372:
required for melting in an ampoule. The melt is normally quenched to glass by pushing it into a water cooled jacket. An advantage of melting in an open atmosphere is the ability of volatile impurities to boil off and be carried away, a significant advantage over sealed systems. For example, no SH- impurity is observed in the absorption spectra of Ga-La-S glasses, compared to very significant quantities in sulphide glasses melted by the sealed ampoule technique.
322:
atmosphere can result in large compositional changes or complete removal of components with low vapour pressures. This process also has the effect of trapping any impurities in the precursors within the glass as thus the precursor purity limits the ultimate quality of the glass that is produced. In addition, impurities can be transferred to the glass from the ampoule walls.
371:
The molten gallium sulfides fluxed the lanthanum compounds and incorporated them into the melt at temperatures much lower than their respective melting points. The viscosity of the melt is low enough, at approximately 1 poise, to allow full mixing without the need for a rocking furnace which is
251:
molecule to the crystal is to break one of the Ga-S dative bonds and replace it with a S anion. This anion links the gallium atom such that its tetrahedral environment is not altered, but what was a tricoordinated S atom now becomes a dicoordinated bridging atom. This process creates a negative
321:
melting. In this technique the required glass precursor materials are sealed under vacuum in a silica ampoule, melted, and then quenched to form a glass within the ampoule. The requirement for the sealed atmosphere is dictated by the volatile nature of many of the precursors which if melted in open
164:; consequently Ga-La-S glass takes a deep orange colour. As with all chalcogenides the phase of the bulk is determined by two key factors; the material composition and the rate at which the molten material is cooled. These variables can be controlled to manipulate the final phase of the material.
211:
crystal shown in (figure 2 below) it should be noticed that two out of three sulfur atoms (S1 and S2) are each bound to three gallium atoms. These sulfur atoms have two normal covalent bonds to two of the gallium atoms. The third Ga-S bond is dative or coordinate covalent (one of the atoms
293:
Although high purity raw elements are now commercially available, with 99.9999% purity routine for many metals, even this level of purity is often not sufficient, particularly for optical fiber applications. More of a concern are commercially available chalcogenide compounds such as
212:
provides both electrons). The third sulfur atom, S3, is bound to just two gallium atoms and is thought to be a bridging atom. The average sulfur coordination number is greater than two; sulfide glasses usually have coordination numbers less than two. Experimentally, Ga
196:. It has been reported that the Ga-S bond lengths in the glassy state are identical to those in the crystalline state. Therefore, it is only necessary to change the bond angles and, thus, it is hypothesised that Ga-La-S has the potential to be a fast switching
273:
behavior of a glass. Similarly, impurities are a major concern for optical components. Impurities in the raw materials and hence in the resulting glass, contribute to the loss of power through an optical component, whether it is in the form of a long
268:
For both the practical application and scientific study of chalcogenide glasses, glass purity is of utmost importance. Varying levels of trace impurities, even at levels of a few parts per million can alter the
526:
Hewak, D.W.; Brady, D.; Curry, R.J.; Elliott, G.; Huang, C.C.; Hughes, M.; et al. (2010). "Chalcogenide glasses for photonics device applications". In
Ganapathy, Senthil Murugan (ed.).
173:
80:
mixture, and readily accept other modifier materials into their structure. This means that Ga-La-S composition can be adjusted to give a wide variety of optical and physical properties.
224:
unit within the Ga-S crystal which has been noted as the glass former. The La-S bond is ionic and likely to be a network modifier. By adding an ionic sulfide to the crystal, like La
554:
Benazeth, S.; Tuilier, M.H.; Loireau-Lozac'h, A.M.; Dexpert, H.; Lagarde, P.; Flahaut, J. (1989). "An EXAFS structural approach of the lanthanum-gallium-sulfur glasses".
