Bismuth-doped zinc aluminosilicate glasses and glass-ceramics with ultra-broadband infrared luminescence

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1 Optil Mterils 29 (27) Bismuth-ope zin luminosilite glsses n glss-ermis with ultr-ron infrre luminesene Mingying Peng,, *, Dnping Chen, Jinrong Qiu,, *, Xiongwei Jing, Congshn Zhu Shnghi Institute of Optis n Fine Mehnis, Chinese Aemy of Sienes, Photon Crft Projet, 295#, Theng Ro, Jiing, Shnghi 218, Chin Grute Shool of the Chinese Aemy of Sienes, Beijing 139, Chin Deprtment of Mterils Siene n Engineering, Zhejing University, Hngzhou 3127, Chin Reeive 16 Jnury 25; epte 5 August 25 Aville online 5 Jnury 26 Astrt Bron infrre luminesene overing the optil teleommunition wvelength region of O, E n S ns ws oserve from ismuth-ope zin luminosilite glsses n glss-ermis. The spetrosopi properties of the glsses n glss-ermis epen on the therml-tretment history. With the pperne of ghnite (ZnAl 2 O 4 ) rystlline phse, the fluoresent pek moves to longer wvelength, ut the fluoresent intensity ereses. The 13 nm fluoresene with FWHM lrger thn 25 nm n lifetime longer thn 6 ls possesses these optil mterils with potentil pplitions in lser evies n ron mplifiers. The ro infrre luminesene from the ismuth-ope zin luminosilite glsses n glss-ermis might e from BiO or ismuth lusters rther thn from Bi 5+ n Bi 3+. Ó 25 Elsevier B.V. All rights reserve. PACS: 42.6.D; 42.7.C; 42.7.K; S; 78.6 Keywors: Infrre luminesene; Glsses n glss-ermis; Bismuth 1. Introution * Corresponing uthors. E-mil resses: mypeng@mil.siom..n (M. Peng), jrq@photon. jst.go.jp (J. Qiu). During pst ees, trnsprent glss-ermi s new type of funtionl mteril hs ttrte muh more n more ttentions euse of its wie pplition in the res of flt pnel isplys, solr onentrtors, optil mplifiers n up-onversion evies, et. [1 5]. The stuies on tive ions, e.g., Ni 2+ n Er 3+, tivte glss-ermis with high luminesent effiieny hve een extensively performe n some promising results hve een hieve [3 5]. In reent yers, expning the gin nwiths of the fier mplifiers n the lser soures to hieve more effiient wvelength ivision multiplexing trnsmission network with higher pity n fster it rte hs eome key n ttrtive ojet for the future evelopment of the optil ommunition. In orer to further evelop new mplifiers or lsers with muh roer nwith, it is essentil to explore new luminesent mterils espeilly overing the nm region. Reently, novel ron infrre luminesene in lm ws oserve with FWHM lrger thn 2 nm n lifetime longer thn 2 ls from ismuth-ope SiO 2 n GeO 2 glsses t room temperture [6,7]. The exellent optil properties for the new ismuth-tivte mterils mke them s the goo nites for the super-ron mplifition gin mei [6,7]. In this pper, we report the oservtion of ron luminesene in lm region from ismuth-ope zin luminosilite glsses n glss-ermis, stuy the /$ - see front mtter Ó 25 Elsevier B.V. All rights reserve. oi:1.116/j.optmt

