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Title:
ALKALI SELENOGERMANATE GLASSES
Document Type and Number:
WIPO Patent Application WO/2014/085237
Kind Code:
A1
Abstract:
Selenogermanate, selenogallo- or selenoindo-germanate glasses that are modified by alkali metals, for example, Na or Li and, as such, are characterized by high alkali ion mobility or conductivity. Ionic conducting chalcogenide glasses have potential application as an electrolyte medium for solid state batteries.

Inventors:
AITKEN, Bruce Gardiner (10235 Beaver Pond Lane, Corning, New York, 14830, US)
CURRIE, Stephen Charles (98 Argonne Street, Corning, New York, 14830, US)
Application Number:
US2013/071428
Publication Date:
June 05, 2014
Filing Date:
November 22, 2013
Export Citation:
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Assignee:
CORNING INCORPORATED (1 Riverfront Plaza, Corning, New York, 14831, US)
AITKEN, Bruce Gardiner (10235 Beaver Pond Lane, Corning, New York, 14830, US)
CURRIE, Stephen Charles (98 Argonne Street, Corning, New York, 14830, US)
International Classes:
C03C3/32; C03C3/253
Domestic Patent References:
WO2013159009A12013-10-24
Foreign References:
US20120135850A12012-05-31
US4542108A1985-09-17
US5846889A1998-12-08
US20060223688A12006-10-05
Other References:
CALVEZ, LAURENT ET AL.: "Influence of gallium and alkali halide addition on the optical and thermo-mechanical properties of GeSe2-Ga2Se3 glass.", APPLIED PHYSICS A., vol. 89, no. 1, 2007, pages 183 - 188, XP019540389
ROZE, MATHIEU ET AL.: "Optical and mechanical properties of glasses and glass-ceramics based on the Ge-Ga-Se system.", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 91, no. 11, 2008, pages 3566 - 3570, XP055257617
ADAM, JEAN-LUC.: "Lanthanides in non-oxide glasses.", CHEMICAL REVIEWS, vol. 102, no. 6, 2002, pages 2461 - 2476, XP055257619
See also references of EP 2925689A4
YOUNG Z, JOURNAL OF THE AMERICAN CERAMIC SOCIETY,US, vol. 90, no. 2, 1 February 2007 (2007-02-01), pages 667 - 669
Attorney, Agent or Firm:
RUSSELL, Michael W (Corning Incorporated, Intellectual Property DepartmentSP-Ti-03-0, Corning New York, 14831, US)
Download PDF:
Claims:
Claims

What is claimed is:

1. A glass composition comprising in mole percent:

45 to 99 percent GeX2;

0 to 50 percent Ga2X3, In2X3, or a combination thereof; and

0.5 to 50 percent M2X, wherein M is an alkali metal, wherein X is Se, S, Te or a combination thereof, wherein at least 50 mole percent of the total X is Se, and wherein the X content is in the range of from 70 to 130% of the stoichiometric amount .

2. A glass composition comprising in mole percent:

45 to 99 percent GeSe2;

0 to 50 percent Ga2Se3, In2Se3, or a combination thereof; and

0.5 to 50 percent M2Se, wherein M is an alkali metal, and wherein the Se content is in the range of from 70 to 130% of the stoichiometric amount.

3. The glass composition according to claim 2, comprising 1 to 40 percent Ga2Se3, In2Se3, or a combination thereof.

4. The glass composition according to claim 2, comprising 1 to 40 percent M2Se.

5. The glass composition according to claim 2, wherein M is Na.

6. The glass composition according to claim 2, wherein (Ga and/or In) /M is greater than 1.

7. The glass composition according to claim 2, wherein M/ (Ga and/or In) is greater than 1.

8. The glass composition according to claim 2, comprising 50 percent or greater GeSe2.

9. The glass composition according to claim 2, comprising 60 percent or greater GeSe2.

10. The glass composition according to claim 2, comprising more than one alkali metal .

11. The glass composition according to claim 2, wherein the alkali metal is Li, Na, K, Rb, Cs or combinations thereof .

12. The glass composition according to claim 2, wherein the alkali metal is Li, Na, or a combination thereof.

13. The glass composition according to claim 2, wherein the alkali metal is Na.

14. The glass composition according to claim 2, further comprising one or more rare earth dopants.

15. The glass composition according to claim 2, comprising 0 to 10 mole percent of rare earth dopants.

16. The glass composition according to claim 2, comprising 0.5 to 10 mole percent of rare earth dopants. The glass composition according to claim 2, wherein the ass is transparent in the infra red spectrum.

