Materials Chemistry and Physics 99 (2006) 494–497

Synthesis of highly luminescent and photostable ZnS:

Ag nanocrystals under microwave irradiation
Wenping Jian, Jiaqi Zhuang, Dawei Zhang, Jie Dai, Wensheng Yang ∗ , Yubai Bai
Alan G. MacDiarmid Laboratory, College of Chemistry, Jilin University, Chuangchun 130012, PR China
Received 31 July 2005; received in revised form 15 November 2005; accepted 27 November 2005

Abstract
ZnS:Ag nanocrystals with Ag doping concentrations of 1 at% was synthesized by using 3-mercaptopropionicacid (MPA) as stabilizer. A ZnS
shell was formed on surface of the ZnS:Ag nanocrystals by the decomposition of Zn–MPA complex under microwave irradiation. The new ZnS
shell passivated the nanocrystal surface and resulted in a significant enhancement of the photoluminescent quantum yield and photostability of the
nanocrystals. Under optimum reaction conditions, quantum yield of the ZnS:Ag nanocrystals increased from 2.5 to 10.2% after the shell growth.
© 2005 Elsevier B.V. All rights reserved.

Keywords: ZnS:Ag nanocrystals; Luminescence; Microwave irradiation; Photostability

1. Introduction
Over the past two decades, great efforts have been put into the
synthesis of highly fluorescent II–VI semiconductor nanocrys-
tals due to their unique properties and potential applications
[1–4]. ZnS is an important type of II–VI semiconductors. Doped
ZnS nanocrystals, such as ZnS:Mn or ZnS:Ag, have attracted
researchers’ attentions during the past decade due to their inter-
esting luminescent properties [5–12]. The doping ions act as
recombination centers for the excited electron–hole pairs and
result in a characteristic luminescence. However, most of the
reported doped ZnS nanocrystals have a low-luminescent quan-
tum yield (QY), especially those synthesized in aqueous solution
[13]. The low QY is commonly attributed to the vast sur-
face of nanocrystals since the surface states are likely to trap
electrons and/or holes and induce the non-radiative recombi-
nation of these charge carriers. The surface of nanocrystals
can be well passivated by epitaxial growth of an inorganic
shell bearing a wider bandgap than the core. Several undoped
core/shell nanocrystals, such as CdSe/CdS, CdSe/ZnS have been
shown to have much higher quantum efficiencies and better
photostability comparing to unpassivated nanocrystals [14,15].
Recently, Yang and Holloway reported the synthesis of highly
luminescent efficient and photostable CdS:Mn/ZnS nanocrys-
∗ Corresponding author. Tel.: +86 431 5168364; fax: +86 431 8923907.
E-mail address: wsyang@mail.jlu.edu.cn (W. Yang).
tals by a reverse micelle method [16]. However, the low yield
of the product and the difficulty to remove the surfactant on
the nanocrystal surface impede practical application of the
nanocrystals.
In this work, we present a microwave assisted epitaxial
growth method to synthesize highly luminescent and photostable
ZnS:Ag nanocrystals. A new ZnS shell is formed on surface of
the ZnS:Ag nanocrystals by decomposition of Zn–thiol complex
under microwave irradiation. The QY and photostability of the
ZnS:Ag nanocrystals are improved greatly after the growth of
the ZnS shell.
2. Experimental
2.1. Chemicals
Analytical grade Zn(Ac)2 ·2H2 O, AgNO3 , Na2 S·9H2 O and NaOH
were obtained from Beijing Chemical Int. and used as received. 3-
Mercaptopropionicacid (MPA, <99%) was purchased from Aldrich. Water used
in all synthesis was high-purity grade with a conductivity of 18.2 M
cm.
2.2. Preparation of ZnS:Ag nanocrystals and microwave assisted
epitaxy growth of ZnS shell
The synthesis process of ZnS:Ag nanocrystals with Ag doping concen-
trations of 1 at% is similar to reference [8]. In a typical experiment, 5 ml of
0.1 M Zn(Ac)2 , 0.5 ml of 0.01 M AgNO3 and 20 ml of 0.1 M MPA were mixed
together, then the solution was diluted to 45.5 ml with water. The pH of the
mixed solution was adjusted to 9.0 with 2 M NaOH. After the purging of air
by N2 bubbing for 30 min, 4.5 ml of 0.1 M Na2 S was quickly injected into

