Jou nal o Alloys and Compounds 380 (2004) 167–172
Op ical in ensi ies o P 3+ions in anspa en oxy luo ide glass
and glass–ce amic. Applica ions o he s anda d and modi ied
Judd–O el heo ies
R.T. Géno aa, I.R. Ma ´
ına, U.R. Rod ´
ıguez-Mendozaa, F. Lahoza,
A.D. Lozano-Go ´
ınb, P. Núñezb, J. González-Pla asc,d,V.La
´
ına,∗
aDepa amen o de F´ısica Fundamen al y Expe imen al, Elec ónica y Sis emas, Uni e sidad de La Laguna, E-38200 La Laguna, Tene i e, Spain
bDepa amen o de Qu´ımica Ino gánica, Uni e sidad de La Laguna, E-38200 La Laguna, Tene i e, Spain
cDepa amen o de F´ısica Fundamen al II, Uni e sidad de La Laguna, E-38200 La Laguna, Tene i e, Spain
dIns i u o de Bioo gánica “An onio González”, Se icio Gene al de Di acción Rx (SIDIX), A . As o ´ısico F ancisco Sánchez s/n,
E-3800 La Laguna, Tene i e, Spain
Abs ac
The op ical cha ac e isa ion o P 3+ions in anspa en SiO2–Al2O3–CdF2–PbF2–YF3based glass and glass–ce amic ha e been pe o med.
F omabso p ion andemission spec a heoscilla o s eng hso he4 2–4 2elec onic ansi ions ha e beenob ained. Thein ensi ypa ame e s
ha ebeencalcula ed using bo h heJudd–O el heo y and he modi ied heo yde elopedby Ko nienko,Kaminskiiand Dunina. Acompa ison
o he expe imen al oscilla o s eng hs, he spon aneous emission p obabili ies and he li e imes o he 3P0le el and hose calcula ed using
he abo e heo e ical p ocedu es has been pe o med o bo h samples. The oo mean squa e de ia ion ound using he s anda d Judd–O el
heo y is la ge han he alue ob ained wi h he modi ied ea men .
© 2004 Published by Else ie B.V.
Keywo ds: Glass–ce amic; Nanos uc u es; P 3+; Op ical p ope ies
1. In oduc ion
T anspa en oxy luo ide glass–ce amics doped wi h lan-
hanide ions ha e ecei ed much a en ion in he ecen
li e a u e due o hei p omising applica ions in op ical de-
ices o elecommunica ion sys ems, such as ibe s, op ical
ampli ie s and solid-s a e lase s [1,2]. These ma ices can
be easily mel ed and handled in ai -a mosphe e, a e a
he mal ea men o he p ecu so glass he subsequen ly
ob ained glass–ce amic s ill shows a la ge anspa ency
and he lan hanide ions a e mainly inco po a ed in luo ide
nanoc ys als (low-ene gy phonon en i onmen s) embedded
in he oxide glassy bulk [1–5]. Mo eo e , hey ha e supe io
mac oscopic (op ical, mechanical, chemical, ...) p ope ies
compa ed o he p ecu so glass [1,2].
The Judd–O el heo y [6–9] is he mos sui able heo y
o cha ac e ise he in ensi ies o o ced elec ic–dipole an-
∗Co esponding au ho . Tel.: +34-922-31-8321;
ax: +34-922-31-8228.
E-mail add ess: [email p o ec ed] (V. La ´
ın).
si ions be ween 4 s a es o lan hanide ions, since he ab-
so p ion and emission p obabili ies o an ion-ma ix com-
bina ion a e gi en as a unc ion o a se o h ee pa ame e s,
i.e. he in ensi y o Judd–O el pa ame e s. Al hough his
heo y has been success ully applied o accoun o he op i-
cal p ope ies o lan hanide ions in solid ma ices, i is well
known ha i wo ks less well in he case o P 3+[8,9]. The
p oblem has always been a emp ing o i all he abso p ion
ansi ion in ensi ies wi h he same se o pa ame e s [8].
The disc epancies come om he heo e ical ea men s
o he con igu a ion mixing, i.e. he opposi e-pa i y exci ed
con igu a ions a e conside ed a away om he g ound
con igu a ion and a e ega ded as comple ely degene a ed.
