Materials with trigonal bipyramidal coordination and methods of making the same

1. A material, having a formula:

AM 1−x M′ x M″ y O 3+y

where A is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof;

M is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof, or M is a 1:1 mixture of M A and M B cations where M A is Zn, Mg, or Cu, and M B is Ti or Sn;

M′ is Mn, Fe, Al, Ga, In, or a combination thereof, M′ is a +3 cation, and at least some M′ 3+ cations are bound to oxygen in trigonal bipyramidal coordination as M′O 5 ;

M″ is Mg, Zn, Cu, or a combination thereof;

x is greater than 0.0 but less than or equal to 0.8;

y is an integer ranging from 0-15;

at least one of M and M′ comprises Al, Ga, or In; and

M is not Al when y=0, M′ is Mn and A is Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu.

2. The material of claim 1 where the material is chromophoric.

3. The material of claim 1 where M is a +3 cation, and at least some M 3+ cations are bound to oxygen in trigonal bipyramidal coordination as MO 5 .

4. The material of claim 3 where y is 0, and the material forms a crystal structure having hexagonal layers comprising MO 5 and M′O 5 trigonal bipyramids alternating with layers of A cations.

5. The material of claim 4 where the crystal structure has a unit cell wherein edge a has a length of 3.50-3.70 Å and edge c has a length of 10-13 Å.

6. The material of claim 5 where the crystal structure has a unit cell wherein edge a has a length of 5.5-7.0 Å and edge c has a length of 10-13 Å.

7. The material of claim 3 where M′ is Mn.

8. The material of claim 7 where Mn is bonded to oxygen with an apical Mn—O bond length of 1.80 Å to 1.95 Å.

9. The material of claim 1 where M′ is Mn and y is 0.

10. The material of claim 1 where A is Y, M is In, M′ is Mn, and y is 0.

11. The material of claim 10 where x is greater than 0.0 and less than 0.75.

12. The material of claim 1 where A is Lu, M is Ga, and M′ is Mn.

13. The material of claim 1 where M is Al and M′ is Mn, and further comprising carbonate, wherein the chromophoric material has the formula AAl 1−x Mn x O 3−z (CO 3 ) z where z is greater than 0.0 and less than or equal to 1.0.

14. The material according to claim 1 selected from YIn 1−x Mn x O 3 , DyIn 1−x Mn x O 3 , HoIn 1−x Mn x O 3 , ErIn 1−x Mn x O 3 , YSc 1−x Mn x O 3 , YFe 1−x In x O 3 , LuGa 1−x Mn x MgO 4 , ScAl 1−x Mn x ZnO 4 , ScAl 1−x Mn x MgO 4 , InGa 1−x Mn x ZnO 4 , InGa 1−x Mn x MgO 4 , ScGa 1−x Mn x ZnO 4 , ScGa 1−x Mn x MgO 4 , LuGa 1−x Mn x ZnO 4 , LuGa 1−x Mn x MgO 4 , LuGa 1−x Mn x Zn 2 O 5 , Y(Cu,Ti) 1−x Al x O 3 , Y(Cu,Ti) 1−x Ga x O 3 , Y(Cu,Ti) 1−x In x O 3 , Y(Cu,Ti) 1−x Fe x O 3 , Yb(Cu,Ti) 1−x Mn x O 3 , Lu(Cu,Ti) 1−x Mn x O 3 , Y(Fe,In) 1−x Mn x O 3 , Y(Mn,In) 1−x Fe x O 3 , (Y,Eu)Mn 1−x In x O 3 , In(In,Ga) 1−x Mn x MgO 4 , and Y(Ga, In) 1−x Mn x O 3 .

