Ceramics International 48 (2022) 8502–8508

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Mid infrared fluorescence characteristics and application of Co2+:ZnS

doped chalcogenide glass-ceramics
Yiming Gui a, b, Xusheng Zhang a, b, Kelun Xia c, Haotian Gan a, b, Lelu He a, b, Yongnian Guan a, b,
Zijun Liu a, b, c, *, Zhiyong Yang d, Xunsi Wang a, b, Shixun Dai a, b, Xiang Shen a, b, c
a
Laboratory of Infrared Materials and Devices, Advanced Technology Research Institute, Ningbo University, Ningbo, 315211, China
b
Key Laboratory of Photoelectric Detection Materials and Devices of Zhejiang Province, Ningbo University, Ningbo, 315211, China
c
Ningbo Institute of Oceanography, Ningbo, 315832, China
d
Hangzhou Institute of Optics and Fine Mechanics, Hangzhou, Zhejiang, 311421, China

A R T I C L E I N F O A B S T R A C T

Keywords: A Co2+:ZnS-doped chalcogenide glass with broadband mid-infrared emission was prepared by using a hot uni­
Glass-ceramics axial pressing process. The refractive index difference (Δn) between matrix glass (As2S5) and crystal (Co2+:ZnS)
Hot-pressing was controlled to be 0.0042 in the emission spectral range of Co2+ to minimize the scattering effect. An ultra­
Mid-infrared fluorescence
broadband mid-infrared emission of 2–4 μm was observed at room temperature in the samples after excitation by
Gas-sensing
using a commercially available laser diode of 1550 nm. The significant changes in the lifetime and fluorescence
intensity of Co2+:ZnS-doped chalcogenide glass were measured in the temperature range of 90–290 K. A reso­
lution of approximately 0.18 K was observed when used as a temperature detector. Furthermore, a gas-sensing
device was built by using the strong and broad emissions of the sample, and the detection sensitivity of butane
reached 56 ppm. These results show that this glass-ceramics can be used as optical sensing of gas and
temperature.

1. Introduction
The mid-infrared (MIR) band includes many baseband absorptions of
gas molecules, especially the 2–5 μm range covering the molecular
fingerprint region. Therefore, MIR incoherent and coherent light sources
are highly desirable in several fields such as national defense, medical
treatment, environmental monitoring, and gas-sensing [1,2]. In partic­
ular, most polluting gases in the atmosphere have vibrational absorption
in the infrared region (e.g.., CH4: ~3.3 μm, H2S: ~2.7 μm, and NH3:
~2.3 μm) [3–5]. However, the mainstream laser is mainly doped with
rare-earth ions, and its emission wavelength is a separated narrow peak,
which cannot cover the molecular fingerprint region. Therefore, the
development of 2–5 μm sources is significant.
In the last decades, II-VI crystals (e.g., ZnS and ZnSe) doped with
transition metal ions (TM2+) (such as Co2+ [6], Cr2+ [7], and Fe2+ [8])
have emerged as excellent MIR gain media, owing to their numerous
advantages such as stable mechanical properties, ultrabroadband
emission spectrum, and large stimulated emission cross-section [6].
Moreover, the solid-state laser with Cr2+-doped II-IV crystals as the core
can achieve continuous MIR laser output [9]. Moreover, Fe2+-doped
II-IV crystals achieves a tunable laser output at low temperatures [10].
Compared with those of Cr- and Fe-doped II-IV crystals, the emission
band (2–4 μm) of Co2+:II-IV crystals coincides with the strong absorp­
tion bands of hydrocarbons and other organic molecules, this is signif­
icant in gas-sensing.
TM2+:II-VI crystals have good optical properties, but cannot be
extended and stretched because of the physical properties thereby
limiting their application. Chalcogenide glass has excellent drawing
performance, a wide infrared transmission range, and low phonon en­
ergy, making it a promising candidate for MIR lasering [11]. Chalco­
genide glasses doped with TM2+:II-VI crystals provide the advantages of
the fiber-forming ability of glasses and the high emission efficiency of
active crystals. In addition, the fiber structure has a large specific surface
area, which improves the heat dissipation efficiency and reduces the
thermal lens effect of the crystal. Therefore, TM2+:II-VI doped chalco­
genide glass-ceramic is effective for fabricating stretchable fluorescence
materials.
The research on the preparation of glass-ceramics mainly focuses on