0254-0584/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2005.11.030
 W. Jian et al. / Materials Chemistry and Physics 99 (2006) 494–497
the solution. The mixture was kept for 15 min at room temperature (25 ± 1 ◦ C)
under magnetic stirring. The obtained ZnS:Ag nanocrystals were precipitated by
ethanol, centrifuged and washed with ethanol for several times, and then dried in
vacuum.
For the ZnS shell growth, first, 5 ml of 0.1 M Zn(Ac)2 and 0.174 ml MPA
were mixed together. The solution was diluted to 49 ml with water. The pH
of the mixed solution was adjusted to 10.3 with 4 M NaOH and degassed by
N2 bubbling for 30 min. The crude powders of ZnS:Ag nanocrystals were dis-
persed in water with the Zn concentration of 0.01 mol l−1 . Thirty millilitres of
ZnS:Ag solution was diluted to 130 ml with water and purged by N2 for 30 min.
Then, 20 ml solution of the Zn–MPA complex was added to the diluted ZnS:Ag
solution, and the mixture was transferred to the Teflon container for microwave
treatment. According to our experiment, we established the optimum reaction
conditions that the inner pressure was 0.6 MPa, reaction time 3 min, and practical
operating power 600 W.
2.3. Photooxidation
All photooxidation experiments were performed in 1 cm quartz cell under
constant airflow with a 500 W high-pressure mercury lamp. The lamp was placed
4 cm directly above the samples. The solution samples were prepared by adjust-
ing the absorbance (optical density, OD) of the nanocrystals at 300 nm to 0.1–0.2.
The fluorescent spectra were recorded at certain time intervals.
2.4. Characterization
UV–vis spectra were recorded on a Varian Cary 100 UV–vis spectropho-
tometer. Photoluminescence (PL) spectra were acquired on an Eidingberg FS
900 spectrometer. X-ray diffraction data were obtained using a Philip X Pert
diffractometer with Cu K␣ radiation (λ = 1.5405 Å). Microwave reaction was
carried out by a microwave digestion system (model MDS-2003F, Shanghai
Sineo Microwave Chemical Technology Co., Ltd.)
3. Results and discussion
In our previous works [17], we confirmed that Zn–MPA com-
plex could form ZnS nanocrystals under microwave irradiation
when the mole ratio of Zn/MPA is 0.25. On the basis of this
experimental result, we deposited ZnS shell on the surface of
ZnS:Ag nanocrystals. Fig. 1 shows the XRD patterns of ZnS:Ag
nanocrystals before and after the shell growth. The diffraction
spectra of two kinds of nanocrystals have three similar charac-
Fig. 1. The XRD patterns of ZnS:Ag doped with 1 at% Ag (a) crude, (b) after
microwave treatment without Zn–MPA complex and (c) after microwave treat-
ment with Zn–MPA complex.
495
teristic peaks index as the (1 1 1), (2 2 0) and (3 1 1) planes of
cubic zinc blende phase. This indicates that the decomposition
product of Zn–MPA complex is ZnS. By using the Scherrer equa-
tion, the particle sizes of the two samples before and after shell
growth are estimated to be about 2.5 and 3.3 nm, respectively
[18]. When ZnS:Ag nanocrystals was treated with microwave
irradiation in absence of the Zn–MPA complex, the particle size
was estimated to be approximately 3.0 nm. Fig. 2 shows the
TEM images of ZnS:Ag nanocrystals before and after the shell
growth. The particles show spherical shape and nearly uniform
size. A little agglomeration is observed due to the evaporation
of solvent. The average diameters of the ZnS:Ag nanocrystals
before and after the shell growth are estimated to be about 2.5
and 3.5 nm, respectively, which are consistent with the XRD
results.
The shell growth was further investigated by the absorption
spectroscopy. Typical results of the ZnS nanocrystal doped with
1% Ag after shell growth are presented in Fig. 3. After the
shell growth, a significant red-shift of the absorption onset is
observed, indicating the increased size of the ZnS:Ag nanocrys-
tals after shell growth. The sample heated under the same
microwave conditions without the presence of Zn–MPA com-
plex shows only smaller red-shift in UV–vis spectrum. The shift
of its absorption onset is considered as the result of Ostwald
ripening of ZnS:Ag nanocrystals under microwave irradiation
conditions. Therefore, the significant red-shift of the absorption
onset means that the increase of the particle size is primarily
contributed to the epitaxial growth of a new ZnS shell by the
decomposition of Zn–MPA complex during the microwave treat-
ments.
Fig. 4A shows the PL spectra of the Ag-doped nanocrys-
tals before and after the shell growth. Compared with that of the
untreated ZnS:Ag nanocrystals, the PL intensity of the nanocrys-
tals after shell growth increases greatly. The quantum yields
of ZnS:Ag nanocrystals were measured in aqueous solution.
The quantum yields of ZnS:Ag nanocrystals increased from
2.5 to 10.2% after the shell growth. For ZnS:Ag nanocrystals
under the same microwave treatment without the presence of
Zn–MPA complex, there is only a little increment of the quan-
tum yield (from 2.5 to 3.1%). ZnS:Ag nanocrystals without ZnS
shell shows a emission at 425 nm and the peak shift to 445 nm
after the growth of ZnS shell. The increase of particle size which
results in the decrease of nanocrystals band gap energy may con-
tribute to the red-shift of the emission. The ZnS:Ag nanocrystals
treated with microwave in absence of Zn–MPA complex show
a emission at 455 nm thought their sizes are smaller than those
with ZnS shell. As shown in Fig. 4B, the undoped 3.0 nm ZnS
nanocrystals also show emission at 455 nm and the shape of the
emission peak is also asymmetry, similar to that of the ZnS:Ag
nanocrystals treated in absence of Zn–MPA complex. This indi-
cates that without shell growth, the microwave treatment is only
effective to eliminate the crystal defects in the nanocrystals, and
thus enhance the surface state-related emission of ZnS. The sig-
nificant increase of Ag-related emission of ZnS:Ag nanocrystals
is primary contributed to the formation of ZnS passivation shell.
We performed a photooxidation experiment to verify the
effect of ZnS shell. As shown in Fig. 5., compared with
496 W. Jian et al. / Materials Chemistry and Physics 99 (2006) 494–497

