Solid solution material of rare earth element fluoride (polycrystal and single crystal), and method for preparation thereof, and radiation detector and test device

• US 7,608,828 B2
• Filed: 04/12/2005
• Issued: 10/27/2009
• Est. Priority Date: 04/12/2004
• Status: Expired due to Fees

• Current Assignee: Stella Chemifa Corporation, Tohoku Techno Arch Co., Ltd.
• Original Assignee: Stella Chemifa Corporation, Tohoku Techno Arch Co., Ltd.
• Inventors: Aoki, Kenji, Satonaga, Tomohiko, Kamada, Kei, Yoshikawa, Akira, Fukuda, Tsuguo
• Primary Examiner(s): Porta; David P
• Assistant Examiner(s): Kim; Kiho
• Application Number:
  US11/578,248
• Publication Number:
  US 20070272898A1
• Time in Patent Office: 1,659 Days
• Field of Search: 250/361.R, 252/301.4 H
• US Class Current: 250/361.00R
• CPC Class Codes: C09K 11/7719 Halogenides C09K11/7716 takes precedence
• CPC Class Codes: C09K 11/7772 Halogenides C09K11/7767 takes precedence
• CPC Class Codes: C30B 29/12 Halides
• CPC Class Codes: G21K 4/00 Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens photographic processes using X-ray intensifiers G03C5/17; discharge tubes comprising luminescent screens H01J1/62; cathode ray tubes for X-ray conversion with optical output H01J31/50

Abstract

A rare earth fluoride solid solution material (polycrystal and/or single crystal) characterized in that the material is obtained by mutually combining a plurality of rare earth fluorides having phase transitions and having different ion radii, respectively, so that the rare earth fluoride solid solution material is free of phase transitions. A rare earth fluoride solid solution material (polycrystal and/or single crystal) characterized in that the material is represented by (RE_yRE′_1−y)F₃ (0.0000<y<1.0000), wherein RE represents one or two or more selected from Sm, Eu, and Gd, and RE′ represents one or two or more selected from Er, Tm, Yb, Lu, and Y. A rare earth fluoride solid solution material (polycrystal and/or single crystal) represented by M_xRE_yRE′_1−x−yF_z., wherein RE is one or two or more selected from Ce, Pr, Nd, Eu, Tb, Ho, Er, Tm, or Yb, RE′ is one or two or more selected from La, Sm, Gd, Dy, Lu, Y, and Sc, and M is one or more of Mg, Ca, Sr, and Ba.

Claims

1. A rare earth fluoride solid solution single crystal wherein said rare earth fluoride solid solution single crystal is represented by M_xRE_yRE′

<sub>1−

x−

y</sub>F_z,

where RE is one or two or more selected from the group consisting of Ce, Pr, Nd, Eu, Tb, Ho, Er, Tm, and Yb,

RE′

is one or two or more selected from the group consisting of La, Sm, Gd, Dy, Lu, Y, and Sc,

M is one or more of Mg, Ca, Sr, and Ba,

0.0000<

y<

1.0000,

1.5000≦

z≦

3.5000, and

0.0000<

x<

0.1500.

2. The rare earth fluoride solid solution single crystal of claim 1, wherein said rare earth fluoride solid solution single crystal has an absolute photoyield ratio between 1 inclusive and 25 exclusive, relative to BGO.

3. The rare earth fluoride solid solution single crystal of claim 1, wherein said rare earth fluoride solid solution single crystal is a scintillator material where M is Sr.

4. A rare earth fluoride solid solution single crystal wherein said rare earth fluoride solid solution single crystal is a rare earth fluoride solid solution material comprising a plurality of mutually combined rare earth fluorides having different ion radii, respectively;

wherein said rare earth fluoride solid solution material includes cations having an averaged ion radius which is in a size equal to or less than an ion radius of La³⁺ and larger than an ion radius of Sm³⁺, or in a size smaller than an ion radius of Gd³⁺ and larger than an ion radius of Er³⁺;

wherein said rare earth fluoride solid solution material includes Ce, and is free of primary phase transitions over a temperature range from room temperature to a melting point of said rare earth fluoride solid solution; and

wherein said rare earth fluoride solid solution single crystal includes an alkaline earth metal (AE) which is one or more of Mg, Ca, Sr, and Ba.

5. The rare earth fluoride solid solution single crystal of claim 4, wherein the content of the alkaline earth metal is 0.0010 to 15.0000 (wt %).

6. A rare earth fluoride solid solution single crystal wherein said rare earth fluoride solid solution single crystal is a rare earth fluoride solid solution material comprising a plurality of mutually combined rare earth fluorides having different ion radii, respectively;

wherein said rare earth fluoride solid solution material includes cations having an averaged ion radius which is in a size equal to or less than an ion radius of La³⁺ and larger than an ion radius of Sm³⁺, or in a size smaller than an ion radius of Gd³⁺ and larger than an ion radius of Er³⁺;

wherein said rare earth fluoride solid solution material includes Ce, and is free of primary phase transitions over a temperature range from room temperature to a melting point of said rare earth fluoride solid solution; and

wherein said rare earth fluoride solid solution material has fluorescence components at least one of which has a decay time of 50 nsec or shorter at a room temperature.