Mo eo e , he ene gy di e ence be ween he s a es o he
g ound and he opposi e-pa i y exci ed con igu a ions is
conside ed cons an . In he case o P 3+ions, he i s
opposi e-pa i y exci ed con igu a ion is 4 15d1and i is lo-
ca ed a a ound 60,000cm−1, wi h an ex ension o a ound
20,000cm−1, so i is ob ious ha he abo e assump ions do
no seem o hold o his i alen ion. Di e en modi ica-
ions o he s anda d Judd–O el heo y ha e been de eloped
0925-8388/$ – see on ma e © 2004 Published by Else ie B.V.
doi:10.1016/j.jallcom.2004.03.025
168 R.T. G´eno a e al./Jou nal o Alloys and Compounds 380 (2004) 167–172
in o de o ake in o accoun he ene gy dependence o he
mul iple s in ol ed in he ansi ion wi h he ene gy o he
4 15d1con igu a ion [10,11].
Tick e al. [12] and Quimby e al. [13] ha e anal-
ysed he op ical p ope ies o hese oxy luo ide glass and
glass–ce amic applying he Judd–O el echnique, bu using
only abso p ion oscilla o s eng hs. Mo eo e , hey ha e
excluded he 3H4→3P2 ansi ion and wo di e en se s
o Judd–O el pa ame e s ha e been ound depending on
he me hod o calcula ion. The pu pose o his wo k is o
comple e he op ical analysis o he P 3+ions in hese ma-
ices using he expe imen al op ical oscilla o s eng hs in
abso p ion and emission. Mo eo e , a compa ison o he
op ical pa ame e s calcula ed using he Judd–O el (J–O)
pa ame e isa ion and he modi ied heo y de eloped by
Ko nienko, Kaminskii and Dunina (K–K–D) is gi en.
2. Expe imen al
The p aseodymium doped oxy luo ide samples used in
his s udy ha e he ollowing chemical composi ion (in
mol%): 30SiO2, 15Al2O3, 29CdF2, 22PbF2,(4−x)YF3and
xP F3(x=0.1 and 1). The samples we e ob ained by
mel ing he ho oughly mixed composi ion in an elec ic
u nace a 1050◦C o 2h and quickly cas ing he mel in o
a slab by p essing be ween wo s ainless s eel pla es a RT.
The anspa en glass–ce amic was ob ained a e a he mal
ea men o he p ecu so glass a 470◦C o 36h.
The X- ay analysis was pe o med in an X’Pe PANaly -
ical di ac ome e on a solid sample by using Cu adia ion.
Op ical abso p ion spec a we e eco ded in a Pe kin-Elme
lambda9 spec opho ome e . Luminescence spec a we e
ob ained by exci ing he samples wi h ligh coming om a
250W halogen lamp h ough a 1/4.5m Spex single-g a ing
monoch oma o . De ec ion was pe o med h ough a 1/4.5m
Spex double-g a ing monoch oma o using a Hamama su
R-928 pho omul iplie . Spec a we e co ec ed om in-
s umen al esponse. Fo li e ime measu emen s a MOPO
pumped lase (pulse wid h 10ns) was used. Fo measu e-
men s a 13K an APD C yogenics helium con inuous- low
c yos a was used.
3. Theo e ical backg ound
The expe imen al measu e o he in ensi y o a lan hanide
ion in a-con igu a ional ansi ion is he a ea unde an ab-
so p ion peak, ha can be ela ed o he ansi ion p oba-
bili y h ough a dimensionless quan i y called he oscilla o
s eng h. Fo ansi ions be ween mul iple s o he 4 Ncon-
igu a ion in andomly-o ien ed sys ems he expe imen al
oscilla o s eng hs co esponding o abso p ion bands can
be ob ained using he ollowing o mula:
=mc2
πe2N2.303OD(λ)
λ2ddλ(1)
whe e mand ea e he elec on mass and cha ge, espec i ely,
c he speed o ligh , N he numbe o abso bing ions in he
uni olume, d he hickness o he sample and OD(λ)is he
op ical densi y as a unc ion o wa eleng h.
