Fluoroindate Glass Co-Doped with Yb³⁺/Ho³⁺ as a 2.85 μm Luminescent Source for MID-IR Sensing

Abstract

This work reports on the fabrication and analysis of near-infrared and mid-infrared luminescence spectra and their decays in fluoroindate glasses co-doped with Yb³⁺/Ho³⁺. The attention has been paid to the analysis of the Yb³⁺ → Ho³⁺ energy transfer processed ions in fluoroindate glasses pumped by 976 nm laser diode. The most effective sensitization for 2 μm luminescence has been obtained in glass co-doped with 0.8YbF₃/1.6HoF₃. Further study in the mid-infrared spectral range (2.85 μm) showed that the maximum emission intensity has been obtained in fluoroindate glass co-doped with 0.1YbF₃/1.4HoF₃. The obtained efficiency of Yb³⁺ → Ho³⁺ energy transfer was calculated to be up to 61% (0.8YbF₃/1.6HoF₃), which confirms the possibility of obtaining an efficient glass or glass fiber infrared source for a MID-infrared (MID-IR) sensing application.

1. Introduction

The MID-infrared (MID-IR) optical sources operating in the 3 μm spectral range have attracted major attention due to their wide field of applications in the medical field, the military, and especially in remote sensing applications [1,2,3,4,5,6,7,8]. The MID-IR differential absorption lidar (DIAL) systems can be used for the construction of novel optical sensors of atmospheric chemistry. The Decadal Survey recommended missions to measure atmospheric constituents including CO₂, CH₄, CO, O₃, NO₂, SO₂, and CH₂O [9]. The atmospheric components noted above have unique and useful characteristic absorption features in the mid-infrared which enable their detection by using optical spectroscopy [10]. Moreover, ~3 μm lasers can be used as the pumping source of optical parametric oscillation (OPO) [11]. Two approaches have been widely investigated: bulk material lasers and fiber-based lasers [12]. Among low-phonon glasses, the fluoroindate glasses are very useful MID-IR photonic materials. Their properties like a wide transmission range (UV—10 μm), low phonon energy (c.a. 510 cm⁻¹) acceptance of high concentration of rare-earth (RE) ions, and thermal stability which enables their fiberization, make them an attractive laser glass for optical fiber fabrication [13,14,15,16]. The main advantages of fluoroindate glasses with respect to the commonly known ZBLAN glasses are lower phonon energy, better thermal stability, and an extended IR absorption edge. Moreover, in comparison to the fluoro-zirconium and chalcogenide materials, it should be stated that fluoroindium glasses have better mechanical properties and resistance to chemical corrosion [17,18,19]. Besides, their nonlinear properties have been used in construction supercontinuum fiber sources operating up to 5.4 μm [20].

In the case of CO₂ detection (2.7–3 μm absorption band), the Ho³⁺-doped fluoroindate glass (⁵I₆ → ⁵I₇ transition) is a promising candidate as a luminescent source of radiation and can be an alternative to semiconductor laser diodes [21]. Spectroscopic properties of the singly Ho³⁺-doped fluoroindate glasses in MID-IR spectral range have been reported before [22]. It should be noted that infrared luminescence studies of RE-co-doped fluoroindate glasses are practically limited to the Er³⁺/Tm³⁺ Er³⁺/Yb³⁺, Tm³⁺/Ho³⁺, and Er³⁺/Ho³⁺ [23,24,25,26].

It is well known that obtaining 2.85 μm efficient emissions from holmium is limited by two problems: the relatively short lifetime of the ⁵I₆ level and the lack of suitable absorption bands matching with the current high power laser diode [27]. The first can be solved by using Pr³⁺ ions as a depopulator to quench the lower level of Ho³⁺: ⁵I₇. The second problem can be solved through sensitization of the Ho³⁺ by Er³⁺ or Yb³⁺ ions and through obtaining luminescence by Yb³⁺, Er³⁺ → Ho³⁺ energy transfer [26,28,29,30,31].

In this paper, the effect of sensitization of holmium by Yb³⁺ ions on the near and mid-infrared emission properties is presented. Having in mind the practical application in MID-IR CO₂ sensors, detailed analyses of the energy transfer mechanisms and RE-co-dopant optimization under commonly used 976 nm laser diode pumping have been performed. To the best of the authors’ knowledge, the emissions and energy transfer properties of the Yb³⁺/Ho³⁺ co-doped fluoroindate glasses have not been investigated before.