15. The material according to claim 1 selected from YIn 0.95 Mn 0.05 O 3 , YIn 0.9 Mn 0.1 O 3 , YIn 0.85 Mn 0.15 O 3 , YIn 0.8 Mn 0.2 O 3 , YIn 0.75 Mn 0.25 O 3 , YIn 0.7 Mn 0.3 O 3 , YIn 0.65 Mn 0.35 O 3 , YIn 0.6 Mn 0.4 O 3 , YIn 0.55 Mn 0.45 O 3 , YIn 0.5 Mn 0.5 O 3 , YIn 0.25 Mn 0.75 O 3 , YIn 0.1 Mn 0.9 O 3 , DyIn 0.9 Mn 0.1 O 3 , DyIn 0.8 Mn 0.2 O 3 , DyIn 0.7 Mn 0.3 O 3 , DyIn 0.6 Mn 0.4 O 3 , DyIn 0.5 Mn 0.5 O 3 , DyIn 0.4 Mn 0.6 O 3 , DyIn 0.3 Mn 0.7 O 3 , DyIn 0.2 Mn 0.8 O 3 , HoIn 0.9 Mn 0.1 O 3 , HoIn 0.8 Mn 0.2 O 3 , HoIn 0.7 Mn 0.3 O 3 , HoIn 0.5 Mn 0.5 O 3 , HoIn 0.3 Mn 0.7 O 3 , HoIn 0.2 Mn 0.8 O 3 , HoIn 0.1 Mn 0.9 O 3 , ErIn 0.9 Mn 0.1 O 3 , ErIn 0.8 Mn 0.2 O 3 , ErIn 0.5 Mn 0.5 O 3 , ErIn 0.2 Mn 0.8 O 3 , YAl 0.1 Cu 0.45 Ti 0.45 O 3 , YGa 0.1 Cu 0.45 Ti 0.45 O 3 , YIn 0.1 Cu 0.45 Ti 0.45 O 3 , YFe 0.1 Cu 0.45 Ti 0.45 O 3 , YFe 0.2 Cu 0.4 Ti 0.4 O 3 , YMn 0.1 Cu 0.45 Ti 0.45 O 3 , YMn 0.2 Cu 0.4 Ti 0.4 O 3 , YMn 0.3 Cu 0.35 Ti 0.35 O 3 , YMn 0.4 Cu 0.3 Ti 0.3 O 3 , YMn 0.5 Cu 0.25 Ti 0.25 O 3 , YMn 0.6 Cu 0.2 Ti 0.2 O 3 , YMn 0.7 Cu 0.15 Ti 0.15 O 3 , YMn 0.8 Cu 0.1 Ti 0.1 O 3 , YMn 0.9 Cu 0.05 Ti 0.05 O 3 , LuMn 0.5 Cu 0.25 Ti 0.25 O 3 , YbMn 0.5 Cu 0.25 Ti 0.25 O 3 , YGa 0.1 In 0.8 Mn 0.1 O 3 , YGa 0.1 In 0.7 Mn 0.2 O 3 , YGa 0.1 In 0.6 Mn 0.3 O 3 , YFe 0.1 In 0.8 Mn 0.1 O 3 , YFe 0.2 In 0.7 Mn 0.1 O 3 , YFe 0.3 In 0.6 Mn 0.1 O 3 , YFe 0.1 In 0.7 Mn 0.2 O 3 , YFe 0.2 In 0.6 Mn 0.2 O 3 , YFe 0.3 In 0.5 Mn 0.2 O 3 , YFe 0.1 In 0.6 Mn 0.3 O 3 , YFe 0.2 In 0.5 Mn 0.3 O 3 , YFe 0.3 In 0.4 Mn 0.3 O 3 , YFe 0.1 In 0.5 Mn 0.4 O 3 , YFe 0.2 In 0.4 O 3 , YFe 0.3 In 0.3 Mn 0.4 O 3 , YFe 0.1 In 0.9 O 3 , YFe 0.2 In 0.8 O 3 , YFe 0.3 In 0.7 O 3 , YFe 0.7 In 0.3 O 3 , YFe 0.8 In 0.2 O 3 , YFe 0.9 In 0.1 O 3 , YSc 0.1 Mn 0.9 O 3 , YSc 0.2 Mn 0.8 O 3 , Y 1.95 Eu 0.05 Mn 0.25 In 0.75 O 3 , Y 1.9 Eu 0.1 Mn 0.25 In 0.75 O 3 , YAl 0.20 Mn 0.80 O 3−z (CO 3 ) z , YAl 0.30 Mn 0.70 O 3−z (CO 3 ) z , YAl 0.40 Mn 0.60 O 3−z (CO 3 ) z , YAl 0.50 Mn 0.50 O 3−z (CO3) z , YAl 0.60 Mn 0.40 O 3−z (CO 3 ) z , YAl 0.70 Mn 0.30 O 3−z (CO 3 ) z , YAl 0.80 Mn 0.20 O 3−z (CO3) z , LuGa 0.99 Mn 0.01 MgO 4 , LuGa 0.97 Mn 0.03 MgO 4 , LuGa 0.95 Mn 0.05 MgO 4 , LuGa 0.90 Mn 0.10 MgO 4 , LuGa 0.85 Mn 0.15 MgO 4 , LuGa 0.97 Mn 0.03 ZnO 4 , LuGa 0.95 Mn 0.05 ZnO 4 , ScAl 0.99 Mn 0.01 MgO 4 , ScAl 0.95 Mn 0.05 MgO 4 , ScAl 0.90 Mn 0.95 MgO 4 , ScAl 0.85 Mn 0.15 MgO 4 , ScAl 0.95 Mn 0.05 ZnO 4 , InGa 0.97 Mn 0.03 ZnO 4 , InGa 0.97 Mn 0.03 ZnO 4 , InGa 0.95 Mn 0.05 ZnO 4 , InGa 0.95 Mn 0.05 MgO 4 , ScGa 0.95 Mn 0.05 ZnO 4 , ScGa 0.95 Mn 0.05 MgO 4 , LuGa 0.99 Mn 0.01 ZnO 4 , LuGa 0.95 Mn 0.05 ZnO 4 , In(In 0.2 Ga 0.8 ) 0.95 Mn 0.05 MgO 4 , LuGa 0.99 Mn 0.01 Zn 2 O 5 , LuGa 0.95 Mn 0.05 Zn 2 O 5 , and In(In 0.2 Ga 0.8 ) 0.95 Mn 0.05 MgO 4 .