* Corresponding author. Laboratory of Infrared Materials and Devices, Advanced Technology Research Institute, Ningbo University, Ningbo, 315211, China.
E-mail address: liuzijun@nbu.edu.cn (Z. Liu).

https://doi.org/10.1016/j.ceramint.2021.12.060
Received 15 October 2021; Received in revised form 23 November 2021; Accepted 6 December 2021
Available online 11 December 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Y. Gui et al.
Fig. 1. Schematic diagram of the preparation process.
the low-temperature melting of mixed crystal and glass [12,13], heat
treatment crystallization [14], and hot uniaxial pressing [15,16]. In the
first method, the stability of TM2+ in its divalent state and the integrity
and insolubility of the crystal at high temperatures are difficult to
maintain. Furthermore, the refractive index of the crystal phase
precipitated by heat treatment is different from that of the remaining
glass phase. Hot uniaxial pressing can eliminate internal pores at low
temperatures and high pressures for obtaining high densification glass
materials. Low-temperature sintering does not change the valence state
of TM2+ and the shape of crystals. Moreover, the hot-pressing method
can freely select glass matrixes to make the refractive index of the
glass-ceramics similar to that of the crystal [17]. This characteristic is
important for the infrared transmission of glass-ceramics. According to
the Rayleigh scattering model, the transmittance of glass-ceramics is
dependent on the following factors [18]:
( 2 )
− 32mLπ 4 n4 a3
n − n20
(1)
4
T = e− εL = e ρλ0 2
, MIR data were acquired by using a Fourier-transform infrared spec­
n2 + 2n0
where ε is the scattering loss, L is the optical path, m is the total mass of
the crystal, ρ is the packing density of the crystal in the glass, and a is the
radius of the crystal. n0 and n are the refractive index of the matrix glass
and the crystal, respectively. λ0 is the wavelength of light in the vacuum.
As expressed by the formula, the scattering is very sensitive to the size of
particles and the refractive index difference(Δn). Therefore, a low Δn
and a small grain size are required [17]. Micron crystals have been re­
ported to exist in highly transparent glass-ceramics, if the refractive
index difference between crystal and glass is lower than 0.01 [19,20]. A
suitable glass component must be determined to minimize Δn as much
as possible, with the matching region being larger than the luminous
region of Co2+.
In this study, Co2+:ZnS crystals were prepared by employing a
thermal diffusion process [1,5]. Then, As2S5 chalcogenide glass was
selected as the matrix for doping and hot-pressing Co2+: ZnS crystals,
and finally, MIR transparent glass-ceramics were prepared. The optical
properties, low-temperature fluorescence and decay of the
glass-ceramics were studied. Furthermore, the temperature and
gas-sensing properties were analyzed.
2. Experiments
Co2+: ZnS crystals were prepared by applying a thermal diffusion
technique. The dopant CoS (powder, 99.5%) and the host ZnS (tablets,
8.3 mm × 8.3 mm) were placed separately at both ends of the high
vacuum (~10− 5 Torr) quartz tube, ensuring that the dopant was trans­
ported to the reaction site of ZnS in a vapor state. The sealed sample was
placed in a tube furnace and the temperature near the doping source was
slightly higher than that in the crystal end. The sample was held at a high
temperature for 40 h and then cooled to room temperature (RT,
approximately 25 ◦ C) within 9 h. Finally, the doped crystal was ground
grinding and polished.
The As2S5 glass was prepared by sealing the raw material in a vac­
uum quartz tube, and placing it in a shaking furnace at 600 ◦ C for 12 h.
Then, the melt was quenched in water and annealed near the glass
transition temperature to reduce the internal stresses. Co2+:ZnS crystal
and As2S5 glass were grinding and mixed for 2–3 h in a grinding bowl.
Then, the powder was introduced into a custom mold and compacted
with a pressure bar. The sample was then heated to 230 ◦ C with a
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Ceramics International 48 (2022) 8502–8508
Fig. 2. XRD pattern of Co2+:ZnS crystals prepared by using the thermal diffu­
sion method.
pressure of 30 MPa. And it was cooled naturally to room temperature
and taken it out of the mold (The schematic diagram of the preparation
process is shown in Fig. 1).
The patterns of X-ray diffraction (XRD) were examined by using a
Bruker D2 X-ray diffractometer. The near-infrared absorption spectrum
was measured by using Perkin-Elmer Lambda-950 spectrophotometer.
trometer. The characteristic glass temperatures, including transition
temperature (Tg), were determined by employing differential scanning
calorimetry (DSC- Q2000, TA, USA) within the measured temperature
range of 0–400 ◦ C and the temperature accuracy was ±1 ◦ C. Infrared
variable angle spectroscopic ellipsometry (IR-VASE Mark II, J. A.
Woollam) was used to measure the linear refractive indices, in which the
angles of incidence were 65◦ and 75◦ . Furthermore, the refractive index
curve of the sample was fitted by using the Sellmeier formula. The
morphology, distribution, and element-mapping images of the micro­
crystals in the glass-ceramics were recorded by applying scanning
electron microscopy (SEM, SU-70, Hitachi). The MIR fluorescence and
attenuation spectra were recorded on a fluorescence spectrometer,
(Edinburgh FLS980, UK) the pump source was a 1550 nm solid-state
laser with a power of 1W.
3. Results and discussion
3.1. Co2+: ZnS crystal properties
Fig. 2 shows the XRD patterns of the Co2+:ZnS crystals prepared by
using thermal diffusion. The diffraction peaks are consistent with those
in the card (PDF #65–9585), indicating that the ZnS crystal remains in
its cubic phase even after Co2+ thermal diffusion. This crystal structure
of ZnS guarantees strong MIR luminescence of Co2+. Moreover, these
cubic crystals have no birefringence effect, and the uniform refractive
index reduces the scattering loss [21].
To calculate the Co2+ doping concentration, the optical density (OD)
of three samples was tested, as shown in Fig. 3(a). The relationship
between the OD and the absorption coefficient (α) of the crystal can be
expressed as [22].
I0
OD(λ) = 1g = αL × 1g e, (2)
I
where OD is the optical density, L is the thickness of the crystal (in cm),
and α is the absorption coefficient of the crystal. Samples Co1, Co2, and
Co3 are shown in the insert of Fig. 3(b), their thicknesses are 1.29 mm,
1.43 mm, and 1.49 mm, respectively, and the calculated concentrations
are 0.24 × 1019 cm− 3, 0.23 × 1019 cm− 3 and 0.42 × 1019 cm− 3,
respectively. All three samples have good MIR transmittance as shown in
Fig. 3(b). Co3 has a slightly lower transmittance owing to lattice defects
Y. Gui et al. Ceramics International 48 (2022) 8502–8508

