Chalcogenide glass

Abstract

Boron-containing network sulfide glass which may be useful in IR transmitting applications, such as IR optics, laser or fiber amplifiers doped with rare earths with emission in the near IR, and methods of making the same.

Claims

1. A glass consisting essentially of, in atomic percent: 0-40 Ge; 0-40 As, Sb, or As+Sb; 0-15 Ga, In, or Ga+In; 0 P; 0-40 Te; greater than 0 B, in an amount up to 20; 50-85 S, Se, or S+Se; 0-15 Tl, Pb, Bi, Sn, or combinations thereof; and 0-20 of an alkali metal, alkaline earth metal, rare earth metal, or combinations thereof, wherein an amount of B or Ge+B included in the glass is non-stoichiometric with respect to an amount of S, Se, or S+Se included in the glass.

2. The glass according to claim 1, wherein the glass is substantially homogenous.

3. The glass according to claim 1, wherein the glass is substantially oxygen free.

4. The glass according to claim 1, wherein the Tl, Pb, Bi, Sn, or combination thereof is present in an amount ranging from 0.05-15 atomic percent of Tl, Pb, Bi, Sn, or combinations thereof.

5. The glass according to claim 1, wherein the alkali metal, alkaline earth metal, rare earth metal, or combination thereof is present in an amount ranging from 0.05-20 atomic percent of an alkali metal, alkaline earth metal, rare earth metal, or combinations thereof.

6. The glass according to claim 1, comprising 0.05-4 atomic percent Ge.

7. The glass according to claim 1, comprising 10-15 percent Ge.

8. The glass according to claim 1, comprising 24-40 percent Ge.

9. The glass according to claim 1, consisting essentially of, in atomic percent: greater than 0 Ge, in an amount up to 40; greater than 0 B, in an amount up to 20; and 50-85 S, Se, or S+Se.

10. The glass according to claim 1, consisting essentially of, in atomic percent: greater than 0 Ge, in an amount up to 40; greater than 0 As, in an amount up to 40; greater than 0 B, in an amount up to 20; and 50-85 Se, or S+Se.

11. The glass according to claim 1, consisting essentially of, in atomic percent: greater than 0 Ge, in an amount up to 40; greater than 0 Ga, in an amount up to 15; greater than 0 B, in an amount up to 20; and 50-85 S, Se, or S+Se.

12. The glass according to claim 1, consisting essentially of, in atomic percent: greater than 0 Ge, in an amount up to 40; greater than 0 B, in an amount up to 20; and 50-85 S, Se, or S+Se.

13. A method for making a glass, the method comprising: providing a precursor glass or crystalline material comprising in atomic percent 0-40 Ge; 0-40 As, Sb, or As+Sb; 0-15 Ga, In, or Ga+In; 0-15 P; 0-40 Te; greater than 0 B, in an amount up to 25; and 50-85 S, Se, or S+Se combining the precursor glass or crystalline material with elemental B; and melting the precursor glass or crystalline material with elemental B to form the glass.

14. The method according to claim 13, wherein the providing the precursor glass or crystalline material comprises forming a powder of the precursor glass or crystalline material.

15. The method according to claim 13, wherein the melting comprises heating the precursor glass or crystalline material with elemental B in a carbon vessel contained in silica.

16. The method according to claim 15, wherein the vessel is a carbon crucible contained in an evacuated silica ampoule.

17. The method according to claim 13, wherein the melting comprises heating the precursor glass or crystalline material with elemental B in a silica ampoule comprising an inert gas.

18. The method according to claim 13, wherein the melting comprises heating the precursor glass or crystalline material with elemental B in a silicon lined vessel.

19. The method according to claim 18, wherein the vessel is a silicon lined fused silica vessel.

20. The method according to claim 13, wherein the glass comprises in atomic percent: 0-40 Ge; 0-40 As; 0-15 Ga; 0-15 P; 0-40 Te; greater than 0 B, in an amount up to 25; and 55-75 S, Se, or S+Se.