2 M. Peng et l. / Optil Mterils 29 (27) epenene of optil properties of the glsses n the glss-ermis on the het-tretment onitions n finlly isuss the infrre fluoresene mehnism. 2. Experimentl Anlyti regents, MgO, ZnO, SrCO 3, BCO 3, NNO 3, SiO 2, Al(OH) 3, H 3 BO 3, ZrO 2, TiO 2 n Bi 2 O 3 were selete s rw mterils. The selete glss ompositions (in mol.%) were (1) 57.3SiO 2 Æ 26.2AlO 1.5 Æ 1.6ZnO Æ.9- BO Æ 4.TiO 2 Æ 1.Bi 2 O 3 (glss 1, herefter), (2) 59.4SiO 2 Æ 22.9AlO 1.5 Æ 6.8ZnO Æ 3.8MgO Æ.9BO Æ 3.9TiO 2 Æ 1.5ZrO 2 Æ 1.Bi 2 O 3 (glss 2, herefter) n (3) 3N 2 O Æ 1Al 2 O 3 Æ 59SiO 2 Æ 1.Bi 2 O 3 (NASB glss, herefter). The 15 g thes orresponing to glss 1 n glss 2, respetively, were weighte n thoroughly homogenize in n lumin mortr, n then melte for one n hlf hours t 16 C in lumin ruiles in ir. The melts were st onto stinless steel plte n then nnele t 7 C for 2 h. Eh otine glss smple ws ut n polishe into piees with the size of 5 5 2mm 3 for ifferent hettretment proesses in smll progrmme eletri furne. The glss smples were het trete in the following progrms: 25 C 2! min 7 C 2! min 7 C 1! min 85 C 6 min! 85 C 12! min 85 C; 9 C or 95 C 12! min 85 C; 9 C or 95 C 5! min 25 C. The hrterize symols for the het-trete smples were employe to lerly illuminte the therml-tretment histories of the ifferent smples. For exmple, h ment tht glss 1 ws het trete t 95 C for 2 h. Hunre grm th for NASB glss smple ws weighte, groun, prehete t 12 C for 2 h n then melt t 155 C for 2 min. The melt ws quenhe onto the steel plte n nnele t 5 C for 1 h. The NASB glss smple ws lso ut n polishe for the mesurements. The polyrystlline power smple of Sr.95 B 4 O 7 :.5Bi ws prepre s follows: stoihiometri mounts of SrCO 3 n H 3 BO 3 together with 3 mol% exess of H 3 BO 3 to ompenste for B 2 O 3 evportion were mixe, groun, prehete t 7 C in lumin ruile in ir for 5 h n then sintere t 85 C for 5 h twie fter regroun. The ifferentil therml nlysis (DTA) urves were otine with CRY-Z Differentil Therml Anlyzer t heting rte of 1 C min 1. Phse ssemlges were hrterize y Bruker D4 X-ry iffrtometer t kv/2 ma with CuK 1 (k = 1.55 Å) s rition soure n ientifie on the sis of JCPDS stnr rs (5-669 for ZnAl 2 O 4, for BTi 2 O 5 n for SrB 4 O 7 ). The optil sorption spetr n the infrre luminesene spetr of the smples were mesure using JASCO V-57 spetrophotometer n ZOLIX SBP3 spetrofluorometer with InGAs etetor t the exittion of the 88 nm lser ioe (LD), respetively. The emission n the exittion spetr were reore on JASCO FP- 65 fluoresene UV Vis spetrofluorometer. The fluoresene lifetime mesurements were rrie out y exiting the smple with moulte 88 nm LD. The signls etete y n InGAs photoetetor in TRIAX55 spetrofluorometer were reore using storge igitl osillosope (Tektronix TDS352). All the mesurements were tken t room temperture. 