production, by chemical solution deposition, of a material having Formula I:

wherein
R stands for a lanthanide,
A stands for an alkaline earth metal, and
x has a value in the range from 0.5 to 1.0,
said material preferably being crystalline.

24 . The method according to claim 23 , wherein the first and at least one of the second or third aqueous solutions are mixed at a ratio corresponding to x to provide said aqueous solution.

25 - 31 . (canceled)

32 . A method for manufacturing a thin film on a substrate, comprising:
rendering the substrate hydrophilic; and preparing the thin film by chemical solution deposition of the aqueous solution according to claim 1 .

Assignees

• Turun Yliopisto

Inventors

• Paturi Petriina
• Paasonen Ville
• Huhtinen Hannu
• Angervo Ilari

Classifications

• C09D1/00

  Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances · CPC title

• C01P2004/03

  obtained by SEM · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01P2002/50

  Solid solutions · CPC title

• C09D7/80

  Processes for incorporating ingredients · CPC title