Fig. 3. Absorption spectra (a), transmission spectra (b) and MIR fluorescence (c) of Co2+:ZnS with different doping concentrations. The inset in (c) is energy dia­
grams and energy transfer channels of Co2+ in ZnS crystals. (d) is the decay spectrum of Co3 monitored at 3030 nm.

Fig. 4. (a) Refractive index spectra of glasses (As–S and Ge-As-S systems) and crystal ZnS. (b) Relationship between crystal size and Rayleigh loss of samples with
different doping concentrations and fixed Δn.

caused by a high doping concentration. of 3030 nm. Then, the test results were fitted by using the following
The energy level structures of Co2+ in the tetrahedral crystal field are formula [25,26]:
depicted in Fig. 3(c). Energy level splitting occurs in the outermost ∫∞ /∫ ∞
d orbital (3d74 S2) of Co2+, and the ground state 4F splitting can be τ= I(t)tdt I(t)dt, (3)
divided into three energy levels: 4T1, 4T2, and 4A2 [23]. A strong ab­ t0 t0

sorption is observed at approximately 1500 nm, corresponding to the

4 where I(t) is the function of luminous intensity with time t. The calcu­
A2→4T1(F) transition, which a conventional laser can pump [24]. The
lated lifetime is approximately 0.17 ms, which is consistent with that
intense emission peaks at approximately 3 μm corresponding to the
4 reported in the literature [27].
T2(F)→4A2 level transition. The emission spectra covering 2200–4200
nm were measured at RT, as shown in Fig. 3(c). We selected the Co3
sample with the most vigorous luminescence intensity to test the decay

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Fig. 5. XRD patterns (a), infrared transmission spectra (b), fluorescence spectra(c) and decay curve of samples with different Co2+:ZnS doping content. The inset
shows the near-infrared photograph of the sample doped with 5 wt% Co2+:ZnS.