2. Materials and Methods

The investigated fluoroindate glasses have the following molar composition (38-x-y)InF₃-20ZnF₂-20SrF₂-16BaF₂-4GaF₃-2LaF₃-xYbF₃–yHoF₃, (x = 0.8; y = 0−1.6). The glass samples were prepared with high purity (99.99%) reagents. After homogenization of the components, 5 g glass bathes were placed in a covered platinum crucible. The 5 g glass sample is only enough for spectroscopic measurements. We are aware of the requirements for the fabrication of cylindrical or planar optical fibers (in bulk or fiber optics)—a larger number of glasses (20 g) are needed. Despite this, an exothermic (crystallization) peak at the 395 °C ΔT parameter (ΔT = Tx − Tg = 88 °C) confirmed the high thermal stability of the glass, which allows for using glasses in an optical fiber drawing process [26]. As someone may not agree with that stability parameter is an indicator for drawing (our team who deal with fiber drawing is not always familiar with this concept), it is known that fluoroindate glasses can be drawn into optical fibers [15,16]. Preparation, melting, and quenching have been done in a glove box (MBraun, Garching, Germany) in a nitrogen atmosphere (O₂, H₂O < 0.5 ppm). Labels and specified lanthanide co-dopant compositions have been included in

Table 1. The molar percentage of holmium and ytterbium fluoride co-dopants.

Glass Sample	Co-Dopants
	(x) YbF3 [mol%]	(y) HoF3 [mol%]
0.8Yb	0.8	0
0.8Yb-0.2Ho	0.8	0.2
0.8Yb-0.4Ho	0.8	0.4
0.8Yb-0.8Ho	0.8	0.8
0.8Yb-1.2Ho	0.8	1.2
0.8Yb-1.4Ho	0.8	1.4
0.8Yb-1.6Ho	0.8	1.6

.

In order to remove oxide impurities from the raw reagents and compensate for the loss of fluorine due to the formation and loss of HF in glass batch ammonium bifluoride (NH₄HF₂) was added as a fluorinating agent (14 wt.% higher amount of excess). The glass batches were firstly fluorinated at 270 °C for 2 h and then melted at 900 °C for 1 h. The melts were poured out onto a stainless teel plate and annealed at 290 °C for 2 h. Spectroscopic measurements in the wide range of 1000–3100 nm were carried out using an Acton 2300i monochromator equipped with a PbSe detector (Teledyne, Princeton Instruments, Acton, MA, USA) with a lock-in detection (Stanford Reseach Systems, Sunnyvale, CA, USA) setup and high power Roithner Lasertechnik GmbH (Vienna, Austria) laser diodes (λ_exc = 976 nm, P_opt(max)=1 W). Infrared transmission spectrum was measured by using Fourier spectrometer Bruker Optics-Vertex70V (Billerica, MA, USA). Luminescence decay measurements were performed using a system PTI QuantaMaster QM40 coupled to a tunable pulsed optical parametric oscillator (OPO), pumped by the third harmonic of a Nd:YAG laser (OpotekOpolette 355 LD, Carlsbad, CA, USA). The laser system was equipped with a double 200 monochromator, a multimode UV-VIS photomultiplier tube (PMT) (R928), and Hamamatsu H10330B-75 detectors controlled by a computer. Luminescence decay curves were recorded and stored by a PTI ASOC-10 oscilloscope (Horiba, Northamption, UK). The accuracy of luminescence decay measurements was close to (±1 µs).

3. Results and Discussion

3.1. Infrared Transmission Spectrum and Hydroxide Group Content

The infrared transmittance spectrum of the prepared fluoroindate glass host (without rare-earth dopants) is presented in Figure 1. As shown, the IR transmission range is approximately up to 10 μm, which is much bigger than those of bismuth-germanate glass (5.5 μm) [32], bismuthate glass (5.5 μm) [33], ZBLAN glass (8 μm) [18], and fluoroaluminate glass (9 μm) [34].