In he s anda d Judd–O el heo y, he elec ic dipole os-
cilla o s eng h o a ansi ion om a mul iple |aJ o a mul-
iple |bJ, wi h an a e age equency ν,isgi enby[6–9]
he ollowing:
ED(aJ,bJ)=8π2mν
3(2J+1)n2hχED
×
λ=2,4,6
Ωλ|aJ||Uλ||bJ|2(2)
whe e his he Planck cons an , χED =n(n2+2)2/9 he
ield co ec ion ac o and n he e ac ion index (n=1.75
o hese samples), 2J+1 he degene acy o mul iple |aJ
and Ωλa e he Judd–O el pa ame e s. The doubly educed
ma ix elemen s ||Uλ|| a e almos independen o he hos ,
and hose calcula ed by Webe o P 3+in LaF3ha e been
used [14].
In o de o ake in o accoun he ene gy dependence o
he mul iple s in ol ed in he op ical ansi ion wi h he en-
e gy o he 4 15d1con igu a ion, Ko nienko, Kaminskii and
Dunina ha e conside ed he non-o hogonali y o he wa e
unc ions o ge he ollowing o mula [11]:
ED(aJ,bJ)=8π2mν
3h(2J+1)n2χED
×
λ=2,4,6
Ωλ|aJ||Uλ||bJ|2[1 +2α(E(aJ)
+E(bJ)−2E(4 N))] (3)
whe e α=(1/2)[E(4 15d1)−E(4 N)], being E(4 N)
and E(4 15d1) he mean ene gies o he g ound and i s
opposi e-pa i y con igu a ions, espec i ely, and E(aJ) and
E(bJ) a e he ene gies o he aJ and bJmul iple s o he
4 Ncon igu a ion (N=2 o he P 3+ion).
The spon aneous emission p obabili y AED(aJ,bJ)o an
elec ic–dipole ansi ion is gi en as he ollowing equa ion:
AED(aJ,bJ)=8π2ν2e2n2
mc3 ED(aJ,bJ)(4)
and he adia i e li e ime τ is gi en by
τ =1

bJ
A(aJ,bJ)(5)
whe e he magne ic–dipole con ibu ions o he spon aneous
emission p obabili ies ha e been conside ed.
4. Resul s and discussion
The X- ay di ac ion pa e ns gi en in Fig. 1 clea ly
show he s uc u al ans o ma ion expec ed a e he he -
mal ea men o he o iginal glass. B oad cu es, ypical o
R.T. G´eno a e al./Jou nal o Alloys and Compounds 380 (2004) 167–172 169
25 50 75
In ensi y (a b. uni s)
2The a
GC
G
Fig. 1. X- ay di ac ion pa e ns o oxy luo ide glass (G) and glass–
ce amic (GC).
s uc u es wi h no long- ange o de , a e ound o he glass
(G), whe eas o he glass–ce amic (GC) he e a e also a
numbe o na ow and ela i ely in ense peaks ha e eals
he coexis ence o a c ys alline phase and a glassy phase.
F om he analysis o hese peaks, i has been concluded
ha his pa ially c ys allised sample con ains cubic luo-
ide c ys alli es o he ␤-PbF2phase (a=5.94Å) and using
he Sche e o mula an a e age size o he c ys als a ound
18nm has been ound.
The oom empe a u e abso p ion spec a o he 1mol%
P 3+-doped oxy luo ide glass and glass–ce amic ha e been
measu ed in he UV-Vis–IR ange (Fig. 2). These spec a
con i m ha he anspa ency o he glass–ce amic is qui e
simila o ha ound in he p ecu so glass since, apa om
hose bands associa ed o he P 3+ions, bo h samples show
he ypical inc ease in he abso bance in he UV-A egion.
The bands co espond o in a-con igu a ional 4 2–4 2elec-
400 500 600 1000 1500 2000 2500
0,3
0,4
0,5
0,6
0,7
25000 20000 10000 5000
3H6
3F2
3F3
3F4
1G4
1D2
3P0
3P1,1I6
3P2
G
GC
Op ical densi y
Wa eleng h (nm)
Ene gy (cm-1)
RT
1 mol% P 3+
Fig. 2. Abso p ion spec a o anspa en oxy luo ide glass (G) and
glass–ce amic (GC) doped wi h 1mol% o P 3+a RT. All ansi ions
s a om he 3H4g ound le el o he indica ed le els.
onic ansi ions, s a ing om he 3H4g ound s a e o he
di e en exci ed le els o he P 3+ion, and all he ansi ions
a e assumed o be elec ic dipole in na u e [13]. As can be
seen, he e a e p ac ically no di e ences in he ene gies o
he ansi ions in he glass and he glass–ce amic, al hough
o he la e he bands a e sha pe and some o hem, such
as 3H4→1D2and 3H4→3F3, clea ly show s uc u e, gi -
ing an expe imen al e idence ha he P 3+ions ha e been
inco po a ed in he luo ide nanoc ys als.