18. A glass composition comprising in mole percent:

45 to 99 percent GeX2;

0 to 50 percent Ga2X3, In2X3, or a combination thereof; and

0.5 to 50 percent M2X + RX, wherein M is an alkali metal, wherein X is Se, S, Te or a combination thereof, wherein at least 50 mole percent of the total X is Se, wherein R is an alkaline earth metal, and wherein the X content is in the range of from 70 to 130% of the

stoichiometric amount.

19. A glass composition comprising in mole percent:

45 to 99 percent GeSe2;

0.5 to 50 percent Ga2Se3, In2Se3, or a

combination thereof; and

0.5 to 50 percent M2Se, wherein M is an alkali metal, and wherein the Se content is in the range of from 70 to 130% of the stoichiometric amount.

Description:
ALKALI SELENOGERMANATE GLASSES

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Serial No. 61/730,678 filed on November 28, 2012, the entire content of which is hereby incorporated by reference.

Field

[0002] This disclosure relates generally to chalcogenide glass compositions and more particularly to infrared (IR)

transmitting or ionic conducting chalcogenide glasses useful for, for example, an electrolyte medium, windows, waveguiding fibers, or host glasses for luminescent dopants.

Background

[0003] US Patent No. 5, 846, 889 "Infrared Transparent Selenide Glasses" discloses alkaline earth Ga and/or In-containing selenogermanate glasses comprising at least 5% RSe (where R = alkaline earth), 0.5-25% Ga2Se3 and/or In 2 Se3, 20-70% GeSe 2 with the provision for rare earth dopants. However, due to the relatively Ga- or In-poor nature of the compositions, it is likely that rare-earth dopants in such glasses are clustered and, therefore, characterized by reduced luminescent

efficiency .

[0004] It would be advantageous to expand the range of the glassforming region of modified selenogermanate glasses which may allow for greater flexibility in tailoring glass

properties such as characteristic temperatures (e.g. T g ) , thermal expansion coefficient, refractive index, conductivity, etc . that may be important for specific applications.

SUMMARY

[ 0005] Significant expansion of the glassforming region of modified selenogermanate glasses allows for greater

flexibility in tailoring glass properties such as

characteristic temperatures (e.g. T g ) , thermal expansion coefficient, refractive index, conductivity, etc. that may be important for specific applications. Moreover, the fact that the alkali to Ga and/or In ratio can be significantly greater than one is expected to result in increased mobility of the alkali modifier and, hence, improved conductivity of such glasses. Moreover, with alkali instead of alkaline earth as a modifier, stable selenogermanate glasses can be made with GeSe 2 contents as low as 50%, resulting in a significantly higher modifier content and, hence, further increase in conductivity.

[ 0006] This disclosure relates to selenogermanate, selenogallo- or selenoindo-germanate glasses that are modified by alkali metals, for example, Na or Li and, as such, are characterized by high alkali ion mobility or conductivity. Ionic conducting chalcogenide glasses have potential application as an

electrolyte medium for solid state batteries. This disclosure also relates to Ga- or In-containing chalcogenide glasses based on GeSe 2 that are modified by the presence of one or more alkali metals, particularly Na and Li. This disclosure also relates too infrared transmitting glasses that could be used in applications ranging from infrared windows and waveguiding fibers to luminescent materials when doped with an appropriate rare earth or transition metal.

[ 0007 ] One embodiment is a glass composition comprising in mole percent : 45 to 99 percent GeX 2 ;

0 to 50 percent Ga2X3, In2X3, or a combination thereof; and

0.5 to 50 percent M 2 X, wherein M is an alkali metal, wherein X is Se, S, Te or a combination thereof, wherein at least 50 mole percent of the total X is Se, and wherein the X content is in the range of from 70 to 130% of the stoichiometric amount .

