JOURNAL OF RARE EARTHS, Vol. 30, No. 5, May 2012, P.

418

Effect of yttrium oxide addition on absorption and emission properties of

bismuth-doped silicate glasses
DAI Nengli (᠈㛑߽)1, WANG Yanshan (⥟ችቅ)1, XU Bing (ᕤ݉) 2, YANG Lüyun (ᴼᮙѥ)1, LUAN Huaixun (Ḓᗔ䆁)1,
LI Jinyan (ᴢ䖯ᓊ)1
(1. Wuhan National Laboratory for Optoelectronics, School of Optoelectronics Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074,
China; 2. Department of Ammunition and Missile, Wuhan Mechanical Technology College, Wuhan 430075, China)

Received 9 October 2011; revised 16 January 2012

Abstract: Y/Bi co-doped silicate glasses were prepared, and the effects of Y2O3 on the absorption and emission properties were investigated by
spectrum measurement. It was found that the absorption intensity in visible region decreases with increase of Y3+ concentration in (70–x)SiO2-
xY2O3-30CaO-1.5Bi2O3 (x=0 mol.%, 1 mol.%, 3 mol.%, 5 mol.%, 7 mol.%) glasses. The emissions centered at 410, 630, 1200 and 1290 nm
were observed under 280, 470, 514 and 808 nm excitation, respectively. The emission intensity had the similar change tendency in the visible
and near infrared region. We also discussed the actual role of Y3+ ions playing in the visible and near infrared emissions of the silicate glasses.
Keywords: bismuth; yttrium; broadband near infrared fluorescence; silicate glasses; rare earths

Owing to the rapid development of optical communica- enhanced by codoping with Y2O3[11]. Compared with ger-
tions, broadband amplifiers and tunable lasers in telecom- manate glass, silicate glass is appropriate matrix for bismuth
munication windows are indispensable for dense wavelength doping due to the compatibility with conventional low loss
division multiplexing (DWDM) network systems. Consid- silica fiber. Therefore, it will be interesting to study the ef-
erable efforts have been devoted to achieve broadband opti- fect of Y2O3 addition on spectroscopic properties of bis-
cal amplification in the past decades, which are mainly fo- muth-doped silicate glasses. In this work, Y/Bi co-doped
cused on the development of rare-earth ions (e.g. Er3+, Pr3+ silicate glasses were prepared, and the effects of Y2O3 addi-
and Tm3+) doped fiber amplifiers (RDFAs) and fiber Raman tion on absorption and emission properties of the Bis-
amplifiers (FRAs). However, the gain bandwidths of RDFAs muth-doped silicate glasses were investigated. The possible
are limited to ~80 nm due to the narrow f-f transitions, and role of Y3+ ions playing in the visible and near infrared lu-
FRAs have complicated system structures and high cost for minescence of bismuth-doped silicate glasses was finally
pump source. So people have been searching for novel mate- discussed.
rials with wide amplification bandwidth as the gain medium
of fiber amplifiers.
1 Experimental
In 2001, Fujimoto et al. reported the near infrared fluo-
rescence centered around 1.3 m with the full width at half The glass samples were prepared by the melting-quenching
maximum (FWHM) lager than 200 nm from bismuth-doped technique. The high-purity reagents CaCO3, SiO2, Bi2O3 and
silica glasses[1] and then realized 1.3 m optical amplifica- Y2O3 were selected as raw materials. The batch correspond-
tion under 800 nm excitation in 2003[2]. It provides us a can- ing to the composition of (70–x)SiO2-xY2O3-30CaO-1.5Bi2O3
didate for the realization of broadband fiber amplifiers and (x=0 mol.%, 1 mol.%, 3 mol.%, 5 mol.%, 7 mol.%, designated
tunable lasers in optical communication wavelength region. as Bi-xY2O3 glasses) was mixed homogeneously in an agate
Subsequently, relevant researches have been carried out on mortar. Then the batch melted at 1550 ºC in an alumina cruci-
various matrix of bismuth-doped glasses (silicate[3–5], phos- ble for 2 h. Consequently the melt was quickly cast onto a
phate[6], borate[7], germanate[8–10]). However, the origin of the stainless steel plate and annealed in an electric furnace at 550
near infrared emission centers is uncertain, and the depend- ºC for 1.5 h to release stress induced during the quenching
ence of its emission intensity on glass composition is not process. The prepared samples were cut into the size of 15
understood. mm×15 mm× 2 mm and polished for optical measurements.
It has been reported that the broadband near infrared emis- The absorption spectra in the wavelength range of
sion in bismuth-doped germanate glasses were remarkably 200–1100 nm were measured by PerkinElmer Lambda 35