61:, which form the basic glass with other glass modifiers added as needed. Gallium-lanthanum-sulfide glasses have a wide range of vitreous formation centered around a
96:
243:
Of all the rare-earth sulfides, lanthanum gives the largest range of vitreous composites. The effect of adding an ionic sulfide modifier such as a La
318:
360:
to form the basic glass with glass modifiers added as needed. This allows melting in an open atmosphere, under a flowing inert gas, typically
125:
temperature of Ga-La-S makes it resistant to thermal damage, it has good chemical durability and unlike many chalcogenides which are based on
1087:
117:
Thermally, the refractive index of Ga-La-S glasses has a strong temperature dependence and low thermal conductivity, which results in strong
686:
17:
325:
The closed nature of the process leads to tightly controlled quality. In addition to the open and closed systems for glass melting,
310:, water or organic impurities. It is not unheard of to find for example, commercial gallium sulphide contaminated with 45% or more
326:
283:
368:
crucible and transferred to a silica tube furnace in a sealed vessel. Melting is typically at 1150 °C for 24 hours.
535:
306:. Although these may have been synthesized from high purity elements, the conversion process itself can readily introduce
1474:
1080:
679:
1479:
1168:
1557:
1073:
410:
Loireau-Lozac'h, Anne-Marie; Guittard, Micheline; Flahaut, Jean (1976). "Verres formes par les sulfures L
140:
solubility and dispersion of the ions in the glass matrix for active devices. Ga-La-S can exist in both
1567:
1552:
672:
391:
Flahaut, J.; Guittard M.; Loireau-Lozac'h, A.M. (1983). "Rare earth sulphide and oxysulphide glasses".
793:
1456:
1132:
1444:
709:
1189:
1008:
1001:
1522:
1335:
1319:
1173:
984:
874:
479:"Spectroscopy of potential mid-infrared laser transitions in gallium lanthanum sulphide glass"
1517:
1401:
1326:
1298:
1286:
1262:
1254:
960:
853:
777:
746:
741:
295:
37:
glasses, referred to as gallium lanthanum sulfide (Ga-La-S) glasses. They are mixtures of La
1406:
1160:
948:
902:
882:
837:
772:
625:
563:
489:
92:
8:
1439:
1431:
1311:
1213:
1197:
1152:
861:
845:
767:
197:
629:
567:
493:
252:
void which can then be filled by a La cation. Electrically, the effect of adding La
1484:
936:
931:
751:
107:
501:
1562:
1347:
1306:
1270:
1221:
1181:
1108:
926:
918:
695:
651:
643:
579:
575:
531:
505:
459:
455:
1028:
812:
732:
633:
571:
497:
451:
364:. Batches of the compounds are prepared in a nitrogen-purged glovebox, placed in a
188:
The structure of Ga-La-S glass consists of Ga-S bonds, with a length of 0.226
122:
103:
1389:
1040:
972:
890:
869:
365:
317:
The conventional method for producing chalcogenide glasses is through the use of
303:
299:
279:
118:
614:"Deposition and characterization of germanium sulphide glass planar waveguides"
478:
390:
1546:
647:
583:
509:
463:
311:
270:
149:
336:
Gallium lanthanum sulfide glasses use essentially non-volatile components La
329:
is emerging as a method to produce high quality chalcogenide glass, in both
1469:
655:
638:
613:
141:
34:
525:
553:
275:
145:
287:
172:
157:
137:
1065:
1096:
825:
330:
193:
189:
161:
133:
664:
220:
has not been observed in a glassy state. There exists however a GaS
409:
817:
314:
through incomplete reaction of the precursors during production.
153:
126:
99:
was discovered in 1976 by
Loireau-Lozac’h, Guittard, and Flahut.
477:
Schweizer, T.; Hewak, D.W.; Samson, B.N.; Payne, D.N. (1997).
361:
307:
596:
290:
as well as serving as nucleation sites for crystallization.
111:
1464:
1000:
282:. These impurities contribute to the optical loss through
476:
132:
A clear advantage over other chalcogenides is its high
114:
and a low maximum phonon energy, approx. 450 cm.