7. The rare earth fluoride solid solution single crystal of claim 6, wherein the content of Ce is 0.0010 to 10.0000 (wt %).

8. The rare earth fluoride solid solution single crystal of claim 6, wherein said rare earth fluoride solid solution single crystal has an absolute photoyield ratio between 1 inclusive and 25 exclusive, relative to Bi₄Ge₃O₁₂ (BGO).

9. The rare earth fluoride solid solution single crystal of claim 6, wherein an oxygen concentration is less than 10,000 wtppm.

10. The rare earth fluoride solid solution single crystal of claim 9, wherein an oxygen concentration is less than 100 wtppm.

11. A radiation detector wherein said radiation detector is provided by mutually combining:

a scintillator comprising the rare earth fluoride solid solution single crystal of claim 6; and

optical response means (photomultiplier tube (PMT), position sensitive photomultiplier tube (PSPMT), photodiode (PD), avalanche photodiode (APD), or the like).

12. A radiographic inspection apparatus wherein said radiographic inspection apparatus is provided with the radiation detector of claim 11 as a radiation detector.

13. The radiographic inspection apparatus of claim 12, wherein said rare earth fluoride solid solution single crystal has fluorescence components at least one of which has a decay time of 2 nsec or shorter at room temperature.

14. The radiographic inspection apparatus of claim 13, wherein said radiographic inspection apparatus is a type of simplex form, or a type combined with either or both of MRI and CT.

15. The radiographic inspection apparatus of claim 13 for a medical image processor, wherein said radiographic inspection apparatus is a type of simplex form, or a type combined with a magnetic resonance imaging (MRI), computed tomography (CT), single photon emission computed tomography (SPECT) apparatus, or a gamma camera, or any combination thereof.

16. The radiographic inspection apparatus of claim 13, wherein said radiographic inspection apparatus is a positron emission tomography PET apparatus.

17. The radiographic inspection apparatus of claim 16, wherein said PET is a two-dimensional PET, a three-dimensional PET, a time of flight (TOF) type PET, a depth of interaction (DOI) type PET, or any combination thereof.

18. The radiographic inspection apparatus of claim 17, wherein said TOF type PET is combined with a position sensitive photomultiplier tube.

19. A rare earth fluoride solid solution single crystal wherein said rare earth fluoride solid solution single crystal is represented by (RE_yRE′

<sub>1−

y</sub>)F₃ (0.2<

y<

0.9), wherein RE represents one or two or more selected from the group consisting of Sm, Eu, and Gd, and RE′

represents one or two or more selected from the group consisting of Er, Tm, Yb, Lu, and Y, except for Gd_yY<sub>1−

y</sub>F₃, Gd_yEr<sub>1−

y</sub>F₃, and Gd_y(YEr)<sub>1−

y</sub>F₃); and

wherein the solid solution material of rare earth element fluoride is free of primary phase transitions over a temperature range from room temperature to a melting point of said rare earth fluoride solid solution; and

wherein said rare earth fluoride solid solution material has fluorescence components at least one of which has a decay time of 50 nsec or shorter at a room temperature.

20. The rare earth fluoride solid solution single crystal of claim 19, wherein said rare earth fluoride solid solution single crystal includes Ce.

21. A rare earth fluoride solid solution single crystal wherein said rare earth fluoride solid solution single crystal is represented by (RE_yRE′

<sub>1−

y</sub>)F₃ (0.0000<

y<

1.0000), where RE represents one or two or more selected from the group consisting of Sm, Eu, and Gd, and RE′

represents one or two or more selected from the group consisting of Er, Tm, Yb, Lu, and Y;

wherein said rare earth fluoride solid solution single crystal includes Ce, and is free of primary phase transitions over a temperature range from room temperature to a melting point of said rare earth fluoride solid solution; and

wherein said rare earth fluoride solid solution material has fluorescence components at least one of which has a decay time of 50 nsec or shorter at a room temperature.

22. The rare earth fluoride solid solution single crystal of claim 21, wherein 0.2000≦

y≦

0.9000.

23. The rare earth fluoride solid solution single crystal of claim 22, wherein 0.6≦

y≦

0.8.

24. The rare earth fluoride solid solution single crystal of claim 21, wherein said rare earth fluoride solid solution single crystal is a scintillator material where RE is Gd, and RE′

is either or both of Lu and Y.

25. The rare earth fluoride solid solution single crystal of claim 24, wherein said rare earth fluoride solid solution single crystal is a scintillator material where RE is Ce.

26. A rare earth fluoride solid solution single crystal, wherein said rare earth fluoride solid solution single crystal is a single crystal and is represented by Gd_yY₁₋

yF₃, Gd_yEr<sub>1−

y</sub>F₃, or Gd_y(YEr)<sub>1−

y</sub>F₃) 0.4≦

y<

0.6); and

wherein said rare earth fluoride solid solution single crystal includes Ce, and is free of primary phase transitions over a temperature range from room temperature to a melting point of said rare earth fluoride solid solution.

27. The rare earth fluoride solid solution single crystal of claim 26, wherein said single crystal is grown by any one of a micro-pulling-down method, Czochralski method, Bridgman method, zone melt method, and Edge-defined Film-fed Growth Method (EFG method).