Foundation item: Project supported by Science and Technology Project of Guangdong (2009A090100044), National High-Technology Research and Development
Program of China ("863"Program) (2011AA030201)
Corresponding author: LI Jinyan (E-mail: [email protected]; Tel.: +86-27-87559463)
DOI: 10.1016/S1002-0721(12)60064-7
DAI Nengli et al., Effect of yttrium oxide addition on absorption and emission properties of bismuth-doped silicate glasses 419

spectrophotometer. The fluorescence spectra in the range of

300–850 nm were measured by a Jasco FP-6500 fluores-
cence spectrophotometer. The fluorescence spectra in the
wavelength range of 800–1650 nm were measured on a
ZOLIX SBP300 spectrophotometer. The fluorescence life-
time measurements were carried out by exciting the samples
with a modulated 808 nm LD at 1300 nm. The signals de-
tected by a InGaAs photodetector in a TRIAX550 spectro-
fluorometer were recorded using a storage digital oscillo-
scope (Tektronix TDS3052). All the measurements were
carried out at room temperature in air.

2 Results and discussion Fig. 2 Fluorescence spectra of the Bi-xY2O3 (x=0 mol.%, 1 mol.%,
3 mol.%, 5 mol.%, 7 mol.%) glasses under 280 and 470 nm
2.1 Absorption spectra excitation, respectively
Fig. 1 presents the absorption spectra of the Bi-xY2O3
glasses, which shows an intensive absorption peak at 470 nm well known that there are various valence states of Bi ions in
and a peak at 750 nm. The peak position of the absorption glass. The fluorescence of Bi3+- and Bi2+-doped crystals and
band around 470 nm shifts from 460 to 479 nm, and the ab- glasses have been investigated in the past decades. In gener-
sorption intensity at the peak wavelength decreases with ally, the excitation peaks of Bi3+ in crystals and glasses can
Y2O3 concentration increased from 0 mol.% to 7 mol.%, be observed in the ultraviolet region and the fluorescence
which shows that Y3+ ions have an obvious effect on the ab- peaks occurs in the ultraviolet, green or red wavelength re-
sorption of Bi-related ions in silicate glasses. For the gion[13–15]. Therefore, the emission around 410 nm is the
Bi-xY2O3 glasses, the increased Y2O3 content can lead to the typical fluorescence of Bi3+ ions. The emission around 630 nm
change of glass optical basicity, which possibly induces the should be ascribed to the electron transition of Bi2+ ions, be-
decreasing of Bi absorption related centers. It also can be cause the absorption band centered at about 470 nm and the
observed from the inset of Fig. 1 that the colors of the glass red luminescence from the glasses are similar with the ab-
samples change gradually from reddish-brown to light color sorption and luminescence from Bi2+ activated centers in
with increased Y2O3 content. There is no obvious absorption crystals[16].
peak in 800–1100 nm wavelength region, which is similar From the above analysis, although we introduced Bi2O3 as
with other bismuth-doped silicate glasses. The strong ab- the original materials in our experiment, there are Bi3+ and
sorption below 350 nm is considered to be the absorption Bi2+ in the Bi-xY2O3 glass samples. Since the high glass
edge of the Bi2O3-containing glasses in our experiment[12]. melting temperature (1550 ºC) can lead Bi2O3 dissociating
into lower valence Bi ions including Bi2+, Bi+ or even Bi, the
2.2 Emission spectra in the visible region absorption intensity decreases with increasing Y2O3 content
The emission property under ultraviolet and visible band (seen in Fig. 1), which indicates that higher Y3+ ion concen-
excitation is helpful for exploring the fluorescence center tration in bismuth-doped silicate glasses prohibits the forma-
and energy level of Bi ions in glasses. Fig. 2 shows the typi- tion of lower valence Bi ions.
cal emission spectra at 410 and 630 nm of the Bi-xY2O3 2.3 Emission spectra in the near infrared region
glasses under 280 and 470 nm excitation, respectively. It is
Fig. 3 shows the fluorescence spectra of the Bi-xY2O3
glasses under 514 nm excitation. The near infrared lumines-
cence centered at 1200 nm covering the wavelength range
from 1000 to 1600 nm is observed. The near infrared fluo-
rescence spectra excited by low cost commercial laser diode
(LD) is especially important for analyzing the potential am-
plification and laser properties of bismuth-doped glasses and
fibers. Fig. 4 presents the fluorescence of the Bi-xY2O3
glasses excited by 808 nm LD, which shows obvious
blue-shift from ~1200 to ~1290 nm compared with the fluo-
rescence spectra of the same sample under 514 nm excita-
tion.
As we all know, 808 nm LD is popular and low cost
Fig. 1 Absorption spectra of the Bi-xY2O3 (x=0 mol.%, 1 mol.%, source for fiber amplifiers and fiber lasers, the dependence
3 mol.%, 5 mol.%, 7 mol.%) glasses (The inset shows the of the emission intensity and the full width at half maximum
photographies of the glass samples)
420 JOURNAL OF RARE EARTHS, Vol. 30, No. 5, May 2012