3. Results n isussion 3.1. Therml stilities of glss 1 n glss 2 DTA urves of glss 1 n glss 2 re illustrte in Fig. 1. The glss trnsition temperture (T g ), rystlliztion onset temperture (T x ) n mximum rystlliztion temperture (T ) re oserve n mrke in Fig. 1. The prmeter, DT = T x T g, n e use to roughly estimte the glss therml stility. If DT is lrger thn 1 C, the glss n e onsiere to hve goo therml stility [8]. As shown in Fig. 1, the vlues of DT for glss 1 n glss 2 re 127 n 122 C, respetively, initing these glss smples re stle ginst evitrifition. Interestingly, the T pek notiely eomes roen n fltten with itions of MgO n ZrO X-ry iffrtion (XRD) ptterns Fig. 2 n present the XRD ptterns of glss 1 n glss 2 efore n fter het-tretments. No pprent iffrtion peks n e oserve for oth the untrete glss 1 n glss 2, implying tht they re vitreous. After hettretments, the iffrtion peks ttriutle to the min rystl phse of ZnAl 2 O 4 re oserve from ll the hettrete smples, together with the pperne of BTi 2 O 5 phse (see Fig. 2). Furthermore, s the het-tretment temperture goes up from 85, 9 to 95 C, the iffrtion peks of ZnAl 2 O 4 eome stronger n shrper, whih shows the inrese in the rystllite size. The verge rystllite size ws lulte y the Sherrer s eqution. The strongest iffrtion pek roun 2h = 37 orresponing to the (311) plne ws selete for the lultions. The size hnges from out 8, 11 to 14 nm n from 6, 9 to 13 nm for glss 1 n glss 2 het-trete t 85, 9 or 95 C, respetively. ENDO EXO Glss 2 Glss 1 T g2 =75 o C T g1 =71 o C T 2 =893 o C T x2 =827 o C T 1 =88 o C T x1 =837 o C Temperture ( o C) Fig. 1. DTA urves of glss 1 n glss 2.

3 558 M. Peng et l. / Optil Mterils 29 (27) h 1-9-2h h 1 ZnAl 2 O 4 Trnsmission (%) h h h () θ () Wvelength (nm) h 1 Intensity (r. units) () h h 2 ZnAl 2 O θ Fig. 2. X-ry iffrtion ptterns of () glss 1 n () glss 2 efore n fter het-tretments. The ottom pttern is from Stnr JCPDS r no for ZnAl 2 O 4. Open irle enotes the iffrtion pek ue to BTi 2 O 5. Trnsmission (%) () h h h Wvelength (nm) Fig. 3. Trnsmission spetr of () glss 1 n () glss 2 efore n fter het-tretments Trnsmission spetr Prtile rii smller thn 15 nm n refrtive inex ifferene (Dn) smller.1 etween the glss n rystls re esirle to keep mteril with goo trnspreny for the prtil purposes [1]. As mentione in Setion 3.2, the rystlline prtile rii re smller thn 15 nm. As reporte in Ref. [1], Dn is less thn.1. Thus, goo trnspreny is preserve for the zin luminosilite glsses n glss-ermis (see Fig. 3). The mximum trnsmissions re lose to 9% for the prent glss 1 n glss 2, ut re little lowere for the het-trete speimens. As the het-tretment temperture inreses, the oy olor of smple turns from light reish rown to reish rown n trnsmission ereses in turn. Three sorption peks t roun 5, 7 n 8 nm shoul e ssigne to the sorptions of ismuth ions [6,7] Infrre fluoresene spetr Fig. 4 shows the infrre fluoresene spetr of glss 1 n glss 2 efore n fter het-tretments in the se of 88 nm exittion. There is ron peke t roun 126 nm with FWHM of 286 nm for glss 1. With the pperne of ZnAl 2 O 4 phse, the pek position suenly moves to the longer wvelength of out 1285 nm with Intensity (r. units) () Reltive intensity (r. units) () h h h Wvelength (nm) h h h Wvelength (nm) Fig. 4. Fluoresene spetr of () glss 1 n () glss 2 efore n fter het-tretments pumpe y 88 nm LD.

