# US 2018/0321393 A1 · Perovskite-type halides and methods thereof

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- Number: US 2018/0321393 A1
- Document ID: US20180321393A1
- Status: Published application
- Kind: A1
- Application number: 15/970,581
- Filed: 2018-05-03
- Published: 2018-11-08
- Earliest claimed: 2017-05-03
- Assignees: University of Tennessee Research Foundation
- Applicants: University of Tennessee Research Foundation
- Inventors: Yuntao Wu; Mariya Zhuravleva; Luis Stand; Charles L. Melcher
- Web page: https://patentgrep.com/patent/US20180321393A1

## CPC

- G01T 1/2023: {Selection of materials}
- C01F 17/36: halogen being the only anion, e.g. NaYF4
- C01G 25/006: {Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements}
- C09K 11/06: containing organic luminescent materials
- G01T 1/201: {using scintillating fibres}
- G01T 1/20185: {Coupling means between the photodiode and the scintillator, e.g. optical couplings using adhesives with wavelength-shifting fibres}
- G01T 1/208: Circuits specially adapted for scintillation detectors, e.g. for the photo-multiplier section
- C01F 17/30: Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 (C01F17/247 - C01F17/294 take precedence)
- C01P 2002/34: perovskite-type (ABO3)
- C01P 2002/52: containing elements as dopants
- C01P 2002/84: by UV- or VIS- data
- G01T: MEASUREMENT OF NUCLEAR OR X-RADIATION (radiation analysis of materials, mass spectrometry G01N23/00; tubes for determining the presence, intensity, density or energy of radiation or particles H01J47/00)
- C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00})
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

Metal halide optical materials (e.g., scintillator materials or persistent phosphors) are described. More particularly, the optical materials include codoped perovskite-type halides, wherein the codoping ion is present at a molar ratio of 5000 parts per million (ppm) or less with respect to all cations. For example, the optical material can be a codoped trihalide having the formula ABX3 where A is one or more alkali metal, B is one or more alkali earth metal, and X is one or more halide that is doped with up to about 10 atomic percent of a dopant ion and codoped with up to about 5000 ppm of one or more isovalent or aliovalent codopant ion, such as a tetravalent ion (e.g., Zr4+), a trivalent ion (e.g., Sc3+, Y3+, Gd3+, or La3+ ion) or a divalent ion (e.g., Mg2+). The codoped material can have modified afterglow compared to a noncodoped material.

## Claims

### Claim 1

An optical material comprising a composition of Formula (I):
[(A1-xMx)(B1-yM′y)]1-zDzX3 (I),
wherein:
0≤x≤0.1 and 0≤y≤0.1, subject to the proviso that at least one of x and y is at least 0.0001;
0.0001≤z≤0.1;
A is Li, Na, K, Rb, Cs, or any combination thereof;
B is Be, Mg, Ca, Sr, Ba, or any combination thereof;
M is In, Tl, or a combination thereof;
M′ is Ce, Pr, Nd, Sm, Eu, Gd, Tb, Yb, Bi, Sb, or any combination thereof;
D is at least one type of monovalent, divalent, trivalent, or tetravalent cation; and
X is F, Cl, Br, I, or any combination thereof.

### Claim 2 (depends on 1)

The optical material of claim 1, wherein 0.0001≤z≤0.005.

### Claim 3 (depends on 1)

The optical material of claim 1, wherein D is a trivalent cation or mixture thereof.

### Claim 4 (depends on 1)

The optical material of claim 1, wherein D is selected from the group consisting of Mg, Sc, Y, Gd, La, Zr, and combinations thereof.

### Claim 5 (depends on 1)

The optical material of claim 1, wherein the optical material comprises a composition of Formula (II):
(AB1-yM′y)1-zDzX3 (II)
wherein:
0.0001≤y≤0.1;
0.0001≤z≤0.1;
A is Li, Na, K, Rb, Cs, or any combination thereof;
B is Be, Mg, Ca, Sr, Ba, or any combination thereof;
M′ is Ce, Pr, Nd, Sm, Eu, Gd, Tb, Yb, Bi, Sb, or any combination thereof;
D is at least one type of monovalent, divalent, trivalent, or tetravalent cation; and
X is F, Cl, Br, I or any combination thereof.

