掺Er3+锗酸盐玻璃的中红外光谱与能量转移研究
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"掺Er3 +的锗酸盐玻璃是一种潜在的中红外应用材料，本文对其光学性质、能级间转移机制以及种群行为进行了深入研究。通过980 nm二极管激光器泵浦，观察到在2.7 μm处的自发辐射跃迁概率和发射截面分别为36.45 s^(-1)和1.61 x 10^(-20) cm^2。实验揭示了中红外发光特性的关键参数，并利用Inokuti-Hirayama模型、速率方程和Dexter理论分析了Er3 +离子在4I11/2和4I13/2能级间的种群动态。此外，通过差示扫描量热法(DSC)评估了样品的热稳定性，以评估其耐热损伤和抗结晶性。这些发现为理解2.7微米发射的Er3 +离子的种群行为提供了理论依据，进一步推动了锗酸盐玻璃在中红外技术领域的应用潜力。"
本文的核心知识点包括：
1. 掺杂材料科学：研究对象是掺Er3 +的锗酸盐玻璃，这是一种用于光学应用的掺杂材料，Er3 +离子作为激活剂增强了玻璃的光学性能。
2. 光学发射特性：在2.7 μm处的自发辐射跃迁概率和发射截面是衡量材料光学性能的重要指标，高值意味着高效的中红外发射。
3. 能量转移机制：通过分析Er3 +离子的4I11/2和4I13/2能级间的跃迁，可以了解能量如何在不同能级之间传递，这对设计高效激光或光放大系统至关重要。
4. Inokuti-Hirayama模型：该模型用于描述多能级系统中的粒子跃迁和能量转移，帮助解释实验观测到的光谱行为。
5. 速率方程：在分析种群动态时，速率方程用于描述离子在不同能级间的转移速率，从而理解发射和吸收过程。
6. Dexter理论：这一理论用于研究近邻离子间的非辐射能量转移，对于了解上转换发光现象尤其重要。
7. 热稳定性研究：通过DSC曲线分析，评估了样品在高温下的稳定性能，这对于实际应用中的耐热性和长期稳定性至关重要。
8. 抗结晶性：研究材料的抗结晶性是确保其在高温环境下保持非晶态结构的关键，这对于保持其光学特性至关重要。
这项研究不仅揭示了掺Er3 +锗酸盐玻璃的光学特性，还提供了深入理解其内部能量转移和种群动力学的理论工具，为进一步优化这种材料的性能和应用提供了基础。
resist the thermal damage and improve output power when incident pumping power is
enhanced.
Recent decades have witnessed the great development of optical glasses, including
fluoride, fluorophosphate, tellurite, bismuthate, germanate glass, etc [13–17]. Among all
kinds of glasses mentioned above, germanate glass has robust mechanical quality, low
maximum phonon energy of 900 cm
−1
and large solubility of rare earth ions [18, 19].
Moreover, the combination of high infrared transmittance in a wide wavelength region (~6.5
μm), superior thermal stability and chemical durability makes it an attractive infrared material
[20, 21]. In the family of germanate glasses, the glasses based on barium gallogermanate
glass (BGG) system possess good optical properties and glass-forming ability [22]. Previous
work has reported optical characteristics of BGG glass acting as a window for high energy
laser system in the near-infrared wavelength range [22]. Unfortunately, germanate glass has
some disadvantages, such as high melting temperature, high viscosity and a high
concentration of hydroxyl groups that cause a strong absorption band around 2.7 μm and
depress the transmittance in 2.5-5 μm region [23]. Fortunately, it has been reported that
fluoride cannot only reduce glass viscosity for the purpose of energy conservation, but also
decrease the content of OH
-
of glass and improve fluorescence efficiency with an efficient
energy transfer of rare earth ions. It has been demonstrated that the properties of BGG glass
can also be modified by adding other components such as La
2
O
3
and Y
2
O
3
[24]. Besides,
germanate glass containing Y
2
O
3
has been investigated for the purpose of structure and near-
infrared emissions [25, 26]. However, population dynamics for mid-infrared radiation, to our
knowledge, have less been reported in Er
3+
doped germanate glass. Previous studies mainly
focused on qualitative analysis of mid-infrared emission spectra [27–29].
The aim of this paper is to investigate mid-infrared spectroscopic properties and energy
transfer mechanism in Er
3+
doped germanate glasses with the substitution of Y
2
O
3
for La
2
O
3
.
Population dynamics of upper and lower levels for Er
3+
:
4
I
11/2
→
4
I
13/2
transition have been
analyzed in detail based on I-H model, rate equation and Dexter’s theory. It is expected that
this work can provide useful guide for investigating population dynamics of mid-infrared
emissions.
2. Experimental procedures
The investigated glasses have the following compositions in mol %: 65GeO
2
-15Ga
2
O
3
-5BaO-
(10-x) La
2
O
3
-xY
2
O
3
-5NaF-0.5Er
2
O
3
(x = 0, 5, 10), denoted as GLY1, GLY2 and GLY3,
respectively. The raw materials were prepared from the high purity GeO
2
, Ga
2
O
3
, BaO,
La
2
O
3
, Y
2
O
3
, NaF and Er
2
O
3
powder. Well mixed raw materials (10 g) were placed in an
alumina crucible and melted at 1400 °C for 50 min in air atmosphere. The melts were quickly
poured on preheated stainless steel mold and annealed for 6 h near the temperature of glass
transition (T
g
). Subsequently, the annealed samples were fabricated and polished to the size of
10 × 10 × 1.5 mm
3
for optical performance measurements.
The glass transition temperature (T
g
), crystallization onset temperature (T
x
) and
crystallization peak temperature (T
p
) were characterized by a NetzschSTA449/C differential
scanning calorimeter (DSC) at a heating rate of 10 K/min. The sample refractive indices and
densities were measured by means of the prism minimum deviation method and the
Archimedes principle using distilled water as immersion liquid, respectively. The absorption
spectra from 350 to 1640 nm were recorded with a Perkin-Elmer Lambda 900UV/VIS/NIR
spectrophotometer with the resolution of 1 nm. The fluorescence spectra in the range of 500-
700 nm and 2600-2800 nm were measured by TRIAX550 spectrophotometer pumped at 980
nm LD with the output power of 600 mW. The decay curves at 1.53 μm fluorescence were
obtained with light pulses of the 980 nm LD with the same power and HP546800B 100-MHz
oscilloscope. The same conditions for different samples were maintained so as to get
comparable results. All the measurements were performed at room temperature.
#217655 - $15.00 USD
Received 29 Jul 2014; revised 11 Sep 2014; accepted 11 Sep 2014; published 22 Sep 2014
(C) 2014 OSA
1 October 2014 | Vol. 4, No. 10 | DOI:10.1364/OME.4.002150 | OPTICAL MATERIALS EXPRESS 2153
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