The s uc u al changes in which he P 3+ions a e in-
ol ed du ing he he mal ea men o he p ecu so glass
a e clea ly e lec ed in he alues o he oscilla o s eng hs
( exp) o he ansi ions co esponding o he abso p ion
bands in he glass–ce amic, ob ained using Eq. (1).As
shown in Table 1, excep o he 3H4→3P0 ansi ion, all
he oscilla o s eng hs inc ease a e he he mal ea men .
A ea u e al eady obse ed in anspa en glass–ce amics
doped wi h E 3+[15]. When wo peaks could no be sep-
a a ed only one oscilla o s eng h has been assigned o
bo h ansi ions, al hough a decon olu ion p ocess has been
pe o med in o de o calcula e he a eas o he 3H4→
3P0,1,2,1I6bands.
As poin ed ou by di e en au ho s [9,11,16], i is wo h
inc easing he numbe o expe imen al oscilla o s eng hs
in he i ing p ocess aking in o accoun hose ob ained
om he ansi ions obse ed in he P 3+luminescence. Fo
his pu pose, 0.1mol% P 3+-doped samples ha e been used
and he emission spec a o he 3P0le el in he glass and
glass–ce amic ha e been measu ed a 13K a e exci ing he
3H4→3P2 ansi ion a 440nm (Fig. 3). The low empe -
a u e condi ion a oids he he maliza ion e ec s ha could
allow he p esence o emission om he 3P1le el, al hough
he emission om he 1D2le el canno be igno ed. This
seems o be ue o he glass in which a con ibu ion can be
500 600 700
22000 20000 18000 16000 14000
In ensi y (a b. uni s)
Wa eleng h (nm)
13 K
0.1 mol% P 3+
G
3H5
1D2
3P0
3H4
3F3,3F4
3F2
3H6
3H5
3H4
GC
G
Ene gy (cm-1)
Fig. 3. Luminescence spec a om he 3P0le el in anspa en oxy luo ide
glass (G) and glass–ce amic (GC) doped wi h 0.1mol% o P 3+a e
exci ing a 440nm he 3H4→3P2 ansi ion a 13K. Emission om he
1D2le el in he glass a e exci ing a 580nm he 3H4→1D2 ansi ion
a 13K is also included o compa ison.
170 R.T. G´eno a e al./Jou nal o Alloys and Compounds 380 (2004) 167–172
Table 1
Expe imen al and calcula ed oscilla o s eng hs (×10−8) o he abso p ion and emission ansi ions o P 3+in anspa en oxy luo ide glass and
glass–ce amic. The calcula ed alues a e ob ained using he s anda d (J–O) and modi ied (K–K–D) Judd–O el heo ies [6,7,11]. The in ensi y pa ame e s
Ωλ(×10−20 cm2) and he ms (×10−6) alues a e also gi en
T ansi ions Glass Glass–ce amic
exp JO KKD,α ixed
(α=1×10−5) KKD,α a .
(α=2.2 ×10−5) exp JO KKD,α ixed
(α=1×10−5) KKD,α a .
(α=2.4 ×10−5)
Abso p ions
3H4→3H6,3F2336 339 283 173 345 369 311 164
3H4→3F3,3F4932 1198 1193 989 1023 1353 1356 1049
3H4→1G419 18 20 20 31 20 22 22
3H4→1D2214 127 161 218 277 144 184 263
3H4→3P0278 286 280 265 246 321 315 296
3H4→3P1,1I6505 426 449 481 633 479 505 551
3H4→3P21096 451 650 1014 1307 510 740 1247
Emissions
3P0→3H518 0 0 0 19 0 0 0
3P0→3H6112 103 164 279 112 117 187 348
3P0→3F238 22 39 52 16 −912 30
3P0→3F3,3F427 135 150 162 23 152 169 184
Ω20.13 0.21 0.25 −0.06 0.06 0.14
Ω44.09 3.94 3.65 4.60 4.42 4.05
Ω66.33 9.10 13.95 7.18 10.41 17.10
ms 2.53 1.92 1.10 3.18 2.48 1.36
The unce ain y o he measu ed oscilla o s eng hs is abou 5%. ms =( exp− calc)2
numbe o oscilla o s eng hs−numbe pa ame e s 1/2.
obse ed as a shoulde in he low-ene gy side o he 3P0→
3H6band and also as an isola ed band a ound 700nm co e-
sponding o he 1D2→3H5 ansi ion. Mo eo e , he p es-
ence o high-ene gy phonons, a ound 900cm−1, associa ed
o bonds wi h silicon and oxygen in he glass a ou s he
non- adia i e de-exci a ion om he 3P0le el o he 1D2
le el [4,5].