However, regarding low-phonon glasses, only ZBLAN and fluoroindate can be drawn into high-quality optical fibers. Fluoroindate glass is one of the infrared materials that offers continuous optical transmission from the ultraviolet to midinfrared without any absorption peaks and can be drawn into good quality fibers, while their transmission window is much wider than standard zirconium fluoride based glass [35]. The absorption band at 3.3 μm shown in the inset of Figure 1 provides information about the hydroxide group content within the structure of each of the produced forms of glass. It is known that OH⁻ groups have a strong negative impact on MID-IR luminescence. The hydroxide concentration and the absorption coefficient at the wavelength of 3.1 µm and can be estimated according to the following equations [32,36]:

$${\alpha }_{O{H}^{-}}\left[c{m}^{-1}\right]=\frac{1}{d}ln\frac{T}{T_b}$$

(1)

$${\alpha }_{O{H}^{-}}\left[ppm\right]=\frac{1000}{d}log\frac{T}{T_b}$$

(2)

where: d—sample thickness, T—the value of the transmittance in the absorption peak, T_b—the value of the transmittance at the baseline.

The calculated absorption coefficient and hydroxide groups content was found to be 0.088 cm⁻¹ and 3.82 ppm, respectively. Since composition of the glasses host is very similar and they were prepared and melted in glove boxes, all glasses were found to have a similar amount of water. The obtained result is better than in fluorophosphate glass (35.5 ppm) [37] as well as fluoroaluminate glass (22.2 ppm) [34]. The reduced OH⁻ content results in an increase in quantum efficiency under the excitation of a 976 nm laser [11].

3.2. Luminescence Properties

Measurements of the emission bands in the Visible (VIS), Near Infrared (NIR), as well as Mid Infrared (MID-IR), enable conducting a comprehensive analysis on the effect of acceptor (Ho³⁺) concentration on the luminescent properties. It is commonly known that the Ho³⁺ ion cannot be pumped by 976 nm. Therefore, holmium levels are populated through a Yb³⁺ → Ho³⁺ energy transfer process. Figure 2 presents 2 μm emissions (Ho³⁺: ⁵I₇ → ⁵I₈) of the fabricated fluoroindate glasses co-doped with a different molar concentration of HoF₃ under a 976 nm laser excitation.

The linear increase of 2 μm luminescence intensity with the increasing of the HoF₃ content was observed. A smaller distance between the donor and acceptor ions leads to the efficient energy transfer from the excited ²F_5/2 energy level of ytterbium. It can be seen that the shape of the luminescence band slightly changes after increasing the Ho³⁺ content. It was presented in the literature that the four Stark emission bands, an equivalent model of four-level system for describing the 2 μm fluorescence band, can be used [38]. The four Stark emission bands centered at 1915, 1965, 2026, and 2078 nm can be distinguished. In the fabricated fluoroindate glasses, the I_2078nm/I_1965nm intensity ratio increases upon increasing the Ho³⁺ content, which also influences the FWHM (Figure 2b) [38].

Figure 3a shows the MID-IR emission spectra of 0.8YbF₃/(0.2–1.6 mol%)HoF₃ co-doped fluoroindate glasses excited at 976 nm. Due to the Ho³⁺: ⁵I₆ → ⁵I₇ transition, the broad and intense luminescence band at 2.85 μm was measured. It was also found that 2.85 μm luminescence intensity increases upon increasing Ho³⁺ ions up to 1.4HoF₃ (0.8Yb-1.4Ho glass) and then reduces with further increasing of HoF₃ (Figure 3b).

Table 2. Comparison of the FWHM of MID-IR emission band in glasses and crystals doped with Ho³⁺.

Material	Dopants	FWHM	Ref.
LuLiF4 crystal	1.58 × 1020 Ho3+ (ions/cm3)	<50 nm	[39]
Chalcogenide glass	1Ho2S3 (wt.%)	43 nm	[40]
Germanate glass	1Yb2O3/0.17Ho2O3 (mol%)	110 nm	[36]
Bismuth-germanate glass	0.75Yb2O3/0.25Ho2O3 (mol%)	71 nm	[32]
Fluoroaluminate glass	2YbF3/0.5HoF3 (mol%)	59 nm	[34]
Fluoroindate glass	0.8YbF3/1.4HoF3 (mol%)	83 nm	This work

shows that the obtained FWHM = 83 nm (Full With at Half Maximum) is only lower than in germanate glass, which indicates that fluoroindate glass is a promising low-honon energy glass for the construction of broadband MID-IR optical sources.