4 M. Peng et l. / Optil Mterils 29 (27) slight erese in intensity. However, s the ZnAl 2 O 4 nnoprtile further grows up, the 1285 nm pek remins unshifte n the intensity ereses ontinuously. For glss 2 n its het-trete smples, the similr se ppers s shown in Fig. 4. The fluoresent pek lies t 126 n 129 nm for glss 2 n its het-trete smples, respetively. In the rystllizing ourse of the glsses, the tive ions, e.g., Ni 2+,Cr 3+ or Er 3+ /Y 3+, will enter the rystlline phse n therefore the luminesene intensity oul e strongly enhne for the glss-ermis [3 5,9]. But se on our experiment results mentione ove, we propose tht the ismuth ions still sty in the resiul glss phse of the forme glss-ermis. The lrger rius ifferene etween ismuth ions (R Bi 3þ = 1.3 Å) n the hoste tions (R Zn 2þ =.74 Å n R Al 3þ =.39 Å) might e the riving fore to prevent ismuth ions from entering the ghnite phse. All the previous investigtions emonstrte tht ooping of luminum into ismuth-ope glsses is inispensle for the ron infrre luminesene [6,7]. Furthermore, in our former stuies on GeO 2 :Al,Bi glsses, we foun tht inresing the luminum ontent will le to the inrese of the infrre fluoresene intensity. Though the rel role of the luminum ions in the genertion of infrre luminesene is unknown up to now, it n e onsiere tht suh ions n homogenously isperse the ismuth ions throughout the glss host to some extent s they o in Al 3+ n N 3+ o-ope sili glss [1]. In sili glss, Al 3+ ions surroun N 3+ ions with the oning ssoition of Al O N n enlrge the sping etween N 3+ ions. An therefore the intertion etween N 3+ ions is wekene n the luminesene effiieny of N 3+ ions is improve [1]. Compre with the untrete glss 1 n glss 2, the Al 2 O 3 onentrtion s ispersnt gent is reltively lower in the resiul glss phse of het-trete speimens, sine prt of Al 2 O 3 is onsume to form the ZnAl 2 O 4 nnoprtiles in the glss ermis. So the intertion etween ismuth ions eomes stronger in the glss-ermis, whih n e verifie y the reution of the fluoresene lifetime from 746 to 666, 631 n 616 ls for 1, h, h n h, respetively, n the fluoresene intensities re therefore wekene s shown in Fig Mehnism of infrre luminesene Nowys, it is still unknown where the ro infrre emission omes from in ismuth-ope glsses [6,7]. Oviously, the lifetime n the positions of oth sorption n emission peks of ismuth-ope SiO 2, GeO 2 n zin luminosilite glsses quite iffer from the Bi 3+ or Bi 2+ ope luminesent mterils previously reporte in literture [11 16]. For exmple, the lifetime in Bi 3+ -ope soium orte or phosphte glsses ws less thn 4 ls [15]. Fujimoto et l. srie the sorption n the emission spetr of SiO 2 :Al, Bi to the Bi 5+ trnsitions etween the groun stte of 1 S n the exite sttes of 3 D 3,2,1 n 1 D 2 [6]. However, t higher temperture, Bi 2 O 3 will reily issoite into the suoxie BiO or even into ismuth metl [17]. We suspet tht the infrre luminesene with the lifetime longer thn 6 ls might originte from the lower-vlene ismuth ut not from Bi 5+ ion. In orer to ientify where the infrre luminesene me from, we prepre the trnsprent n olorless NASB glss n the light-pink polyrystlline smple of Sr.95 B 4 O 7 :.5Bi. As well known, high-vlent Bi 5+ ion