On he o he hand, he inco po a ion o he P 3+ions in
he cubic luo ide nanoc ys als a e he he mal ea men
gi es ise o a comple e di e en 3P0luminescence pa e n
compa ed o ha o he p ecu so glass. As can be obse ed
in Fig. 3, he 1D2emission seems o be less impo an in he
glass–ce amic due o a s uc u al-induced dec ease o he
mul iphonon de-exci a ion. This hypo hesis has been con-
i med using op ical spec oscopic echniques in his ma e-
ial bu doped wi h Eu3+ions. Analysing he ib onic bands
be o e and a e he he mal ea men , i has been ound
a ela i e dec ease o he elec on–phonon coupling o he
Eu3+ions wi h he high-ene gy phonons o he glass phase
and a ela i e inc ease o his coupling wi h he low-ene gy
phonons, a ound 300cm−1, o he luo ide nanoc ys als in
he glass–ce amic [4,5]. Mo eo e , his e ec may explain
he di e en expe imen al alues obse ed in he li e ime
o he 3P0le el, i.e. 19.6␮s in he glass and 26.4␮sin
he glass–ce amic, which gi es ise o di e en mul iphonon
de-exci a ion p obabili ies.
Conside ing he oscilla o s eng h o he 3H4→3P0ab-
so p ion ansi ion, he Eq. (4) and he a io o a eas o he
isible emission bands ela i e o ha o he 3P0→3H4
emission, he alues o he oscilla o s eng hs o he lumi-
nescence ansi ions om he 3P0le el ha e been ob ained
(see Table 1). The con ibu ion o he 1D2luminescence o
he band cen ed a 605nm band has been es ima ed aken
in o accoun he 1D2→3H5band a ea.
As a i s s ep in he heo e ical calcula ion, he in ensi y
pa ame e s Ωλha e been ob ained by i ing he expe imen-
al oscilla o s eng hs o all he ansi ions measu ed om
he abso p ion spec a. Applying he Judd–O el heo y o
he glass and he glass–ce amic, low and nega i e alues
o Ω2pa ame e ha e been ob ained, esul s ha do no
ha e any physical sense wi hin his heo y. The la ges dis-
co dance is ound o he 3H4→3P2 ansi ion, being his
one o he p oblems when he s anda d Judd–O el app ox-
ima ion is applied o P 3+[9]. Only he 3H4→3F2 an-
si ion has a signi ican dependency on ||U2||, and since
he 3H4→3P2 ansi ion has a ela i ely la ge oscilla o
s eng h and only depends on he ||U4|| and ||U6||,in
he i ing p ocess he la e ansi ion o ces la ge alues o
he Ω4and Ω6pa ame e s. I is usually ound in he li e a-
u e ha one o he abo e ansi ions has no been aken in o
accoun in he i ing p ocess.
On he o he hand, using he Ko nienko–Kaminskii–
Dunina ea men , his p oblem is comple ely sol ed when
αis allowed o a y in he i ing p ocess, being he ms al-
ues much lowe han applying he Judd–O el heo y. Using
he modi ied heo y, la ge posi i e alues o Ω2a e ob-
ained (12.29 o he glass and 19.44 o he glass–ce amic)
and he alues o Ω4a e simila in he glass and he
glass–ce amic o bo h heo ies. Conce ning he Ω6pa am-
e e , i is well known ha la ge alues ha e been usually
ound o P 3+ions [8] bu hey a e wo imes la ge using
he modi ied ea men compa ed o he Judd–O el heo y
R.T. G´eno a e al./Jou nal o Alloys and Compounds 380 (2004) 167–172 171
Table 2
Expe imen al and calcula ed spon aneous emission p obabili ies (s−1) and li e ime (␮s) o he 3P0le elo P
3+in anspa en oxy luo ide glass and
glass–ce amic. The calcula ed alues a e ob ained using he s anda d (J–O) and modi ied (K–K–D) Judd–O el heo ies [6,7,11]
T ansi ions Glass Glass–ce amic
Aexp AJO AKKD,α ixed
(α=1×10−5)AKKD,α a .