In the case of low phonon fluoroindate glasses co-doped with Yb³⁺/Ho³⁺ ions, the upconversion process cannot be neglected. Two emission bands at 542 nm and 650 nm corresponding to the ⁵F₄,⁵S₂ → ⁵I₈ and ⁵F₅ → ⁵I₈ transitions of Ho³⁺ ions have been observed (Figure 4). It can be seen that the intensity of the green emission band reduces monotonically with the increasing of Ho³⁺ content. A similar effect has been observed in fluoroaluminate glass [34]. Reduced upconversion luminescence (reduced ESA2) allows us to get enhanced MID-IR emissions (Ho³⁺: ⁵I₆ → ⁵I₈). This was also confirmed by shortening the lifetime of the Ho³⁺: ⁵I₆ level.

3.3. Energy Transfer Mechanism between Yb³⁺and Ho³⁺, Energy Transfer Efficiency

To explain the 2.85 μm, 2 μm, and upconversion emissions as well as the energy transfer mechanism in Yb³⁺/Ho³⁺ under 976 nm laser excitation, the energy level diagram was proposed based on the previous investigations and presented in Figure 5 [32,41].

Firstly, under 976 nm excitation, the Yb³⁺: ²F_5/2 was populated directly through the ground state absorption process. Then, part of the energy was transferred to the Ho³⁺: ⁵I₆ level by a phonon-assisted (PAET): Yb³⁺: ²F_5/2 → Ho³⁺: ⁵I₆ energy transfer. Part of Ho³⁺ ions could relax radiatively due to Ho³⁺: ⁵I₆ → ⁵I₇ (2.85 μm) and Ho³⁺: ⁵I₆ → ⁵I₈ (1200 nm). Another part of Ho³⁺ ions relaxed nonradiatively to the Ho³⁺: ⁵I₇ level, which is responsible for 2 μm emissions (Ho³⁺:⁵I₇ → ⁵I₈). Due to the low phonon energy of the fluoroindate glasses (510 cm⁻¹) upconversion mechanisms also had to be analyzed. Simultaneously, another excited Yb³⁺ ion populated the Ho³⁺: ⁵S₂(⁵F₄) level due to the energy transfer upconversion process (ETU). Some of the ions relaxed non-radiatively to the Ho³⁺: ⁵F₅ level and the red emission (⁵F₅ → ⁵I₈) occurred. In addition, ions at Ho³⁺: ⁵I₆ level were populated to the upper Ho³⁺: ⁵S₂(⁵F₄)_, ⁵F₅ levels through excited-state absorption (ESA1 and ESA2). Finally, the green emission corresponding to the ⁵S₂(⁵F₄) → ⁵I₈ transition took place [41].

To determine the efficiency of energy transfer mechanisms, the luminescence decays in the fabricated glasses were analyzed. First of all, we focused on the depopulation process in the Yb³⁺: ²F_5/2 level as a function of holmium ions. Shortening of the Yb³⁺: ²F_5/2 lifetime occurred due to the Yb³⁺ → Ho³⁺ energy transfer. Figure 6 shows the luminescence decays of ²F_5/2 level under 976 nm excitation. All measured luminescence decays were fitted by the single exponential curve. In singly Yb³⁺-doped fluoroindate glass, the measured lifetime is 2.25 ms and in Yb³⁺/Ho³⁺ co-doped glasses, the lifetime decreases with successive introduction of Ho³⁺ ions.

This effect confirms that Yb³⁺ is a suitable sensitizer in fabricated glasses and can efficiently transfer the energy to Ho³⁺ ions through a phonon-assisted process. According to ²F_5/2 (Yb³⁺) lifetime changes, the efficiency of Yb³⁺ → Ho³⁺ energy transfer can be estimated by the following equation:

$${\eta }_{Yb\to Ho}=1-\frac{{\tau }_{Yb\left(Ho\right)}}{{\tau }_{Yb}}$$

(3)

where τ_Yb(Ho) and τ_Yb are the lifetimes of ²F_5/2 level in glasses co-doped with Yb³⁺/Ho³⁺ ions and singly doped with Yb³⁺ ions, respectively. In the fabricated glass, the maximum efficiency of ET was estimated to be close to 61% for the sample with 0.8YbF₃/1.6HoF₃ (Figure 7).