260:
is to give the glass an essentially ionic character.
86:
611:
1544:
612:Huang, C.C.; Hewak, D.W.; Badding, J.V. (2004).
426:" [Glasses formed by rare earth sulphides La
418:des terres rares avec le sulfure de gallium Ga
1081:
680:
597:Sanghera, J.S.; Aggarwal, I.D., eds. (1998).
232:, it is possible to modify the crystalline Ga
106:, a transmission window covering most of the
1088:
1074:
687:
673:
637:
549:
547:
171:
1095:
521:
519:
327:chalcogenide chemical vapour deposition
14:
1545:
544:
386:
384:
192:, and La-S bonds of length 0.293
129:, its glass components are non-toxic.
1069:
694:
668:
516:
528:Photonic glasses and glass-ceramics
381:
148:phases, in a glassy phase, it is a
24:
156:of 2.6 eV corresponding to a
25:
1579:
556:Journal of Non-Crystalline Solids
263:
136:content which allows excellent
110:and extending to about 10
87:History and physical properties
31:Gallium lanthanum sulfide glass
605:
590:
470:
403:
102:Optically, Ga-La-S has a high
13:
1:
502:10.1016/s0022-2313(96)00387-0
375:
91:The glass forming ability of
1002:Organogallium(III) compounds
601:. Boca Raton, FL: CRC Press.
576:10.1016/0022-3093(89)90186-5
456:10.1016/0025-5408(76)90099-4
167:
7:
444:Materials Research Bulletin
240:into a vitreous structure.
33:is the name of a family of
10:
1584:
18:Gallium lanthanum sulphide
1104:
805:
786:
760:
725:
702:
176:Figure 2. The covalent Ga
434:with gallium sulphide Ga
486:Journal of Luminescence
639:10.1364/opex.12.002501
185:
599:Infrared Fiber Optics
530:. Research Signpost.
333:and bulk glass form.
175:
184:crystalline network.
121:. However, the high
93:gallium(III) sulfide
1558:Lanthanum compounds
630:2004OExpr..12.2501H
568:1989JNCS..110...89B
494:1997JLum...72..419S
198:phase change memory
108:visible wavelengths
488:. 72–74: 419–421.
186:
1568:Non-oxide glasses
1553:Gallium compounds
1540:
1539:
1063:
1062:
1059:
1058:
696:Gallium compounds
624:(11): 2501–2505.
537:978-81-308-0375-3
450:(12): 1489–1496.
296:germanium sulfide
97:lanthanum sulfide
16:(Redirected from
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393:Glass Technology
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123:glass transition
104:refractive index
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1201:
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1177:
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1140:
1136:
1125:
1122:
1121:
1120:
1116:
1113:
1112:
1111:
1109:
1100:
1094:
1064:
1055:
1052:
1048:
1044:
1036:
1032:
1024:
1020:
1016:
1012:
996:
992:
988:
980:
976:
968:
964:
956:
952:
944:
940:
922:
914:
910:
906:
898:
894:
886:
878:
865:
857:
849:
841:
833:
829:
821:
801:
797:
782:
756:
736:
721:
717:
713:
698:
693:
663:
610:
606:
595:
591:
552:
545:
538:
524:
517:
481:
475:
471:
441:
437:
433:
429:
425:
421:
417:
413:
408:
404:
389:
382:
378:
366:vitreous carbon
359:
355:
351:
347:
343:
339:
304:arsenic sulfide
300:gallium sulfide
