Electron. Mater. Lett., Vol. 11, No. 2 (2015), pp. 187-192
Preparation of Ternary Cd
1-x
Zn
x
S Nanocrystals with Tunable Ultraviolet
Absorption by Mechanical Alloying
Qi Zhang,
1
Huihui Zhang,
1
Limin Liu,
1
Shaohua Li,
2
James B. Murowchick,
2
Clarissa Wisner,
3
Nickolas Leventis,
3
Zhonghua Peng,
2,
*
and Guolong Tan
1,
*
1
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,
Wuhan University of Technology, Wuhan 430070, China
2
Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110, USA
3
Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409, USA
(received date: 8 October 2014 / accepted date: 12 November 2014 / published date: 10 March 2015)
1. INTRODUCTION
Alloyed semiconductor nanocrystals (NCs) enable band
gap engineering through both size control and composition
tuning.
[1-3]
Although wet chemical routes have shown to be
viable and attractive in preparing alloyed NCs with
controlled uniform size and shape,
[3-6]
mechanical alloying is
a far simpler and more versatile technique in preparing
composition-tunable NCs.
[7-11]
Starting from the corresponding
elemental powders, chemically homogenous alloyed NCs
with sizes less than 10 nm can be prepared by simple
mechanical alloying. The composition of the resulting NCs
can be precisely controlled by varying the elemental loading
ratios. For example, we have recently demonstrated that
ternary CdSe
x
S
1-x
[12]
and CdTe
x
Se
1-x
[13]
NCs in the entire
composition range (x = 0 - 1) can be successfully prepared
by mechanical alloying. The ternary CdSeS NCs exhibit
strong absorption in the visible range, whereas the CdTeSe
NCs extend the absorption to the near infrared (IR) range (up
to 1400 nm). Here, we extend the same approach to prepare
ternary Cd
x
Zn
1-x
S NCs, where the cation atomic compositions
are manipulated. The resulting NCs exhibit band gap
energies ranging from the ultraviolet (UV) to the visible
region depending on the atomic ratio of Cd to Zn.
CdZnS alloys, with direct and wide band gaps ranging
from 2.42 to 3.67 eV in their bulk state, are some of the most
appealing materials for applications in photonics and
optoelectronics.
[5,14-18]
Their NCs have narrow, tunable, and
symmetric emission spectra and are photochemically stable.
The band gap of CdZnS NCs is affected more by the
composition than the size of the nanocrystals.
[19,20]
In this
work, we report the synthesis of ternary Cd
x
Zn
1-x
S NCs, their
structural evolution during the mechanical alloying process,
and their intrinsic optical spectra.
Composition-tunable ternary Cd Zn S nanocrystals are among the most
extensively studied alloyed semiconductor nanocrystals. However, they are
almost exclusively prepared by wet chemical routes, which lead to surface-
capped nanoparticles. Herein, we present a simple mechanical alloying process
to prepare uncapped Zn Cd S nanocrystals throughout the entire composition
range. The resulting nanocrystals have average sizes smaller than 9 nm, are
chemically homogenous, and exhibit linear lattice parameter-composition and
close-to-linear band-gap-composition relationships. Continuous lattice contraction
of the Cd Zn S nanocrystals with the atomic Zn concentration results in a
successional enlargement of their band gap energies expanding from the
visible region to the ultraviolet (UV) region, demonstrating the ability for
precise control of band gap engineering through composition tuning and
mechanical alloying.
Keywords: CdZnS, ternary semiconductor, nanocrystals, mechanical alloying,
optics
DOI: 10.1007/s13391-014-4327-8
*Corresponding author: PengZ@umkc.edu
*Corresponding author: gltan@whut.edu.cn
©KIM and Springer