To analyze the overall distribution of excitation energy in Yb³⁺/Ho³⁺ ions, the luminescence decays of Ho³⁺: ⁵I₆ and ⁵I₇ levels were also measured (Figure 8). It can be seen that the lifetime of ⁵I₆ level decreased slightly with an increasing Ho³⁺ concentration. This reduction leads to the limitation of ESA2 process [34], hence strong quenching in upconversion luminescence at 546 nm (Ho³⁺: ⁵S₂ + ⁵F₄) was observed (Figure 4). Simultaneously, the weak upconversion emission can promote the Ho³⁺: ⁵I₆ → ⁵I₇ transition, where the monotonical increase in 2.85 µm emission intensity occurs up to 1.4HoF₃ co-doped glasses (Figure 3). The decay curves of the ⁵I₇ energy level of the fluoroindate glass co-doped with Yb³⁺/Ho³⁺ ions were shown in Figure 8b. In this case, we can see that the addition of Ho³⁺ ions also reduces the lifetime at the wavelength of 2 µm (Ho³⁺:⁵I₇ → ⁵I₈). Based on the simplified energy diagram of Yb³⁺ and Ho³⁺ ions, we deduced that a shorter decay time on ⁵I₇ level can restrain the ESA1 process and amplify the intensity of 2µm emission. Moreover, the faster radiative relaxation of ⁵I₇ than ⁵I₆ level supports inversion in the ions population between these levels, which is beneficial for the population accumulation of upper level of ~2.85 µm emissions, which originated from Ho³⁺: ⁵I₆ → ⁵I₇ transition [42].

In both analyzed cases, decay curves are not linear, hence we used a double-exponential function to estimate the average lifetime. In the case of double-exponential decay of luminescence, we used a known equation for calculating the average lifetime of higher energy levels in Ho³⁺ ions. The luminescence intensity could be described by the sum of two exponential decay components from:

$$\mathrm{I}\left(\mathrm{t}\right)={\mathrm{A}}_1\exp \left(-\frac{\mathrm{t}}{{\tau }_1}\right)+{\mathrm{A}}_2\exp \left(-\frac{\mathrm{t}}{{\tau }_2}\right)$$

(4)

where τ₁ and τ₂ were short- and long-decay components, respectively. Parameters A₁ and A₂ were fitting constants. Then, the average lifetime <τ> was given by:

$$\langle \tau \rangle =\frac{{\mathrm{A}}_1{\tau }_1^2+{\mathrm{A}}_2{\tau }_2^2}{{\mathrm{A}}_1{\tau }_1+{\mathrm{A}}_2{\tau }_2}.$$

(5)

Calculated values of lifetimes of ⁵I₆ and ⁵I₇ levels are listed in

Table 3. Calculated lifetimes of ⁵I₆ and ⁵I₇ levels in Ho³⁺ ions.

Glass Code	Lifetime @1200 nm [ms]	Lifetime @2000 nm [ms]
0.8Yb_0.2Ho	5.13	1.69
0.8Yb_0.4Ho	5.01	1.41
0.8Yb_0.8Ho	4.84	1.10
0.8Yb_1.2Ho	4.98	0.89
0.8Yb_1.4Ho	4.71	0.77
0.8Yb_1.6Ho	4.27	0.88

.

The decrease in decay time with increasing Ho³⁺ concentration can be explained as the increased probability of the energy migration process between Ho-Ho pairs. A similar effect has been observed in barium gallo-germanate glasses [43].

4. Conclusions

Fluoroindate glasses co-doped with Yb³⁺/Ho³⁺ were fabricated and their spectroscopic properties under 976 nm laser diode excitation were characterized. The infrared transmission spectrum a indicates low OH⁻ content (single ppm level) in the fabricated fluoroindate glass. It confirms that the quenching of the MID-nfrared luminescence is strongly limited. In particular, the effect of Ho³⁺ sensitization by Yb³⁺ ions on luminescence spectra in the VIS, NIR, and MID-IR spectral ranges was analyzed. The maximum intensity of 2.85 μm emissions (Ho³⁺:⁵I₆ → ⁵I₇) has been obtained in glass co-doped with 0.8YbF₃/1.4HoF₃. Simultaneously, the reduction of the green emissions with increasing Ho³⁺ content was observed. This effect was a result of the reduced lifetime of the Ho³⁺:⁵I₆ level (thus the ESA2 process). Finally, enhancement of the 2.85 μm luminescence took place. Analysis of the luminescence decay curves revealed that Ho³⁺ ions are efficiently sensibilizated. The maximum efficiency of Yb³⁺ to Ho³⁺ energy transfer was calculated to be up to 61%.

In summary, based on our results, the effective sensitization of Ho³⁺ in fluoroindate glasses for NIR and especially MID-IR emission can be realized by Yb³⁺. The fabricated glass can be used as a bulk glass or glass fiber luminescence source of 2.85 μm radiation for CO₂ absorption-based sensing.