J Sol-Gel Sci Technol DOI 10.

1007/s10971-013-3030-9

ORIGINAL PAPER

Band edge emission of ZnS nanoparticles prepared by excess of thiourea as a source of sulfur
S. Wageh Ahmed A. Al-Ghamdi F. Yakuphanoglu

Received: 5 February 2013 / Accepted: 1 April 2013 Springer Science+Business Media New York 2013

Abstract We have synthesized ZnS nanoparticles capped with mercaptoacetic acid with band edge emission at 327 nm (3.79 eV). The synthetic procedure for producing the band edge emission is mainly dependent on the reuxing time and on using a high ratio of sulfur source at the preparation time to diminish the sulfur deciency trapping centers. The effect of reuxing time showed the presence of shallow levels due to the interstitial sulfur and zinc ions for the short reuxing time samples up to 11 h, whereas, the prolonged reuxed samples showed the diminishing of the shallow levels. The photoluminescence exhibits a band edge emission with a narrow full width at half maximum for the dispersed samples in aqueous solution and the photoluminescence excitation elucidated the transition energies of the shallow traps and the band edge. In addition, the bound excitons and the spinorbitsplit off energy transitions are identied from the photoluminescence excitation. Huang Rhys factor S was determined from the difference between the photoluminescence excitation and photoluminescence spectra. The obtained value of S is agreeing well with published value obtained from the temperature dependence of the band gap of ZnS.
S. Wageh A. A. Al-Ghamdi F. Yakuphanoglu Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia S. Wageh (&) Physics and Engineering Mathematics Department, Faculty of Electronic Engineering, Menoua University, Menouf 32952, Egypt e-mail: wageh1@yahoo.com F. Yakuphanoglu (&) Department of Physics, Faculty of Science, Firat University, Elazig, Turkey e-mail: fyhan@hotmail.com

Keywords ZnS Nanoparticles UVVis Absorption Luminescence Luminescence excitation

1 Introduction Semiconductor nanocrystals have been receiving a great attention of the scientic and engineering researchers in the recent years, due to their fascinating optical and electronic properties. The quantum connement in nanocrystals induces a discretization of electronic states, very much like in atoms and molecules. The resulting physical properties of the nanocrystals depend on their size and can thus be tuned by varying their dimensions. These properties and the preparation of the nanocrystals have been extensively studied theoretically and experimentally by a lot of researchers including our group, in particular for II-VI semiconductor quantum dots [115]. Among II-VI, zinc sulde nanocrystals have been extensively studied due to their outstanding physical properties. Bulk zinc sulde is a semiconductor with a wide direct band gap energy in the near-UV region of the electromagnetic spectrum. Consequently, ZnS nanocrystals will be promising materials for absorption and emission in UV region. In addition, ZnS nanocrystal will be transparent from the mid-IR through the visible region and may be useful in optical phase modulation, IR antireection coatings, light guiding and ultraviolet detectors. So, an extensive work is required for preparation of nanoparticles of superior quality and more efcient luminescence. It is desired to prepare the band edge emission of the nanoparticles for fundamental science and applications. Chemical methods have recently been extensively applied to synthesis and design of materials with new structures and properties because the suitable solvents/stabilizing agents can prevent the particles from agglomeration.