280:infrared window
266:
259:
255:
250:
246:
239:
235:
231:
227:
223:
219:
215:
210:
206:
183:
179:
170:
119:thermal lensing
89:
83:
78:
74:
70:
66:
62:
60:
56:
52:
48:
44:
40:
28:
23:
22:
15:
12:
11:
5:
1581:
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1529:
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1467:
1462:
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1442:
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1433:
1429:
1421:
1412:
1404:
1399:
1395:
1391:
1387:
1380:
1371:
1362:
1353:
1345:
1341:
1337:
1333:
1328:
1321:
1317:
1313:
1309:
1304:
1300:
1296:
1292:
1288:
1284:
1280:
1276:
1272:
1268:
1264:
1260:
1256:
1252:
1245:
1236:
1227:
1219:
1215:
1211:
1207:
1203:
1199:
1195:
1191:
1187:
1183:
1179:
1175:
1171:
1166:
1162:
1158:
1154:
1150:
1146:
1142:
1138:
1134:
1130:
1123:
1114:
1105:
1102:
1101:
1093:
1092:
1085:
1078:
1070:
1061:
1060:
1057:
1056:
1054:
1050:
1046:
1042:
1038:
1034:
1030:
1026:
1022:
1018:
1014:
1010:
1006:
1004:
995:
994:
990:
986:
982:
978:
974:
970:
966:
962:
958:
954:
950:
946:
942:
938:
934:
929:
924:
920:
916:
912:
908:
904:
900:
896:
892:
888:
884:
880:
876:
872:
867:
863:
859:
855:
851:
847:
843:
839:
835:
831:
827:
823:
819:
815:
809:
807:
803:
802:
800:
799:
795:
790:
788:
787:Gallium(I,III)
784:
783:
781:
780:
775:
770:
764:
762:
758:
757:
755:
754:
749:
744:
739:
734:
729:
727:
723:
722:
720:
719:
715:
711:
706:
704:
700:
699:
692:
691:
684:
677:
669:
662:
661:
618:Optics Express
604:
589:
543:
536:
515:
469:
439:
435:
431:
427:
423:
419:
415:
411:
402:
379:
377:
374:
357:
353:
349:
345:
341:
337:
319:sealed ampoule
265:
262:
257:
253:
248:
244:
237:
233:
229:
225:
221:
217:
213:
208:
204:
181:
177:
169:
166:
88:
85:
76:
72:
71: : 30% La
68:
64:
58:
54:
50:
46:
42:
38:
26:
9:
6:
4:
3:
2:
1580:
1569:
1566:
1564:
1561:
1559:
1556:
1554:
1551:
1550:
1548:
1533:
1521:
1519:
1516:
1514:
1483:
1481:
1478:
1476:
1473:
1471:
1468:
1466:
1463:
1461:
1455:
1453:
1443:
1441:
1438:
1436:
1430:
1428:
1405:
1403:
1400:
1398:
1388:
1386:
1346:
1344:
1334:
1331:
1324:
1318:
1316:
1310:
1308:
1305:
1303:
1297:
1295:
1285:
1283:
1269:
1267:
1261:
1259:
1253:
1251:
1220:
1218:
1212:
1210:
1196:
1194:
1188:
1186:
1180:
1178:
1172:
1170:
1167:
1165:
1159:
1157:
1151:
1149:
1131:
1129:
1107:
1106:
1103:
1098:
1091:
1086:
1084:
1079:
1077:
1072:
1071:
1068:
1053:
1039:
1037:
1027:
1025:
1007:
1005:
1003:
999:
993:
983:
981:
971:
969:
959:
957:
947:
945:
935:
933:
930:
928:
925:
923:
917:
915:
901:
899:
889:
887:
881:
879:
873:
871:
868:
866:
860:
858:
852:
850:
844:
842:
836:
834:
824:
822:
816:
814:
811:
810:
808:
804:
798:
792:
791:
789:
785:
779:
776:
774:
771:
769:
766:
765:
763:
759:
753:
750:
748:
745:
743:
740:
738:
731:
730:
728:
724:
718:
708:
707:
705:
701:
697:
690:
685:
683:
678:
676:
671:
670:
667:
657:
653:
649:
645:
640:
635:
631:
627:
623:
619:
615:
608:
600:
593:
585:
581:
577:
573:
569:
565:
562:(1): 89–100.