(α=2.2 ×10−5)Aexp AJO AKKD,α ixed
(α=1×10−5)AKKD,α a .
(α=2.4 ×10−5)
3P0→3H422077 22643 21783 20203 19536 25524 24567 22497
3P0→3H51436 0 0 0 1512 0 0 0
3P0→3H69526 7467 10732 16454 8940 8467 12247 20163
3P0→3F22979 543 866 1015 1260 −220 256 575
    
3P0→3F3,3F42145 0 0 0 1790 0 0 0
4796 4613 4279 5389 5187 4750
3P0→1G4– 821 790 733 – 917 883 808
3P0→1D2–01 1 – 00 0
Li e ime 3P0τexp τJO τKKD
(α=1×10−5)
τKKD
(α=2.2 ×10−5)
τexp τJO τKKD
(α=1×10−5)
τKKD
(α=2.4 ×10−5)
19.6 27.6 25.9 23.4 26.4 – 23.2 20.5
o bo h samples. Al hough posi i e alues o Ω2ha e
been ob ained i seems ha hey a e oo la ge i one ealises
he la ge deg ee o unce ain y in i s de e mina ion.
Some au ho s [9,11,16] ha e sugges ed ha he es ima ion
o Ω␭, and ␣, pa ame e s using only da a ob ained om he
op ical abso p ion spec um con ains la ge e o s. The e o e,
he s anda d and modi ied Judd–O el app oxima ions a e
applied bu using bo h abso p ion and emission da a. When
using he modi ied me hod he ␣pa ame e has been ixed o
he expec ed alue (α=1×10−5) o i has been allowed o
a y. Resul s a e gi en in Table 1. The bes imp o emen is
ha now a posi i e alue o Ω2is ob ained using bo h heo-
ies o he glass, al hough a nega i e alue is s ill ound ap-
plying he s anda d me hod o he glass–ce amic. Mo eo e ,
he alues o Ω2a e much lowe han hose ob ained by he
modi ied me hod analysing only he abso p ion da a. The
alues o Ω4a e simila o hose ob ained be o e aking in o
accoun only abso p ion da a, whe eas Ω6inc eases la gely
when he modi ied me hod is applied. In gene al, he ms de-
ia ion dec eases when he Ko nienko–Kaminskii–Dunina
ea men is applied, gi ing he bes ag eemen when he α
pa ame e a ies (see Table 1). In his sense, he ailu e o
he i o he oscilla o s eng h o he 3H4→3P2 ansi-
ion is again o e come. Howe e , i is wo h no ing ha ap-
plying bo h heo ies he ag eemen is no e y good o he
emission oscilla o s eng hs.
Table 2 lis s he expe imen al spon aneous emission p ob-
abili ies and hose calcula ed using he in ensi y pa ame e s
gi en in Table 1. The ailu e o bo h heo ies is e lec ed in
hese esul s since a poo ag eemen is ound, al hough he
expe imen al li e imes o he le el 3P0a e simila o hose
calcula ed using Eq. (5).
On he o he hand, Goldne and Auzel [17] ha e ques-
ioned he ac ha he ene gy o he 4 15d1con igu a ion
could be conside ed as a i ing pa ame e . The alues ob-
ained o he αpa ame e in he abo e analysis, a ound
2.3×10−5 o bo h samples, co espond o a 4 15d1ene gy
o a ound 22,000cm−1. This alue o he αpa ame e is
qui e simila o ha ound by Ko nienko e al. [11] al hough,
as i was al eady poin ed ou by hese au ho s, he expec ed
alue is 1 ×10−5. I is clea ha his alue is no compa i-
ble wi h he expe imen al esul s [18], bu i is necessa y in
o de o ob ain a good i [19]. This esul may be oughly
aken as an e idence o he g ea pe cen age o con igu a-
ion mixing in he wa e unc ions o he P 3+4 2con ig-
u a ion s a es, especially o high lying ene gy le els such
as 3P2.