3.2. Properties of glass-ceramics
The light scattering directly affects the infrared transmittance and
limits the application of glass-ceramics. A shown in equation (1), the
bigger the grain size and Δn, the larger is the of Rayleigh scattering. The
calculation results were shown in Fig. 4(b). Therefore, we studied the
changing trends of As–S and Ge-As-S systems. Both systems can achieve
a refractive index within the working band. As As2S5 (Tg = 142 ◦ C) has a
lower transition temperature than Ge35As10S55 (Tg = 368 ◦ C), it is easier
to achieve hot-pressing densification. Finally, the As2S5 component was
selected as the doping matrix, and an Δn of 0.0042 was obtained as
shown in Fig. 4(a).
The XRD patterns of the samples were tested and the results are
shown in Fig. 5(a). It can be seen that the doped ZnS crystal in hot-
pressed glass-ceramics exhibits a typical cubic phase without addi­
tional miscellaneous peaks. Therefore, the hot-pressing process does not
lead to the crystallization of the matrix glass and change the crystal
structure. The diffraction peak intensity increases significantly with an
increase of in the doped crystal content, indicating that the crystallinity
increases. In addition, we calculated the average grain size as to be 165
nm by using the Scherrer Equation [28].
The MIR transmittance spectra of hot-pressed samples are shown in
Fig. 5(b). The maximum transmittance of the undoped glass samples is
very close to the level of molten glass (approximately 65%), indicating
that the hot-pressing process can suitably maintain the infrared trans­
mittance of chalcogenide glasses. The transmittance of 1 wt% doped

Fig. 6. High-magnification SEM image (a) and element-mapping images of Zn (b), As (c), S (d) and Co(e).

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Fig. 7. Emission spectra of 5 wt% Co2+:ZnS doped glass-ceramic under variable temperature (a) and variable temperature decay curves (b).

samples can also be maintained above 55%. However, the scattering

effect becomes evident with the increase in the doping concentration,
especially in the short band (2–5 μm), where the transmittance decreases
significantly with an increase in the Co2+:ZnS crystal concentration
owing to the scattering caused by large crystal particles. As observed in
the SEM images in the inset of Fig. 6(a), some micron-sized particles are
still responsible for the scattering loss. The strongest absorption peak is
located at 2.9 μm, 4 μm, and 6.3 μm, which can be attributed to the
impurity absorption of OH-, S–H, and H2O [29]. As the absorption peak
of samples does not increase significantly with different doping con­
centrations, it is considered that these impurities contribute to As2S5.
Therefore, the absorption peak can be removed by purifying the raw
materials.
The MIR fluorescence spectra of samples with different doping con­
centrations are shown in Fig. 5(c). All the samples have prominent Co2+
characteristic luminescence peaks. As the concentration of doped Co2+:
ZnS crystals increases, the fluorescence intensity increases with no sig­
Fig. 8. Relationship between signal intensity difference and temperature. The
nificant shift in the peak position. Fig. 5(d) shows the decay of the 5 wt% inset shows the basic noise.
Co2+:ZnS doped glass-ceramic monitored at 3030 nm. The fitting life of
the crystal in the glass-ceramic is 0.19 ms, and there is no essential
signal-to-noise ratio (SNR), SNR is defined as “signal amplitude/noise
change in the life of the pure crystal (0.17 ms).
standard deviation” [30,31]. The detector’s noise is shown in the inset of
The morphology and the distribution of Co2+:ZnS in the glass-
Fig. 8, and the standard deviation is 3.571. The calculation formula for
ceramics were characterized by employing high-resolution SEM and
sensitivity S is
energy dispersive X-ray spectroscopy. As shown in Fig. 6, the distribu­
tion of the elements in the glass-ceramic is observed intuitively through 1
S = σT/I = σ × , (4)
the element mapping image. The distribution of Zn and S is consistent k
with the crystal shape, and the crystal contour, respectively. However,
no distinct color pattern is observed for Co owing to the low Co2+ where T is the temperature, I is the change of signal strength, σ is the
concentration. noise standard deviation and K is the intensity slope. The calculated
sensitivity of the system is 0.18k, which is close to the sensitivity of the
rare-earth doped organic framework fluorescence temperature sensor
3.3. Sensing application of glass-ceramic [32].
Fig. 7 (b) shows the decay of the sample at different temperatures,
A low-temperature environment will weaken the non-radiative reaching 0.57 ms at 90 K. The multiphonon relaxation increases slowly
multiphonon relaxation and improve the luminescence efficiency. as the temperature increases. When the temperature exceeds 200 K, the
Thus, we studied the temperature-dependent luminescence character­ multiphonon relaxation rate increases rapidly, resulting in a significant
istics of the sample. The variable temperature spectra of 5 wt% Co2+: decrease in the lifetime, as shown in inset of Fig. 7 (b), this is consistent
ZnS-doped As2S5 samples, ranging from 90 K to 290 K, prepared by using with the variation in fluorescence intensity presented in Fig. 7 (a).
a liquid nitrogen refrigeration system, were measured and are shown in Therefore, the decay time can be used to calibrate the results of fluo­
Fig. 7(a). It can be seen that the fluorescence intensity increases rescence temperature sensing. For example, it can establish a compa­
significantly as the temperature decreases. Therefore, different tem­ rable database to improve the reliability of the detection system.
peratures can be measured by monitoring the fluorescence intensity. The To fully utilize the spectrum covering 2–4 μm, we choose butane
fluorescence temperature sensor belongs to a non-contact temperature (C4H10) as the detected gas and explore the detection ability of the
measurement technology, it has a high reaction speed and can detect the system using 5 wt% Co2+:ZnS doped glass-ceramic as a MIR light source.
temperature change in small objects [28]. Detection sensitivity is an C4H10 is an alkane whose intrinsic absorption peak of the C–H bond is at
important parameter for measuring the performance of a sensing system. 3.3 μm. As shown in Fig. 9, both ends of the detection device are sealed
System sensitivity is defined as the ratio of the concentration to the