[ 0008] One embodiment is a glass composition comprising in mole percent :

45 to 99 percent GeSe 2 ;

0 to 50 percent Ga2Se3, In 2 Se3, or a combination thereof; and

0.5 to 50 percent M 2 Se, wherein M is an alkali metal, and wherein the Se content is in the range of from 70 to 130% of the stoichiometric amount.

[ 0009] One embodiment is a glass composition comprising in mole percent :

45 to 99 percent GeX 2 ;

0 to 50 percent Ga 2 X3, In 2 X3, or a combination thereof; and

0.5 to 50 percent M 2 X + RX, wherein M is an alkali metal, wherein X is Se, S, Te or a combination thereof, wherein at least 50 mole percent of the total X is Se, wherein R is an alkaline earth metal, and wherein the X content is in the range of from 70 to 130% of the

stoichiometric amount.

[ 00010] One embodiment is a glass composition comprising in mole percent:

45 to 99 percent GeSe 2 ; 0.5 to 50 percent Ga2Se3, In2Se3, or a

combination thereof; and

0.5 to 50 percent IfeSe, wherein M is an alkali metal, and wherein the Se content is in the range of from 70 to 130% of the stoichiometric amount.

[00011] Additional features and advantages of the will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description.

[00012] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework for understanding the nature and character of the invention as it is claimed.

DETAILED DESCRIPTION

[00013] Reference will now be made in detail to various embodiments .

[00014] One embodiment is a glass composition comprising in mole percent:

45 to 99 percent GeX 2 ;

0 to 50 percent Ga2X3, In2X3, or a combination thereof; and

0.5 to 50 percent M 2 X, wherein M is an alkali metal, wherein X is Se, S, Te or a combination thereof, wherein at least 50 mole percent of the total X is Se, and wherein the X content is in the range of from 70 to 130% of the stoichiometric amount .

[00015] One embodiment is a glass composition comprising in mole percent:

45 to 99 percent GeSe2; 0 to 50 percent Ga2Se3, In2Se3, or a combination thereof; and

0.5 to 50 percent M 2 Se, wherein M is an alkali metal, and wherein the Se content is in the range of from 70 to 130% of the stoichiometric amount.

[ 00016] One embodiment is a glass composition comprising in mole percent:

45 to 99 percent GeX 2 ;

0 to 50 percent Ga 2 X 3 , In 2 X 3 , or a combination thereof; and

0.5 to 50 percent M 2 X + RX, wherein M is an alkali metal, wherein X is Se, S, Te or a

combination thereof, wherein at least 50 mole percent of the total X is Se, wherein R is an alkaline earth metal, and wherein the X content is in the range of from 70 to 130% of the stoichiometric amount.

[ 00017 ] One embodiment is a glass composition comprising in mole percent:

45 to 99 percent GeSe 2 ;

0.5 to 50 percent Ga 2 Se3, In 2 Se3, or a

combination thereof; and

0.5 to 50 percent M 2 Se, wherein M is an alkali metal, and wherein the Se content is in the range of from 70 to 130% of the stoichiometric amount.

[ 00018] In one embodiment, the (Ga and/or In) /R ratio is greater than 1. Having this ratio greater than 1 may provide rare-earth "declustering" . In another embodiment, the alkali to Ga and/or In ratio is greater than 1. Having this ratio greater than 1 may provide increased mobility of the alkali modifier and, hence, improved conductivity of such glasses. [ 00019] The glass composition according to some embodiments, comprises 45 to 99 mole percent GeSe 2 , for example, 45 or greater percent GeSe2, for example, 50 or greater percent GeSe 2 , for example, 55 or greater percent GeSe 2 , for example, 60 or greater percent GeSe 2 , for example, 65 or greater percent GeSe 2 , for example, 70 or greater percent GeSe 2 , for example, 71 or greater percent GeSe 2 , for example, 72 or greater percent GeSe 2 , for example, 73 or greater percent GeSe 2 , for example, 74 or greater percent GeSe 2 , for example, 75 or greater percent GeSe 2 , for example, 76 or greater percent GeSe 2 . The amount of GeSe 2 can be any numerical value in the range of from 45 to 99 mole percent, for example from 50 to 75 mole percent.