often exists in the ompouns, e.g., NBiO 3 or KBiO 3, ontining lkli oxies with higher siity [18,19]. The optil siity lulte from the empiril formul propose y Duffy [2,21] is.612 for the NASB glss,.515 for glss 1 n.516 for glss 2. Aoring to the optil siity theory [21], the upper oxition stte of opnt is usully fvorle in glss with higher siity. Thus, the higher vlent Bi 5+ ions shoul e more preferre in NASB glss thn in glss 1 n glss 2. If the infrre luminesene omes from Bi 5+ ions, the infrre emission shoul lso e oserve from NASB glss s well s from glss 1 n glss 2. However, no ro infrre emission ut only the typil sorption n emission ue to Bi 3+ ions n e etete in the NASB glss with higher N 2 O ontent t room temperture s inite in Fig. 5. So the infrre luminesene is not from Bi 5+ n Bi 3+ ions. The ompoun of SrB 4 O 7 possesses the strong reuing ility n the trivlent RE 3+ ions (RE = Eu, Sm, Y, Tm, N) uilt into this mtrix n e esily reue to RE 2+ even though SrB 4 O 7 :RE is prepre in n oxiizing tmosphere of ir (The trivlent Sm, Tm or N ions re usully iffiult to e reue to their ivlent form in most of other host ompouns even prepre in N 2 +H 2.) [16,22 24]. So it is possile tht the Bi 3+ ions ope into SrB 4 O 7 re prtilly reue to the lower-vlene forms suh s ivlent ions (Stnr eletroe potentil u # (Sm 3+ /Sm 2+ )= 1.15 V, u # (Eu 3+ /Eu 2+ )=.429 V, u # (Bi 3+ /Bi + ) =.2 V, u # (Bi 3+ /Bi) =.38 V). Blsse et l. reporte the o-existene of Bi 3+ n Bi 2+ in SrB 4 O 7, ut they i not stuy the luminesene in the ner infrre Intensity (r. units) P1 1 S 3 P1 1 S ' 3 P1 1 S Wvelength (nm) Fig. 5. Exittion n emission spetr of NASB glss (: k em = 433 nm; : k ex = 34 nm) n glss 1 (similr to glss 2) (: k em = 452 nm; : k ex = 342 nm). Assignments re se on Refs. [11 15]. '

5 56 M. Peng et l. / Optil Mterils 29 (27) region [16]. At the exittion of 88 nm-lser, wek ron emission in the region of nm ws oserve from Sr.95 B 4 O 7 :.5Bi, implying tht the infrre luminesene might initite from lower-vlent ismuth (see Fig. 6). At high temperture, Bi 2 O 3 n e prtilly onverte into tomi ismuth metl [17]. If the resulting ismuth toms hve hne to eome ggregte, ismuth lusters like Bi 2 n e forme. Fink et l. foun the emission in the spetrl region of 762 m 1 (1312 nm) 78 m 1 (1282 nm) from Bi 2 in gs phse, ut they i not present the lifetime t [25]. Reently, Fink n Shestkov et l. isovere the X 2 2 P 3/2! X 1 2 P 1/2 emissions in lm with ritive lifetime of 48 ± 1 ls from BiO in gs phse [25,26]. In view of the similrity in emissionpek positions n lifetime etween BiO in gs phse, glss 1 n glss 2, we propose tht the infrre luminesene might e from BiO issolve in glss 1 n glss 2. The more ientifie onlusion oul not e me t this moment, euse we nnot rule out the other possiility tht the infrre luminesene origins from the ismuth luster, e.g., Bi 2. Given tht the infrre luminesene is relly from BiO, the oserve sorptions t 5, 7 n 8 nm n e ssigne to X 1! (H, I), X 1! A 2 n X 1! A 1 respetively, n the emission pek t 126 nm n e to X 2! X 1 [26]. In untrete glss 1 n glss 2, Bi 3+ emissions re oserve exept the 126 nm fluoresene (see Fig. 5); while in the het-trete smples, no emissions from Bi 