Fig. 2. TEM image of ZnS:Ag nanocrystals (A) before and (B) after shell growth.

Fig. 3. The absorption spectra of ZnS:Ag doped with 1 at% Ag (a) crude, (b) Fig. 5. The relative PL intensity of three kinds of ZnS:Ag nanocrystals with
after microwave treatment without Zn–MPA complex and (c) after microwave 1 at% Ag during photooxidation. (a) Crude, (b) after microwave treatment with-
treatment with Zn–MPA complex. out Zn–MPA complex and (c) after microwave treatment with Zn–MPA complex.

Fig. 4. (A) The photoluminescence spectra of the ZnS:Ag nanocrystals with 1 at% Ag (a) crude, (b) after microwave treatment without Zn–MPA complex and (c)
after microwave treatment with Zn–MPA complex. The excitation wavelength was at 300 nm. (B) The photoluminescence spectra of (a) the ZnS:Ag nanocrystals
with 1 at% Ag after microwave treatment with Zn–MPA complex, (b) the 3.0 nm undoped ZnS nanocrystals and (c) the 3.0 nm ZnS:Ag nanocrystals without shell
growth. The excitation wavelength was at 300 nm.
 W. Jian et al. / Materials Chemistry and Physics 99 (2006) 494–497
Fig. 6. Schematic diagram of energy levels of the ZnS:Ag nanocrystals.
the initial PL intensity of the nanocrystals, the PL inten-
sity of the ZnS:Ag nanocrystals with the ZnS shell decreased
only about 50% when the photooxidation time was up to
55 min. Whereas for the crude and microwave treated ZnS:Ag
nanocrystals, the luminescence almost disappeared after 10 min.
Since the surface defect is more active than other site, they
can act as growth center during the formation of the new
ZnS shell. Deposition of the new ZnS shell on the sur-
face of ZnS:Ag nanocrystals further eliminates the surface
defects, thus reduces the non-radiative transition possibility,
leading to the increased luminescent efficiency and improved
photostability.
The doping silver ions in the obtained ZnS:Ag nanocrys-
tals may exist in two forms, which is supposed to be simi-
lar to those in Ag-doped CdS colloid [19–20]. A small frac-
tion of the silver ions are incorporated into ZnS lattice, while
the remaining part of the silver ions exist in the form of an
Ag2 S phase. The anion vacancies formed in the attachment
region between the Ag2 S and ZnS phases will act as elec-
tron donors while the silver ions incorporated into ZnS lat-
tice act as an acceptor defect (Ag centers) and give rise to
localized energy level near the valence band [20]. The mech-
anism for the luminescence from ZnS:Ag nanocrystals may
be interpreted by the energy diagram shown in Fig. 6. In our
experiments, the thermal energy provided by microwave irra-
diation promotes the silver ions to diffuse into random Zn2+