[ 00020] In one embodiment, the glass composition comprises more than one alkali metal. In some embodiments, the alkali metal is Na, K, Li, Cs, or combinations thereof. In some embodiments, the alkali metal is Na, Li, or a combination thereof .

[ 00021] The glass composition can comprise 0.5 to 50 mole percent Ga 2 Se 3 , In 2 Se 3 , or a combination thereof, for example, 0.5 or greater percent Ga 2 Se 3 , In 2 Se 3 , or a combination thereof, for example, 1 or greater percent, for example, 2 or greater percent, for example, 3 or greater percent, for example, 4 or greater percent, for example, 5 or greater percent, for example, 6 or greater percent, for example, 7 or greater percent, for example, 8 or greater percent, for example, 9 or greater percent, for example, 10 or greater percent, for example, 11 or greater percent, for example, 12 or greater percent, for example, 13 or greater percent, for example, 14 or greater percent, for example, 15 or greater percent, for example, 16 or greater percent, for example, 17 or greater percent, for example, 18 or greater percent, for example, 19 or greater percent, for example, 20 or greater percent, for example, 21 or greater percent, for example, 22 or greater percent, for example, 23 or greater percent, for example, 24 or greater percent, for example, 25 or greater percent, for example, 26 or greater percent, for example, 27 or greater percent, for example, 28 or greater percent, for example, 29 or greater percent, for example, 30 or greater percent, for example, 31 or greater percent, for example, 32 or greater percent, for example, 33 or greater percent, for example, 34 or greater percent, for example, 35 or greater percent, for example, 36 or greater percent, for example, 37 or greater percent, for example, 38 or greater percent, for example, 39 or greater percent, for example, 40 or greater percent, for example, 41 or greater percent, for example, 42 or greater percent, for example, 43 or greater percent, for example, 44 or greater percent, for example, 45 or greater percent. The amount of Ga2Se3, In2Se3, or a combination thereof can be any numerical value in the range of from 0.5 to 50 mole percent, for example, 1 to 50 mole percent, for example, 2 to 50 mole percent, for example, 3 to 50 mole percent, for example, 4 to 50 mole percent, 5 to 50 mole percent, for example, 5 to 45 mole percent, for example, 5 to 40 mole percent, for example, 5 to 35 mole percent. The glass in one embodiment comprises Ga2Se3 and not In2Se3. The glass in one embodiment comprises In 2 Se 3 and not Ga 2 Se 3 .

[ 00022 ] The glass composition can further comprise one or more rare earth dopants, for example, 0 to 10 mole percent of the rare earth dopants, for example, greater than 0 to 10 mole percent of the rare earth dopants, for example, 0.5 to 10 mole percent of the rare earth dopants, for example, 1 to 10 mole percent of the rare earth dopants, for example, 1 to 9 mole percent of the rare earth dopants. The amount of rare earth dopants can be any numerical value in the range of from 0 to 10 mole percent.

[ 00023] The glass composition according to one embodiment comprises 0.5 to 50 percent M 2 Se, for example, 1 or greater percent, for example, 2 or greater percent, for example, 3 or greater percent, for example, 4 or greater percent, for example, 5 or greater percent, for example, 6 or greater percent, for example, 7 or greater percent, for example, 8 or greater percent, for example, 9 or greater percent, for example, 10 or greater percent, for example, 11 or greater percent, for example, 12 or greater percent, for example, 13 or greater percent, for example, 14 or greater percent, for example, 15 or greater percent, for example, 16 or greater percent, for example, 17 or greater percent, for example, 18 or greater percent, for example, 19 or greater percent, for example, 20 or greater percent, for example, 21 or greater percent, for example, 22 or greater percent, for example, 23 or greater percent, for example, 24 or greater percent, for example, 25 or greater percent, for example, 26 or greater percent, for example, 27 or greater percent, for example, 28 or greater percent, for example, 29 or greater percent, for example, 30 or greater percent, for example, 31 or greater percent, for example, 32 or greater percent, for example, 33 or greater percent, for example, 34 or greater percent, for example, 35 or greater percent, for example, 36 or greater percent, for example, 37 or greater percent, for example, 38 or greater percent, for example, 39 or greater percent, for example, 40 or greater percent, for example, 41 or greater percent, for example, 42 or greater percent, for example, 43 or greater percent, for example, 44 or greater percent, for example, 45 or greater percent. The amount of Ga2Se3, In2Se3, or a combination thereof can be any numerical value in the range of from 0.5 to 50 mole percent, for example, 1 to 50 mole percent, for example, 2 to 50 mole percent, for example, 3 to 50 mole percent, for example, 4 to 50 mole percent, 5 to 50 mole percent, for example, 5 to 45 mole percent, for example, 5 to 40 mole percent, for example, 5 to 35 mole percent. The amount of lY^Se can be any numerical value in the range of from 0.5 to 50 mole percent.