Fig. 5 The dependence of the fluorescence intensity and the full width
Fig. 3 Fluorescence spectra of the Bi-xY2O3 (x=0 mol.%, 1 mol.%,
at half maximum (FWHM) on Y2O3 concentration in the
3 mol.%, 5 mol.%, 7 mol.%) glasses under 514 nm excitation
Bi-xY2O3 (x=0 mol.%, 1 mol.%, 3 mol.%, 5 mol.%, 7 mol.%)
glasses

Fig. 4 Fluorescence spectra of the Bi-xY2O3 (x=0 mol.%, 1 mol.%,

3 mol.%, 5 mol.%, 7 mol.%) glasses excited by 808 nm LD Fig. 6 Fluorescence decay curves of the Bi-xY2O3 (x= 0 mol.%,
3 mol.%, 7 mol.%) glasses pumped by 808 nm LD measured
(FWHM) on the Y2O3 concentration in the Bi-xY2O3 glasses by monitoring 1290 nm emission at room temperature
under 808 nm LD excitation is shown in Fig. 4. The FWHM
is in the range of 170–195 nm for various Y2O3 contents. On emission centers) and decrease the non-radiation transitions
the other hand, the near infrared emission intensity is a little between Bin+ ions. Based on the above analysis, we suggest
enhanced as x<3 mol.%. While x>5 mol.%, the emission in- that Y3+ ions play dispersing role in the visible and near in-
tensity decreases rapidly. Since the radius of Y (RY=0.18 nm) frared emission centers in Y/Bi co-doped silicate glasses.
matches that of Bi ions (RBi=0.16 nm), the Y3+ ions will sur- Furthermore, Y3+ ions might be related to the formation of
round the Bi-related centers and enlarge the center-to-center near infrared emission centers in bismuth-doped silicate
spacing in the bonding association of Si–O–Bi. Conse- glasses. But further investigations are necessary to clarify the
quently, the interaction between these emission centers will mechanism of the infrared luminescence observed in bis-
be weakened and the energy loss due to concentration muth-doped silicate glasses.
quenching will be reduced. Therefore, the emission intensity
both in the visible region and in the near infrared region is
3 Conclusions
enhanced when the Y2O3 concentration is as low as x<3
mol.%. However, the emission intensity both in the visible The analysis of absorption and emission properties al-
region and in the near infrared region decreases rapidly as lowed us to draw a conclusion that the Y3+ ions played a dis-
x>5 mol.%. This may occur because the absorption intensity persing role in the visible and infrared emission centers in
decreased with the increased Y2O3 concentration in Y/Bi co-doped glasses. Since the absorption intensity of Bi
400–1100 nm region. In fact, the absorption intensity at 514 ions in visible region decreased with increased Y2O3 content,
and 808 nm as x=7 mol.% is about half of that as x=3 mol.%. Y3+ ions might be related to the formation of near infrared
We measured the fluorescence decay curve at 1290 nm emission centers in bismuth-doped silicate glasses. The Y-Bi
excited by 808 nm LD at room temperature (seen in Fig. 6). co-doped silicate glass might be very useful for broadband
The estimated fluorescence lifetime is 443, 455 and 479 s fiber amplifiers and widely tunable lasers.
when x=0 mol.%, 3 mol.%, 7 mol.%, respectively. This in-
crement of fluorescence lifetime indicates that the addition
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DAI Nengli et al., Effect of yttrium oxide addition on absorption and emission properties of bismuth-doped silicate glasses 421

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