16. A composition, comprising:

a material having a formula AM 1−x M′ x M″ y O 3+y where A is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof; M is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof, or M is a 1:1 mixture of M A and M B cations where M A is Zn, Mg, or Cu, and M B is Ti or Sn; M′ is Mn, Fe, Al, Ga, In, or a combination thereof, M′ is a +3 cation, and at least some M′ 3+ cations are bound to oxygen in trigonal bipyramidal coordination as M′O 5 ; M″ is Mg, Zn, Cu, or a combination thereof; x is greater than 0.0 but less than 1.0; y is 0 or an integer from 1-6; at least one of M and M′ comprises Al, Ga, or In; and M is not Al when y=0, M′ is Mn and A is Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; and

at least one additional component.

17. The composition of claim 16 where the composition is a paint, an ink, a glass, a plastic, or a decorative cosmetic preparation.

18. The composition of claim 16 where the composition is a paint or an ink, and the at least one additional component is a binder, a solvent, a catalyst, a thickener, a stabilizer, an emulsifier, a texturizer, an adhesion promoter, a UV stabilizer, a flattener, a preservative, or a combination thereof.

19. The composition of claim 15 where the composition is a glass, and the at least one additional component is an oxide of silicon, boron, germanium, or a combination thereof.

20. The composition of claim 16 where the material is selected from YIn 1−x Mn x O 3 , DyIn 1−x Mn x O 3 , HoIn 1−x Mn x O 3 , ErIn 1−x Mn x O 3 , YSc 1−x Mn x O 3 , YFe 1−x In x O 3 , LuGa 1−x Mn x MgO 4 , ScAl 1−x Mn x ZnO 4 , ScAl 1−x Mn x MgO 4 , InGa 1−x Mn x ZnO 4 , InGa 1−x Mn x MgO 4 , ScGa 1−x Mn x ZnO 4 , ScGa 1−x Mn x MgO 4 , LuGa 1−x Mn x ZnO 4 , LuGa 1−x Mn x MgO 4 , LuGa 1−x Mn x Zn 2 O 5 , Y(Cu,Ti) 1−x Al x O 3 , Y(Cu,Ti) 1−x Ga x O 3 , Y(Cu,Ti) 1−x In x O 3 , Y(Cu,Ti) 1−x Fe x O 3 , Yb(Cu,Ti) 1−x Mn x O 3 , Lu(Cu,Ti) 1−x Mn x O 3 , Y(Fe,In) 1−x Mn x O 3 , Y(Mn,In) 1−x Fe x O 3 , (Y,Eu)Mn 1−x In x O 3 , In(In,Ga) 1−x Mn x MgO 4 , and Y(Ga, In) 1−x Mn x O 3 .