[ 00024 ] In some embodiments, the Se content is in the range of from 70 to 130% of the stoichiometric amount. "% excess Se", in Table 2, refers to the amount of Se in excess of the stoichiometric amount. The latter is the amount of Se when the components are a2Se, Ga2Se3 and GeSe2 but in chalcogenide glasses, one can move off stoichiometry . Example 10 is an example of where the Se content is 10% less than the

stoichiometric amount.

[ 00025] The glass, in some embodiments, is transparent in the infra red spectrum.

[ 00026] Significant expansion of the glassforming region of alkali selenogermanate glasses allows for greater flexibility in tailoring glass properties such as characteristic

temperatures (e.g. T g ) , thermal expansion coefficient, refractive index, etc. that may be important for specific applications. Moreover, as noted above, the fact that the Ga and/or In to alkaline earth ratio is typically greater than one results in the efficient dispersal of rare earth dopants and, hence, improved luminescence.

[ 00027 ] The exemplary glasses were all prepared using typical chalcogenide glass melting/forming procedures. lOg batches of elements (Na, Ga, Ge, Se) were loaded into fused silica ampoules in a N 2 -filled glovebox. The fused silica ampoules were coated on the inside surface with a thin silicon film. The ampoules were evacuated to ~10 ~5 Torr, flame sealed and then heated to ~950°C in a rocking furnace. After melting, the ampoules were quenched in room temperature water to convert the selenide melts to glass.

[ 00028] Another way to minimize/eliminate reaction between silica and the alkali in the batch is to use standard

practices to make a precursor material (either glass or sometimes polycrystalline) whose composition is that of the final desired one minus the a 2 Se fraction. The precursor material is then powdered, mixed with the appropriate amount of a2Se (or other alkali selenide) , loaded into a carbon crucible, for example, vitreous C that is contained within a silica ampoule. The latter assembly is evacuated, sealed, heated in a furnace (not a rocking one as then the molten contents might spill out) to melt the batch, and then quenched to form the glass.

[ 00029] Exemplary glass compositions are tabulated below, with the first rows expressing the composition in terms of the molar percentages of the various selenide components and with the second rows expressing the composition in terms of atomic percent. Although the alkali metal in all cited examples is Na, analogous glasses are to be expected when Na is replaced by Li or Cs . The glass transition temperature (T g ) and the onset of crystallization (T x ) were measured by differential scanning calorimetry (DSC) .

[ 00030] Exemplary glass compositions are shown in Tables 1- 3. Table 1

Table 2

Example 7 8 9 10 11 mol%

Na 2 Se 10 25 40 7.5 15

Ga 2 Se 3 15 0 0 32.5 25

GeSe 2 75 75 60 60 60

%excess Se 0 0 0 -10 0

Na 6.06 16.67 26.67 4.38 8.57

Ga 9.09 0 0 18.98 14.29

Ge 22.73 25 20 17.52 17.14

Se 62.12 58.33 53.33 59.12 60

Table 3

[ 00031] It will be apparent to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from its spirit or scope. Thus, it is intended that the present disclosure cover modifications and variations provided within the scope of the appended claims and their equivalents.