561:
557:
550:
548:
539:
533:
529:
522:
520:
511:
507:
503:
499:
495:
491:
487:
480:
473:
465:
461:
457:
453:
449:
446:(in French).
445:
406:
398:
394:
387:
385:
380:
373:
369:
367:
363:
334:
332:
328:
323:
320:
315:
313:
312:gallium oxide
309:
305:
301:
297:
291:
289:
285:
281:
277:
272:
271:spectroscopic
264:Manufacturing
261:
241:
201:
199:
195:
191:
174:
165:
163:
159:
155:
151:
150:semiconductor
147:
143:
139:
135:
130:
128:
124:
120:
115:
113:
109:
105:
100:
98:
94:
84:
81:
36:
32:
27:Type of glass
19:
806:Gallium(III)
621:
617:
607:
598:
592:
559:
555:
527:
485:
472:
447:
443:
405:
396:
392:
370:
335:
324:
316:
292:
267:
242:
202:
187:
160:of 475
131:
116:
101:
90:
82:
35:chalcogenide
30:
29:
761:Gallium(II)
703:Gallium(-V)
276:glass fiber
146:crystalline
1547:Categories
726:Gallium(I)
399:: 149–156.
376:References
288:scattering
284:absorption
200:material.
158:wavelength
138:rare-earth
1099:compounds
1097:Lanthanum
648:1094-4087
584:0022-3093
510:0022-2313
464:0025-5408
331:thin film
203:In the Ga
168:Chemistry
134:lanthanum
1563:Sulfides
656:19475087
53:, and Ga
626:Bibcode
564:Bibcode
490:Bibcode
442:].
154:bandgap
152:with a
127:arsenic
1432:La(OH)
883:Ga(CN)
875:Ga(OH)
654:
646:
582:
534:
508:
462:
352:and Ga
278:or an
142:glassy
63:70% Ga
1457:LaYbO
1336:La(NO
1312:LaMnO
1287:La(IO
1214:LaCoO
1153:LaAlO
1110:La(CH
1029:Ga(CH
973:Ga(CH
891:Ga(NO
482:(PDF)
362:argon
308:oxide
1475:LSCF
1470:LSAT
1465:LLZO
1402:LaOF
1327:LaNi
1320:LaNi
1190:LaCl
1174:LaBr
1169:LBCO
1133:La(C
1119:COO)
1041:Ga(C
1009:Ga(C
977:COO)
932:GaSb
919:GaPO
846:GaCl
838:GaBr
813:GaAs
794:GaCl
778:GaTe
773:GaSe
747:GaBr
742:GaCl
652:PMID
644:ISSN
580:ISSN
532:ISBN
506:ISSN
460:ISSN
344:, La
286:and
144:and
95:and
45:, La
1518:LaS
1504:LaO
1500:105
1480:LSM
1440:LaP
1307:LaN
1299:LaI
1263:LaH
1255:LaF
1241:LaO
1202:(CO
1182:LaC
1161:LaB
927:GaP
907:(SO
870:GaN
862:GaI
854:GaF
818:GaH
768:GaS
752:GaI
634:doi
572:doi
560:110
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452:doi
302:or
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1390:La
1358:(C
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1271:La
1265:10
1237:72
1228:36
1198:La
989:Te
985:Ga
965:Se
961:Ga
949:Ga
937:Ga
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826:Ga
733:Ga
714:Ga
710:Mg
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298:,
194:nm
190:nm
162:nm
112:μm
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1019:2
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963:2
955:3
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832:6
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436:2
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358:3
356:S
354:2
350:3
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346:2
342:3
340:S
338:2
258:3
256:S
254:2
249:3
247:S
245:2
238:3
236:S
234:2
230:3
228:S
226:2
222:4
218:3
216:S
214:2
209:3
207:S
205:2
182:3
180:S
178:2
77:3
75:S
73:2
69:3
67:S
65:2
59:3
57:S
55:2
51:3
49:O
47:2
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41:S
39:2
20:)
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