21. A glass consisting essentially of, in atomic percent: 0 Ge; greater than 0 As, Sb, or As+Sb in an amount up to 40; 0-15 Ga, In, or Ga+In; 0 P; 0-40 Te; greater than 0 B, in an amount up to 25; 50-85 S, Se, or S+Se; 0-15 Tl, Pb, Bi, Sn, or combinations thereof; and 0-20 of an alkali metal, alkaline earth metal, rare earth metal, or combinations thereof, wherein an amount of B+(As, Sb, or As+Sb) included in the glass is non-stoichiometric with respect to an amount of S, Se, or S+Se included in the glass.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) The invention can be understood from the following detailed description either alone or together with the accompanying drawing figures.

(2) FIG. 1 is a graph showing compositional dependence of Tg for Ge.sub.20B.sub.10xP.sub.xS.sub.70 glasses, wherein x is the atomic percent of P.

(3) FIG. 2 is an 11 B magic-angle-spinning nuclear magnetic resonance (MAS NMR) spectrum of Example 11 glass (Ge.sub.20B.sub.2.5P.sub.7.5S.sub.70) in Table 2.

DETAILED DESCRIPTION

(4) Reference will now be made in detail to various embodiments of the invention.

(5) One embodiment is a glass comprising in atomic percent: 0-40 Ge; 0-40 As; 0-15 Ga; 0-15 P; 0-40 Te; greater than 0-25 B; and 55-75 S, Se, or S+Se.

(6) The glass according to one embodiment, further comprises 0-15 Sn, Sb, or Sn+Sb, for example, greater than 0-15, for example, 0.05-15, for example, 0.5-15, for example, 1-15.

(7) The glass according to one embodiment, further comprises 0-20 alkali metal, alkaline earth metal, rare earth metal, or combinations thereof, for example, Na and/or Ba, for example, greater than 0-20, for example 0.05-20, for example, 0.5-20, for example, 1-20.

(8) The glass according to one embodiment, further comprises 0-15 Tl, Pb, Bi, Sn, or combinations thereof, for example, greater than 0-15, for example, 0.05-15, for example, 0.5-15, for example, 1-15.

(9) In some embodiments, the glass is substantially homogenous. The glass can be substantially oxygen free, for example, free of intentionally added oxygen. Oxygen free is advantageous for maintaining excellent optical properties (e.g. IR transmission), and any oxygen contamination tends to bind with boron, reducing the effectiveness of boron addition to these glasses. In the case of P-containing glasses, oxygen might also find P and reduce durability of the glass. Homogeneous glasses are advantageous for thermal stability and especially optical performance of these materials.

(10) The glass, according to one embodiment, comprises greater than 0-40 percent Ge, for example, 0.05-40, for example, 0.5-40, for example, 1-40. The glass, according to one embodiment, comprises 0-4 percent Ge. The glass, according to one embodiment, comprises 10-15 percent Ge. The glass, according to one embodiment, comprises 24-40 percent Ge.

(11) The glass, according to one embodiment, comprises greater than 0-40 As, for example, 0.05-40, for example, 0.5-40, for example, 1-40.

(12) The glass, according to one embodiment, comprises greater than 0-15 Ga, for example, 0.05-15, for example, 0.5-15, for example, 1-15.

(13) The glass, according to one embodiment, comprises greater than 0-15 P, for example, 0.05-15, for example, 0.5-15, for example, 1-15.

(14) The glass, according to one embodiment, comprises 55-75 S, Se, or S+Se, for example 60-75.

(15) The glass, according to one embodiment, comprises 0-40 Te, for example, greater than 0-40 Te, for example, 0.05-40, for example, 0.5-40, for example, 1-40.