Mo eo e , Auzel e al. [19] analysing E 3+-doped glasses
ha e emphasised ha he degene acy o he 2S+1LJle els
in ol ed in he op ical ansi ion has o be aken in a mo e
ealis ic way in o de o compa e calcula ed and expe imen-
al oscilla o s eng hs and calcula e quan um e iciencies.
In he Judd–O el heo y he degene acy o he g ound mul-
iple gi es ise o a weigh ing ac o , he (2J+1) ac o in
Eqs. (2) and (3), ha assumes ha all he S a k le els o he
g ound s a e a e equally popula ed [9]. As poin ed ou by
Auzel e al. [19], he silica glasses ha e a la ge maximum
S a k spli ing (a ound 700cm−1 o he 3H4mul iple in
his glass) compa ed wi h o he oxide and luo ide glasses,
hus his assump ion does no hold and an al e na i e s a-
is ical weigh ac o should be in oduced. Following he
me hod desc ibed by Auzel o E 3+-doped glasses [20,21]
bu analysing he 3P0→3H4emission o he P 3+ions in
hesesamples, i has been ound ane ec i eweigh ing ac o
[(2J+1)−1]e ∼
=1.12 (2J+1)−1 o he glass, and a lowe
co ec ion o he glass–ce amic. On he o he hand, i is
wo h no ing ha in glasses he e is a con inuous dis ibu ion
o local s uc u es o he lan hanide ions ha co e s om
weak o s ong c ys al- ields en i onmen s and, e en hough
o la ge S a k spli ing he Bol zman dis ibu ion gi es
ise o non-equally popula ed le els, he numbe o s ong
c ys al- ield en i onmen s is much less han he medium and
weak ones, o which mo e equally popula ions exis . How-
e e , i is also ue ha he la ge he (odd) c ys al- ield he
la ge he ansi ion p obabili y. As a conclusion, om hese
ac s and since he co ec ions a e wi hin he in e al o e o

172 R.T. G´eno a e al./Jou nal o Alloys and Compounds 380 (2004) 167–172
o he Judd–O el pa ame e s, hey ha e no been used in his
s udy.
Finally, i is wo h no ing ha aking in o accoun ab-
so p ion and emission da a he sequence Ω2<Ω
4<Ω
6
is held o e e y i ing p ocess, as ound in se e al hos s
[9]. Mo eo e , some empi ical co ela ions o he in ensi y
pa ame e and he local s uc u e o he lan hanide ions
ha e been s a ed [9]. As a gene al conclusion, he Ω2pa-
ame e inc eases wi h he asymme y o he local s uc u e
and wi h he deg ee o co alency o he lan hanide–ligand
bonds, whe eas he Ω6pa ame e dec eases wi h he deg ee
o co alency. The Ω4pa ame e is ela ed o bulk p ope -
ies o he samples [9]. Fo he ma ices in ol ed in his
s udy no clea conclusions can be ex ac ed om he Ω2
pa ame e , since i s la ge unce ain y, bu i s sligh dec ease
a e he he mal ea men o he p ecu so glass oge he
wi h he sligh inc ease o he Ω6pa ame e could be un-
de s ood as due o a change o he lan hanide local s uc u e
owa ds a mo e ionic en i onmen , as i is ound in luo ide
nanoc ys als.
5. Conclusions
Applying basic op ical spec oscopic echniques o
P 3+-doped oxy luo ide glass and glass–ce amic he ex-
pe imen al oscilla o s eng hs in abso p ion and emission
ha e been measu ed. The in ensi y pa ame e s ha e been
calcula ed by using bo h he s anda d Judd–O el heo y
and he modi ied heo y de eloped by Ko nienko, Kamin-
skii and Dunina. As a gene al conclusion, he modi ied
heo y gi es a be e ag eemen when he ene gy di e ence
be ween con igu a ions is allowed o a y, al hough he i
o he spon aneous emission p obabili ies is no e y good
when applying bo h heo ies. Mo eo e , he change in he
alues o he in ensi y pa ame e s om he glass o he
glass–ce amic seems o con i m ha he lan hanide ions a e
inco po a ed in he luo ide nanoc ys als a e he he mal
ea men .
Acknowledgemen s
The au ho s a e indeb ed o D . J.J. Rome o (Dp o. de
F´
ısica de Ma e iales, Uni . Au ónoma de Mad id) o p o-
iding he li e ime measu emen s. This esea ch has been
suppo ed by Minis e io de Ciencia y Tecnolog´
ıa (MAT
2001-3363).
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