lattice sites. The formation of the ZnS shell provides more space
for Ag ions and prevent the segregation of Ag on the parti-
cle surface [17]. As a result, more doped Ag ions can occupy
the Zn2+ lattice sites and act as effective luminescent centers.
This also contributes to the enhancement of the luminescent
quantum yield.
497
4. Conclusions
In this work, ZnS shell was deposited on surface of ZnS:Ag
nanocrystals by a microwave assisted epitaxy growth method.
Growth of the shell was induced by thermal decomposition of
Zn–MPA complex under microwave irradiation. The quantum
yield of the nanocrystals was enhanced significantly after the
shell growth. The formation of ZnS shell during the microwave
treatment can eliminate the surface defects and avoid the segre-
gation of Ag+ on the particle surface. This work will be helpful
for the preparation of doped nanocrystals with qualified PL
intensity.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China and the Key Project of Chinese Ministry
of Education.
References
[1] H. Weller, Angew. Chem. Int. Ed. 32 (1993) 41.
[2] M.J. Bruchez, M. Moronne, P. Gin, S. Weiss, A.P. Alivisatos, Science 281
(1998) 2013.
[3] X. Peng, Chem. Eur. J. 8 (2002) 338.
[4] T. Jin, F. Fujii, H. Sakata, M. Tamura, M. Kinjo, Chem. Commun. 22 (2005)
2829.
[5] R.N. Bhargava, D. Gallagher, X. Huang, A. Nurmrikko, Phys. Rev. Lett.
72 (1994) 416.
[6] B. Xia, I.W. Lenggovo, K. Okjuyama, Chem. Mater. 14 (2002) 4969.
[7] S. Sapra, A. Prakash, A. Ghangrekar, N. Periasamy, D.D. Sarma, J. Phys.
Chem. B 109 (2005) 1663.
[8] L. Sun, C. Liu, C. Liao, C. Yan, J. Mater. Chem. 9 (1999) 1655.
[9] J. Huang, Y. Yang, S. Xue, B. Yang, S. Liu, J. Shen, Appl. Phys. Lett. 70
(1997) 2335.
[10] B.L. Abramsa, L. Williams, J.S. Bang, P.H. Holloway, J. Appl. Phys. 97
(2005) 3521.
[11] H.H. Choi, M. Ollinger, R.K. Singh, Appl. Phys. Lett. 82 (2003) 2494.
[12] J.-S. Bang, B. Abrame, B. Wagner, P.H. Holloway, J. Appl. Phys. 95 (2004)
7873.
[13] A.A. Bol, A. Meijerink, J. Phys. Chem. B 105 (2001) 10197.
[14] B.O. Dabbousi, J. Rodriguez-Viejo, F.V. Mikulec, J.R. Heine, H. Mat-
toussi, R. Ober, K.F. Jensen, M.G. Bawendi, J. Phys. Chem. B 101 (1997)
9463.
[15] X. Peng, M.C. Schlamp, A.V. Kadavanich, A.P. Alivisatos, J. Am. Chem.
Soc. 119 (1997) 7019.
[16] H. Yang, P.H. Holloway, Adv. Funct. Mater. 14 (2004) 152.
[17] W. Jian, J. Zhuang, L. Wang, J. Dai, W. Yang, Y. Bai, J. Phys. Chem. B,
submitted for publication.
[18] B.D. Cullity, Elements of X-ray Diffraction, Addison-Wesley, Boston,
1956, p. 99.
[19] L. Spanhel, H. Weller, A. Fojtik, A. Henglein, Ber. Bunseges. Phys. Chem.
91 (1987) 88.
[20] J.F. Reber, M. Rusek, J. Phys. Chem. 90 (1986) 87.