(16) Another embodiment is a method for making a glass, the method comprises:

(17) providing a precursor glass or crystalline material comprising in atomic percent 0-40 Ge, 0-40 As, 0-15 Ga, 0-15 P, 0-40 Te, and 55-75 S, Se, or S+Se;

(18) combining the precursor glass or crystalline material with elemental B; and melting the precursor glass or crystalline material with elemental B to form the glass.

(19) Providing the precursor glass or crystalline material comprises, in one embodiment, forming a powder of the precursor glass or crystalline material. In one embodiment, the melting comprises heating the precursor glass or crystalline material with elemental B in a carbon vessel contained in silica. The vessel can be a carbon crucible contained in an evacuated silica ampoule. A silica ampoule which has been backfilled with an inert gas such as argon, nitrogen, or a combination thereof can also be used. The melting can comprise heating the precursor glass or crystalline material with elemental B in a silicon lined vessel. The vessel can be an evacuated and sealed silicon lined fused silica vessel. The glass made by the methods described herein can comprise in atomic percent: 0-40 Ge; 0-40 As; 0-15 Ga; 0-15 P; 0-40 Te; greater than 0-25 B; and 55-75 S, Se, or S+Se.

EXAMPLES

(20) Table 1, Table 2, Table 3, Table 4, Table 5, and Table 6 show exemplary glasses, according to embodiments of the invention where composition is expressed in terms of atomic %. All cited examples are transparent glasses, although their transparency in the visible is limited as noted by the indicated color. Glass transition temperature (Tg) was measured by differential scanning calorimetry. FIG. 1 is a graph showing compositional dependence of Tg for Ge.sub.20B.sub.10xP.sub.xS.sub.70 glasses. The Tg increase from 305 to 340 C. as P is substituted for B is due to partial conversion of 3-coordinated B to 4-coordinated B. The presence of the latter species is confirmed by the sharp NMR resonance at 10 ppm, as indicated in FIG. 2. FIG. 2 is an 11 B MAS NMR spectrum of Example 11 (Ge.sub.20B.sub.2.5P.sub.7.5S.sub.70). The dominant resonance at 55 ppm is due to 3-coordinated B. The sharp resonance at 10 ppm indicates the presence of 4-coordinated B, which species is stabilized by the presence of P. The DSC data for Examples 3, 9-11 in the Tables are plotted as a function of composition in FIG. 1 and show that Tg attains a maximum value for a B/P ratio near unity. This behavior is due to the partial conversion of 3- to 4-coordinated B with rising P concentration. The presence of 4-coordinated B in these P-codoped glasses is demonstrated by the sharp resonance at 10 ppm in the 11 B MAS NMR spectrum of Example 11.

(21) TABLE-US-00001 TABLE 1 Atomic Example % 1 2 3 4 5 6 7 8 Ge 27.5 25 20 15 35 30 25 20 As P B 2.5 5 10 15 5 10 15 20 S 70 70 70 70 60 60 60 60 color yel- yel- yel- yel- red red red red low low low low Tg 383 350 305 288 354 ~350 356 ~350

(22) TABLE-US-00002 TABLE 2 Atomic Example % 9 10 11 12 13 14 15 Ge 20 20 20 8.3 7.9 7.3 As 16.6 15.8 14.6 23.8 P 2.5 5 7.5 B 7.5 5 2.5 5 10 16.7 5 S 70 70 70 70.1 66.4 61.5 71.3 color yel- yel- yel- orange orange orange orange low low low Tg 320 338 337

(23) TABLE-US-00003 TABLE 3 Atomic Example % 16 17 18 19 20 Ge 20 25.5 10 As 22.5 21.3 Ga 7.4 P 8.8 B 10 15 1.3 5 20 S 67.5 63.8 70 62.1 70 color orange dk orange yellow amber yellow Tg

(24) TABLE-US-00004 TABLE 4 Atomic Example % 21 22 23 Ge 9.5 9.5 9.5 As 19 19 19 B 5 5 5 Se 59.9 53.2 33.3 Te 6.7 13.3 33.3 color black black black Tg