21. The composition of claim 16 where the material is selected from YIn 0.95 Mn 0.50 O 3 , YIn 0.9 Mn 0.1 O 3 , YIn 0.85 Mn 0.15 O 3 , YIn 0.8 Mn 0.2 O 3 , YIn 0.75 Mn 0.25 O 3 , YIn 0.7 Mn 0.3 O 3 , YIn 0.65 Mn 0.35 O 3 , YIn 0.6 Mn 0.4 O 3 , YIn 0.55 Mn 0.45 O 3 , YIn 0.5 Mn 0.5 O 3 , YIn 0.25 Mn 0.75 O 3 , YIn 0.1 Mn 0.9 O 3 , DyIn 0.9 Mn 0.1 O 3 , DyIn 0.8 Mn 0.2 O 3 , DyIn 0.7 Mn 0.3 O 3 , DyIn 0.6 Mn 0.4 O 3 , DyIn 0.5 Mn 0.5 O 3 , DyIn 0.4 Mn 0.6 O 3 , DyIn 0.3 Mn 0.7 O 3 , DyIn 0.2 Mn 0.8 O 3 , HoIn 0.9 Mn 0.1 O 3 , HoIn 0.8 Mn 0.2 O 3 , HoIn 0.7 Mn 0.3 O 3 , HoIn 0.5 Mn 0.5 O 3 , HoIn 0.3 Mn 0.7 O 3 , HoIn 0.2 Mn 0.8 O 3 , HoIn 0.1 Mn 0.9 O 3 , ErIn 0.9 Mn 0.1 O 3 , ErIn 0.8 Mn 0.2 O 3 , ErIn 0.5 Mn 0.5 O 3 , ErIn 0.2 Mn 0.8 O 3 , YAl 0.1 Cu 0.45 Ti 0.45 O 3 , YGa 0.1 Cu 0.45 Ti 0.45 O 3 , YIn 0.1 Cu 0.45 Ti 0.45 O 3 , YFe 0.1 Cu 0.45 Ti 0.45 O 3 , YFe 0.2 Cu 0.4 Ti 0.4 O 3 , YMn 0.1 Cu 0.45 Ti 0.45 O 3 , YMn 0.2 Cu 0.4 Ti 0.4 O 3 , YMn 0.3 Cu 0.35 Ti 0.35 O 3 , YMn 0.4 Cu 0.3 Ti 0.3 O 3 , YMn 0.5 Cu 0.25 Ti 0.25 O 3 , YMn 0.6 Cu 0.2 Ti 0.2 O 3 , YMn 0.7 Cu 0.15 Ti 0.15 O 3 , YMn 0.8 Cu 0.1 Ti 0.1 O 3 , YMn 0.9 Cu 0.05 Ti 0.05 O 3 , LuMn 0.5 Cu 0.25 Ti 0.25 O 3 , YbMn 0.5 Cu 0.25 Ti 0.25 O 3 , YGa 0.1 In 0.8 Mn 0.1 O 3 , YGa 0.1 In 0.7 Mn 0.2 O 3 , YGa 0.1 In 0.6 Mn 0.3 O 3 , YFe 0.1 In 0.8 Mn 0.1 O 3 , YFe 0.2 In 0.7 Mn 0.1 O 3 , YFe 0.3 In 0.6 Mn 0.1 O 3 , YFe 0.1 In 0.7 Mn 0.2 O 3 , YFe 0.2 In 0.6 Mn 0.2 O 3 , YFe 0.3 In 0.5 Mn 0.2 O 3 ,YFe 0.1 In 0.6 Mn 0.3 O 3 , YFe 0.2 In 0.5 Mn 0.3 O 3 , YFe 0.3 In 0.4 Mn 0.3 O 3 , YFe 0.1 In 0.5 Mn 0.4 O 3 , YFe 0.2 In 0.4 Mn 0.4 O 3 , YFe 0.3 In 0.3 Mn 0.4 O 3 , YFe 0.1 In 0.9 O 3 , YFe 0.2 In 0.8 O 3 , YFe 0.3 In 0.7 O 3 , YFe 0.7 In 0.3 O 3 , YFe 0.8 In 0.2 O 3 , YFe 0.9 In 0.1 O 3 , YSc 0.1 Mn 0.9 O 3 , YSc 0.2 Mn 0.8 O 3 , Y 1.95 Eu 0.05 Mn 0.25 In 0.75 O 3 , Y 1.9 Eu 0.1 Mn 0.25 In 0.75 O 3 , YAl 0.20 Mn 0.80 O 3−z (CO 3 ) z , YAl 0.30 Mn 0.70 O 3−z (CO 3 ) z , YAl 0.40 Mn 0.60 O 3−z (CO 3 ) z , YAl 0.50 Mn 0.50 O 3−z (CO 3 ) z , YAl 0.60 Mn 0.40 O 3−z (CO 3 ) z , YAl 0.70 Mn 0.30 O 3−z (CO 3 ) z , YAl 0.80 Mn 0.20 O 3−z (CO 3 ) z , LuGa 0.99 Mn 0.01 MgO 4 , LuGa 0.97 Mn 0.03 MgO 4 , LuGa 0.95 Mn 0.05 MgO 4 , LuGa 0.90 Mn 0.10 MgO 4 , LuGa 0.85 Mn 0.15 MgO 4 , LuGa 0.97 Mn 0.03 ZnO 4 , LuGa 0.95 Mn 0.05 ZnO 4 , ScAl 0.99 Mn 0.01 MgO 4 , ScAl 0.95 Mn 0.05 MgO 4 , ScAl 0.90 Mn 0.95 MgO 4 , ScAl 0.85 Mn 0.15 MgO 4 , ScAl 0.95 Mn 0.05 ZnO 4 , InGa 0.97 Mn 0.03 ZnO 4 , InGa 0.97 Mn 0.03 ZnO 4 , InGa 0.95 Mn 0.05 ZnO 4 , InG 0.95 Mn 0.05 MgO 4 , ScGa 0.95 Mn 0.05 ZnO 4 , ScGa 0.95 Mn 0.05 MgO 4 , LuGa 0.99 Mn 0.01 ZnO 4 , LuGa 0.95 Mn 0.05 ZnO 4 , In(In 0.2 Ga 0.8 ) 0.95 Mn 0.05 MgO 4 , LuGa 0.99 Mn 0.01 Zn 2 O 5 , LuGa 0.95 Mn 0.05 Zn 2 O 5 , and In(In 0.2 Ga 0.8 ) 0.95 Mn 0.05 MgO 4 .

22. The composition of claim 16 where the material is YIn 1−x Mn x O 3 , and x is greater than 0.0 and less than 0.75.

23. The composition of claim 16 , further comprising at least one additional material, wherein the at least one additional material is chromophoric.