### Claim 6 (depends on 5)

The optical material of claim 5, wherein 0.01≤y≤0.05.

### Claim 7 (depends on 5)

The optical material of claim 5, wherein 0.001≤z≤0.005.

### Claim 8 (depends on 5)

The optical material of claim 5, wherein A is K.

### Claim 9 (depends on 5)

The optical material of claim 5, wherein B is Ca, Sr, or a combination thereof.

### Claim 10 (depends on 5)

The optical material of claim 5, wherein M′ is Eu.

### Claim 11 (depends on 5)

The optical material of claim 5, wherein y is 0.03.

### Claim 12 (depends on 5)

The optical material of claim 5, wherein D is a trivalent cation or a combination thereof.

### Claim 13 (depends on 5)

The optical material of claim 5, wherein D is Mg, Sc, Y, Gd, La, Zr, or a combination thereof.

### Claim 14 (depends on 13)

The optical material of claim 13, wherein D is Sc.

### Claim 15 (depends on 13)

The optical material of claim 13, wherein D is Mg or Zr.

### Claim 16 (depends on 5)

The optical material of claim 5, wherein X is I.

### Claim 17 (depends on 1)

The optical material of claim 1, wherein the optical material comprises a composition of Formula (III):
(KCa1-yEuy)1-zDzX3 (III),
wherein:
0.01≤y≤0.1;
0.0001≤z≤0.005;
D is Mg, Zr, one or more trivalent cations, or a combination thereof; and
X is Cl, Br, I or any combination thereof.

### Claim 18 (depends on 17)

The optical material of claim 17, wherein y is 0.03.

### Claim 19 (depends on 17)

The optical material of claim 17, wherein 0.001≤z≤0.005.

### Claim 20 (depends on 17)

The optical material of claim 17, wherein X is I.

### Claim 21 (depends on 17)

The optical material of claim 17, wherein D is Mg, Sc, Y, Gd, La, Zr, or any combination thereof.

### Claim 22 (depends on 21)

The optical material of claim 21, wherein D is Sc, Zr, or Mg.

### Claim 23 (depends on 1)

The optical material of claim 1, wherein the optical material has reduced afterglow compared to an optical material where D is absent.

### Claim 24 (depends on 1)

The optical material of claim 1, wherein the optical material has increased afterglow compared to an optical material where D is absent.

### Claim 25 (depends on 1)

The optical material of claim 1, wherein the optical material is a single crystal material.

### Claim 26 (depends on 1)

A radiation detector comprising a photon detector and an optical material of claim 1.

### Claim 27 (depends on 26)

The radiation detector of claim 26, wherein the detector is a medical diagnostic device, a device for oil exploration, or a device for container or baggage scanning.

### Claim 28 (depends on 26)

A method of detecting gamma rays, X-rays, cosmic rays and/or particles having an energy of 1 keV or greater, the method comprising using the radiation detector of claim 26.

### Claim 29 (depends on 1)

A method of preparing an optical material of claim 1, wherein the method comprises heating a mixture of raw materials above their respective melting temperatures.

### Claim 30 (depends on 29)

The method of claim 29, wherein the method comprises:
(a) providing a mixture of raw materials, wherein the raw materials are provided in a stoichiometric ratio according to Formula (I):
[(A1-xMx)(B1-yM′y)]1-zDzX3 (I),
wherein:
0≤x≤0.1 and 0≤y≤0.1, subject to the proviso that at least one of x and y is at least 0.0001;
0.0001≤z≤0.1;
A is Li, Na, K, Rb, Cs, or any combination thereof;
B is Be, Mg, Ca, Sr, Ba, or any combination thereof;
M is In, Tl, or a combination thereof;
M′ is Ce, Pr, Nd, Sm, Eu, Gd, Tb, Yb, Bi, Sb, or any combination thereof;
D is at least one type of monovalent, divalent, trivalent, or tetravalent cation; and
X is F, Cl, Br, I, or any combination thereof;
(b) sealing the mixture in a sealed container;
(c) heating the mixture to about 20° C. above the melting point of the raw material having the highest melting point for a period of time;
(d) cooling the mixture to about room temperature; and
(e) optionally repeating steps (c) and (d).