(25) TABLE-US-00005 TABLE 5 Atomic Example % 24 25 26 27 28 29 30 31 Ge 15.8 15 7 28.5 27 As 28.5 15.8 15 14 20 18.8 P B 5 5 10 20 20 25 5 10 S 59 60 56.3 Se 66.5 63.3 60 66.5 63 Na color black dark dark orange orange orange dark dark red red red red Tg 155 260 267 267 200 238

(26) TABLE-US-00006 TABLE 6 Atomic Example % 32 33 34 35 36 Ge 20 20 20 20 21.4 As P 7.5 5 2.5 B 2.5 5 7.5 10 11.4 S 62.3 Se 70 70 70 70 Na 5 color dark dark dark dark amber red red red red Tg 250 276 279 270

(27) Initial experimental attempts to synthesize these glasses used typical chalcogenide glass preparation techniques in which appropriate mixtures of the elements are loaded into a fused silica ampoule. The latter is subsequently evacuated, sealed and then heated in a rocking furnace for at least 24 h prior to quenching the resultant liquid into a glass. When a glass with the composition of example 2 was prepared in this fashion, chemical analysis showed that the resultant material contained 0.75 wt % Si, indicating significant reaction between the batch and the wall of the fused silica ampoule. Moreover, the analyzed B/Ge ratio was found to be 0.11, considerably less than the nominal value of 0.20, indicating incomplete dissolution of B in the glass.

(28) In order to overcome the slow B dissolution kinetics, a novel batch consisting of a mixture of elemental B and ground, premelted glass comprising the remainder of the composition was used. For example, in the case of the 25Ge:5B:70S composition of Example 2, a 26.32Ge:73.685 glass was first prepared. After grinding into powder, 19.738 g of this glass was mixed with 0.263 g B. Then, in order to eliminate reaction between B and the silica ampoule, this batch was loaded into a vitreous C crucible that had been previously inserted into a silica ampoule. The latter was then evacuated and sealed as above, and then heated in a vertical furnace for 3 h at 900 C. Chemical analysis of the resultant clear yellow glass showed the presence of only 0.15 wt % Si and the B/Ge ratio to be 0.18, i.e. very close to the nominal value of 0.20.

(29) We have since also obtained similar results using the same glass+B batch and melting this in a fused silica ampoule whose walls had been coated with a thin Si film.

(30) The above methods have also proved effective in dealing with B-containing As sulfide, GeAs sulfide as well as GeGa sulfide compositions. In the former case, a batch with the nominal composition of As.sub.25B.sub.5S.sub.70, i.e. very similar to that of Example 15 (As.sub.23.75B.sub.5S.sub.71.25), was used to prepare a glass by conventional methods. The resultant material, although glassy, was translucent due to the presence of much undissolved B powder in suspension. However, when Example 15 was made in a vitreous C crucible using elemental boron plus premelted As.sub.25S.sub.75 glass powder as the As and S source for the batch, the resultant material was a transparent orange glass.

(31) There are advantages to the glass by virtue of the methods used to make the glass in that the described methods greatly reduce the level of oxygen contamination experienced by other methods. Thus the composition of the described glasses are much closer to the nominal composition and are also more homogeneous. If oxygen is intentionally added (as opposed to being incorporated as an impurity or as a byproduct of the synthesis procedure), at some point this results in phase separation.

(32) A B-free version of Example 19 in Table 3 , i.e. the base GeGa sulfide was melted and required rapid quenching in order to avoid crystallization. However, the B-containing version, Example 19, can be cooled slowly without showing signs of crystallization. So, at least in this instance, one of the benefits of adding B is stabilization of the glass against devitrification.

(33) Embodiments of the glass described herein are useful for IR transmitting applications, such as IR optics, laser or fiber amplifiers doped with rare earths with emission in the near IR. In such applications they could be regarded as being advantaged on account of their relatively good transparency in the visible as well, particularly the glasses denoted as being yellow, with next best being those designated as orange.

(34) It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.