24. The composition of claim 16 , further comprising at least one additional material according to claim 1 .

25. A method for making a material having a formula AM 1−x M′ x M″ y O 3+y where A is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof; M is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof, or M is a 1:1 mixture of M A and M B cations where M A is Zn, Mg, or Cu, and M B is Ti or Sn; M′ is Mn, Fe, Al, Ga, In, or a combination thereof, M′ is a +3 cation, and at least some M′ 3+ cations are bound to oxygen in trigonal bipyramidal coordination as M′O 5 ; M″ is Mg, Zn, Cu, or a combination thereof; x is greater than 0.0 but less than 1.0; y is 0 or an integer from 1-6; at least one of M and M′ comprises Al, Ga, or In; and M is not Al when y=0, M′ is Mn and A is Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu, the method comprising:

providing powders comprising metals desired in the material;

combining the powders in stoichiometric quantities to achieve a desired final ratio of the metals in the material;

heating the powders at a temperature of about 700° C. to about 1500° C. for about 2 hours to about 20 hours to produce the material.

26. The method of claim 25 where the powders are metal oxides or metal nitrates.

27. The method of claim 26 , further comprising, after combining the powders in stoichiometric quantities, pressing the powders into a pellet before heating.

28. The method of claim 27 , further comprising:

grinding the pellet after heating to produce a powder;

pressing the powder into a pellet; and

heating the pellet at a temperature of 700-1500° C. for 2-20 hours.

29. The method of claim 25 where the material has the formula YIn 1−x Mn x O 3 .

30. A method for varying color in a material having a formula AM 1−x M′ x M″ y O 3+y where A is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof; M is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof, or M is a 1:1 mixture of M A and M B cations where M A is Zn, Mg, or Cu, and M B is Ti or Sn; M′ is Mn, Fe, Al, Ga, In, or a combination thereof, M′ is a +3 cation, and at least some M′ 3+ cations are bound to oxygen in trigonal bipyramidal coordination as M′O 5 ; M″ is Mg, Zn, Cu, or a combination thereof; x is greater than 0.0 but less than 1.0; y is 0 or an integer from 1-6; at least one of M and M′ comprises Al, Ga, or In; and M is not Al when y=0, M′ is Mn and A is Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; and where the material has a color that varies along a color continuum as x increases, the method comprising:

providing powders comprising metals desired in the material;

selecting a value of x to provide a desired color along the color continuum;

combining the powders in stoichiometric quantities according to the value of x; and

heating the powders at a temperature of about 700° C. to about 1500° C. for about 2 hours to about 20 hours to produce the material with the desired color.

31. A method for making a composition, comprising:

providing a material having a formula AM 1−x M′ x M″ y O 3+y where A is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof; M is Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Zn, In, Ga, Ti, Sn, Fe, Mg, or a combination thereof, or M is a 1:1 mixture of M A and M B cations where M A is Zn, Mg, or Cu, and M B is Ti or Sn; M′ is Mn, Fe, Al, Ga, In, or a combination thereof, M′ is a +3 cation, and at least some M′ 3+ cations are bound to oxygen in trigonal bipyramidal coordination as M′O 5 ; M″ is Mg, Zn, Cu, or a combination thereof; x is greater than 0.0 but less than 1.0; y is 0 or an integer from 1-6; at least one of M and M′ comprises Al, Ga, or In; and M is not Al when y=0, M′ is Mn and A is Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu;

combining the material with at least one additional component to produce the composition.

32. The method of claim 31 where providing the material comprises:

providing powders comprising metals desired in the material;

combining the powders in stoichiometric quantities to achieve a desired final ratio of the metals in the material; and

heating the powders at a temperature of about 700° C. to about 1500° C. for about 2 hours to about 20 hours to produce the material.

33. The method of claim 31 where the material has the formula YIn 1−x Mn x O 3 .