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Fig. 9. Schematic diagram of a gas-sensing device.
Fig. 10. Fluorescence spectra with and without filling C4H10 gas (a) and fluorescence intensity change at 3380 nm with different C4H10 concentrations (b).
Fig. 11. Relationship between signal intensity difference and gas concentra­
tion. The insert shows the basic noise.
with CaF2 windows to form an absorption cell. The doped glass-ceramic
is fixed at one end of the absorption cell as a MIR light source, and the
other end is fixed with an InSb detector to detect the change in fluo­
rescence intensity. The gas to be measured flows through the gas input
and output ports. The volume of the gas chamber is fixed, and we can
control the concentration by accurately controlling the filled volume of
butane.
The fluorescence spectra in a vacuum and pure-C4H10-filled state
were measured and normalized, as shown in Fig. 10(a). Two prominent
absorption peaks are observed at 3380 nm and 3150 nm; 3380 nm is the
absorption peak of C4H10, and 3150 nm is the absorption peak of the
additional gas in butane.To facilitate the detection of gas leakage, an
odorant is usually added to the commercialized gas tank. Thus, we infer
that the absorption peak at 3150 nm belongs to the artificially added
impurity gas in the butane gas tank.
According to the transformation of Lambert–Beer law, the expression
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of gas concentration C is [22].
ln(I0 /I)
C= , (5)
α(λ)L
where I0 is the initial incident light intensity, α(λ) represents the ab­
sorption coefficient, and L is 40 cm representing the interaction distance
between light and gas. A different concentration of C4H10 gas was filled
into the absorption cell, and the corresponding emission intensity was
recorded as shown in Fig. 10(b). Based on equation (4) and Fig. 11, the
noise standard deviation of the detector is calculated to be 8.537, and
the sensitivity of the system reaches 56 ppm. The wavelength we used in
the gas sensing experiment (approximately 3300 nm) is different from
that used in the temperature sensing experiment (approximately 2900
nm). And the detector has large noise at the long wavelength, so the
signal standard deviation is different. Compared with relevant studies
[33], the sensitivity is significantly improved. The detection sensitivity
can be further improved by increasing the SNR of the detector and
prolonging the interaction distance between light and gas.
4. Conclusion
Co2+:ZnS-doped As2S5 glass-ceramics with exhibiting both the
ductility of glass and the excellent luminescence of crystals, properties
were prepared by using the hot-uniaxial pressing process. The prepared
samples exhibited good infrared transmittance owing to the well-
matched refractive index between crystal and glass. The results of MIR
emissions and XRD showed that the emission peaks and XRD peaks of
the crystal did not change after hot-pressing, indicating that the process
did not affect the crystal structure. The emission intensity and decay of
the samples varied with temperature, indicating that they can be used to
characterize the temperature change. Furthermore, we built a gas de­
tector with a detection sensitivity of 56 ppm to C4H10. Therefore, the
infrared transmittance and fluorescence intensity of the sample can be
further improved to rended it as a potential candidate for a MIR light
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source.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This study was supported by the National Natural Science Founda­
tion of China (61975086 and 61605095), the Zhejiang Provincial Nat­
ural Science Foundation of China (LY19F050004), Key Research and
Development Program of Zhejiang Province (2021C01025), and the K.
C. Wong Magna Fund at Ningbo University.
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