3+ ut only 126 nm emission n e foun, whih proves tht the 126 nm fluoresene is not from Bi 3+. Mye, the trivlent ismuth ions re reue to lower vlene stte in the het-trete smples. As ompre with untrete glss 1 n glss 2, the infrre-fluoresene intensities of the het-trete smples re eviently lowere, whih might e interprete y the following three resons: (1) the erement of ispersing gents of Al 2 O 3 in the glss phse of the het-trete smples les to the intertion enhnement etween the tivtors s isusse in Setion 3.4; (2) the ismuth-onentrtion inresing in the glss phse of the Intensity (r. units) Wvelength (nm) Fig. 6. Fluoresene spetrum of Sr.95 B 4 O 7 :.5Bi prepre in ir when pumpe y 88 nm LD. het-trete smples results in onentrtion-quenhing, euse ismuth nnot e uilt into the ZnAl 2 O 4 phse; (3) the pump energy loss ue to the pumping light sttering inreses s nnorystls grow up. 4. Conlusions Bron infrre luminesene overing O ( nm), E ( nm) n S ( nm) ns in the optil teleommunition region ws oserve from ismuth-ope zin luminosilite glsses n glssermis. The fluoresent intensity, lifetime n pek position epen on the therml-tretment history. With the pperne of ghnite (ZnAl 2 O 4 ) rystlline phse, fluoresent pek moves to longer wvelength. The ro 13 nm fluoresene with FWHM lrger thn 25 nm n lifetime longer thn 6 ls possesses these optil mterils with potentil pplitions in lser evies n ron mplifiers. The ro infrre luminesene from ismuth-ope zin luminosilite glsses n glss-ermis might e from BiO or ismuth lusters rther thn from Bi 5+ n Bi 3+. Aknowlegements Mingying Peng woul like to thnk Prof. E.H. Fink for helpful isussions out mehnism nlysis uring the evelopment of this rtile. This work is finnilly supporte y the Ntionl Nturl Siene Fountion of Chin (Grnt No , 2526 n 6377), Shnghi Committee of Siene n Tehnology (Grnt No. 4XD118), Shnghi Nnotehnology Promotion Center (Grnt No. 352 nm42) n the Stte Key L for Avne Photoni Mterils n Devies, Fun University. Referenes [1] G.H. Bell, L.R. Pinhney, J. Am. Cerm. So. 82 (1) (1999) 5. [2] L.R. Pinhney, J. Non-Cryst. Solis 255 (1999) 171. [3] K. Tnk, T. Muki, T. Ishihr, K. Hiro, N. Sog, S. Sogo, M. Ashi, R. Kto, J. Am. Cerm. So. 76 (11) (1993) [4] B.N. Smson, L.R. Pinkney, J. Wng, G.H. Bell, N.F. Borrelli, Opt. Lett. 27 (15) (22) 139. [5] Y. Wng, J. Ohwki, Appl. Phys. Lett. 63 (24) (1993) [6] Y. Fujimoto, M. Nktsuk, Jpn. J. Appl. Phys. (21) L279. [7] M. Peng, J. Qiu, D. Chen, X. Meng, L. Yng, X. Jing, C. Zhu, Opt. Lett. 29 (17) (24) [8] L. Neinre, S. Jing, B. Hwng, T. Luo, J. Wtson, N. Peyghmrin, J. Non-Cryst. Solis 255 (1999) 97. [9] G. Boulon, Mter. Chem. Phys. 16 (1987) 31. [1] I. Thoms, S. Pyne, G. Wilke, J. Non-Cryst. Solis 151 (1992) 183. [11] G. Boulon, B. Moine, J. Bouret, R. Reisfel, Y. Klisky, J. Lumin. 18 (19) (1979) 924. [12] R. Reisfel, L. Boehm, J. Non-Cryst. Solis 16 (1974) 83. [13] Z. Pei, Q. Su, J. Zhng, Soli Stte Commun. 86 (6) (1993) 377. [14] D. Vn e Voort, G. Blsse, J. Soli Stte Chem. 99 (1992) 4. [15] S. Prke, R.S. We, J. Phys. Chem. Solis 34 (1973) 85. [16] G. Blsse, A. Meijerink, M. Nomes, J. Zuiem, J. Phys. Chem. Solis 55 (2) (1994) 171.

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