Eu3+和Er3+掺杂NaLu1-xYbxF4纳米玻璃陶瓷：微观结构与光学性质
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"Eu3 +和Er3 +掺杂的NaLu1-xYbxF4（x = 0〜1）固溶自结晶纳米玻璃陶瓷：微观结构和光谱学"
这篇研究文章着重讨论了 Eu3+ 和 Er3+ 掺杂的NaLu1-xYbxF4固溶自结晶纳米玻璃陶瓷的制备方法、微观结构和光学性质。这种新型材料通过玻璃自结晶技术首次被成功合成，这是一种创新的纳米晶嵌入玻璃陶瓷的制备工艺。在该过程中，Eu3+ 或 Er3+ 掺杂剂被证实已经有效地融入了晶格结构，这是通过扫描透射电子显微镜（STEM）和光谱分析得出的。
进一步的热处理促进了材料的结晶化，降低了纳米晶体的表面积-体积比，这对于提高含有镧系元素激活剂（如Eu3+和Er3+）的NaLu1-xYbxF4纳米晶体的光学性能至关重要。在980纳米近红外激光的激发下，Er3+掺杂的NaLu1-xYbxF4纳米晶体展现出显著的上转换效应，这意味着它们可以在较低能量的光激发下发射出较高能量的光子。这种特性在光通信、生物成像和太阳能转换等领域有着潜在的应用价值。
文章还指出，这种自结晶策略为设计和开发具有可调节光学特性的新型透明纳米复合材料提供了广阔的可能性。通过改变 Eu3+ 和 Er3+ 的掺杂比例以及调整 x 值（x = 0 至 1），可以实现对材料光学性质的精细调控，从而满足不同的应用需求。
这项工作揭示了Eu3+ 和 Er3+ 掺杂的NaLu1-xYbxF4纳米玻璃陶瓷的先进制备技术和优异的光学特性，为未来的光学材料研究与开发开辟了新的路径。关键词包括玻璃陶瓷、上转换、光学材料、纳米晶体以及NaLuF4，表明这些是该研究领域的核心概念。
Journal of the European Ceramic Society 35 (2015) 3673–3679
Contents lists available at www.sciencedirect.com
Journal of the European Ceramic Society
journal homepage: www.elsevier.com/locate/jeurceramsoc
Eu
3+
and Er
3+
doped NaLu
1−x
Yb
x
F
4
(x =0∼ 1) solid-solution
self-crystallization nano-glass-ceramics: Microstructure and optical
spectroscopy
Zhongyi Wan
a
, Daqin Chen
a,∗
, Yang Zhou
a
, Ping Huang
b
, Jiasong Zhong
a
, Mingye Ding
a
,
Hua Yu
a
, Zhenguo Ji
a
a
College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, PR China
b
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002,
PR China
article info
Article history:
Received 18 January 2015
Received in revised form 21 May 2015
Accepted 26 May 2015
Available online 4 June 2015
Keywords:
Glass ceramics
Upconversion
Optical materials
Nanocrystals
Naluf
4
abstract
NaLu
1−x
Yb
x
F
4
solid-solution nanocrystals embedded glass ceramics were successfully fabricated via the
glass self-crystallization route for the first time. Importantly, the Eu
3+
or Er
3+
dopants are demonstrated
to enter into the crystalline lattice by scanning transmission electron microscopy mapping and optical
spectroscopy analysis. Further crystallization treatment is advantageous to improving the crystallinity
and reducing surface-to-volume of NaLu
1−x
Yb
x
F
4
nanocrystals where lanthanide activators reside, which
induces great enhancement of optical performance of nanostructured glass ceramics. Under 980 nm
near-infrared laser excitation, multi-color upconversion luminescence tuning from green to yellow and
finally to red was easily realized by simply modifying Lu/Yb ratio in the glass ceramics containing Er
3+
:
NaLu
1−x
Yb
x
F
4
(x =0∼ 1) nanocrystals. It is expected that such glass self-crystallization strategy may offer
a great opportunity to design and develop other new transparent nano-composites with a wide range of
tunable optical properties.
© 2015 Elsevier Ltd. All rights reserved.
1. Introduction
Nowadays there is a widespread study on the trivalent
lanthanide (Ln
3+
) ions doped upconversion (UC) luminescence
materials owing to their potential application in the solid-state
laser, three-dimensional display, bio-label, sensor, catalysis, and
solar cell, etc [1–6]. Therefore, searching highly efficient UC mate-
rials is highly valuable. It is well known that the crystals structures
affect the UC luminescence performance, so it is particularly impor-
tant to choose the appropriate host materials [7–10]. Oxyfluoride
glass ceramics (GCs) combine the advantage of the mechanical and
chemical stability of the oxide glass and the low phonon energy
of the precipitated fluoride crystal, which may become a desirable
choice as the UC bulk hosts [11–23]. Generally, GCs were fabricated
via controllable crystallization by heating precursor glasses (PGs)
with specially designed compositions at a suitable temperature for
the prescribed time of period [24]. To realize efficient UC lumi-
nescence, the homogenous precipitation of the desired fluoride
∗
Corresponding author. Tel.: +86 571 87713542; fax: +86 571 87713542.
E-mail address: dqchen@hdu.edu.cn (D. Chen).
nanocrystals (NCs) and the partition of the optically activators into
the fluoride lattice are necessary. In addition, transparency of GCs is
another factor needing consideration, which can be achieved when
the size of the precipitated NCs is far smaller than the wavelength
of the visible light.
So far, many fluoride NCs, such as REF
3
(RE = La – Lu), MF
2
(M = Pb, Ca, Sr, Ba), NaREF
4
(RE = Y, Gd, Lu), LiYbF
4
and KYb
2
F
7
,
embedded GCs have been reported [11–23]. The incorporation of
activators into fluoride lattice is generally based on the Ln
3+
diffu-
sion process in the previously reported GC systems. Unfortunately,
such process strongly depends on the crystallization temperature.
For the low crystallization temperature, the diffusion coefficient
of Ln
3+
in glass is low, which impedes their incorporation into
crystalline host, whereas, for the high ceramization temperature,
the fluoride crystals will grow up quickly, which degrades the
transparency of GCs. Therefore, precisely control crystallization to
realize optimal microstructure and optical performance of GC still
a formidable task.
Herein, transparent GCs containing cubic NaLu
1−x
Yb
x
F
4
solid-
solution NCs were successfully synthesized for the first time.
Different to the cases reported previously, such GCs, with appro-
priately designing oxyfluoride glass composition, were directly
http://dx.doi.org/10.1016/j.jeurceramsoc.2015.05.031
0955-2219/© 2015 Elsevier Ltd. All rights reserved.
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