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Among the stabilizing and capping agents carboxylic acids and thiol groups capped semiconductor particles have the ability to vary the functional groups at the surfaces and, thus, regulating the chemical behavior of the particles. This opens the eld of doing chemistry with the preformed particles and built-up of larger structures consisting of nanocrystals of one kind, hetero-atomic structure made from different semiconductor materials, or even the connection of semiconductor and metal particles. In view of this information, this work concerns with the preparation of ZnS nanoparticles capped with meracaptoacetic acid which have the carboxyl and thiol groups. It is very useful to obtain nanoparticles which have the band edge emission. Nanoparticles with band edge emission will be promising as an active material for various optoelectronic applications [1620]. Without the band edge emission we cant get the size-tunable emissions of the nanoparticles. In conclusion, we have synthesized ZnS nanoparticles capped with mercaptoacetic acid in N, N-dimethylformamide (DMF), Zn (CH3COO)22H2O as a source of zinc ions and thiourea as a source of sulfur ions. The synthesized nanoparticles have a high intensity band edge emission with a small band width at 327 nm (3.79 eV). The synthesizing route is mainly dependent on the using of high ratio of the source of sulfur to solve the problem of sulfur deciency. It is known that, the sulfur deciency creates a trapping center which strongly affects on the band edge emission for sulde compounds.

D/Max2000 powder diffractometer with CuKa radiation. Ultraviolet absorption spectra were measured using a Shimadzu UV-3101 PC spectrometer. The photoluminescence (PL) and photoluminescence excitation (PLE) were taken by SPEX uorology model FL3-21 spectrouorometer. All optical measurements were conducted at room temperature which was at that time 20 C.

3 Results and discussion 3.1 X-ray powder diffraction and nanoparticles sizes Zinc sulde crystallizes in zinc-blende and wurtzite phases, with cubic and hexagonal crystal structures, respectively. The two phases are characterized by a cation tetrahedral coordination and contain close-packed sulfur layers with zinc atoms occupying one half of the tetrahedral interstices. We have studied the crystal structure of precipitated ZnS nanoparticles by X-ray diffraction technique. Figure 1 shows the wide angle XRD patterns of F and G samples. The calculated inter-planer distances for the diffraction peaks (100)H, 3.131 A ((002)H, appeared for F sample are 3.206 A , (111)C), 2.710 A (200)C, 2.575 A, 2.271 A, 2.1795 A 2.058 A (110)H, 1.865 A, 1.860 A, 1.818 A, 1.762 A (103)H ((200)H, (311)C). However the d values for the and 1.612 A (100)H, diffraction peaks appeared for G-sample are 3.206 A (002)H, (111)C, 2.935 A (101)H, 2.702 A (200)C, 3.125 A , 1.916 A ((110)H, (220)C), 1.864 A , 1.711 A (103)H 2.553 A ((200)H, (311)C). We have compared the and 1.692 A observed diffraction lines with the standard diffraction lines of hexagonal and cubic structures [21, 22]. In addition, the relative percentage errors of the observed inter-planer distances relative to the standard d values of hexagonal and cubic structure are calculated as follows:   dObserved d  Relative percentage error 100 1 d where, d(observed) represents the experimental inter-planer distance value and d is the standard value of the interplanar distance. According to the comparison of the relative intensity and the relative percentage errors with the standard hexagonal and cubic structures, the structure of F sample matched the cubic modications of ZnS better than the hexagonal one. Whereas, the structure of G sample is close to the hexagonal structure relative to F sample due to the appearance of (101) reection. We can attribute this change in the structure for the sample G to the longer stirring time of the sample during precipitation of the nanoparticles. Besides the main peaks characteristics to cubic and the hexagonal structures, other small reections appeared for F and G samples. These peaks may be due to

2 Experimental We have synthesized ZnS nanoparticles using mercaptoacetic acid as the capping agent, zinc acetate as a source of zinc and thiourea as a source of sulfur. The starting molar ratio of Zn(CH3COO)22H2O: thiourea: mercaptoacetic acid is 1:2:2.4. Briey, a solution of Zn (CH3 COO)22H2O and thiourea in dimethylformamide (DMF) followed by the addition of mercaptoacetic acid then the pH was adjusted to pH = 9 by adding 2 M NaOH solution, under vigorous stirring in an N2 atmosphere. The solutions were reuxed for different times (up to17 h) at a temperature of 13 C. Five samples were prepared called A, B, C, D and E with reuxing times 4, 5, 11, 13 and 17 h, respectively. Another sample prepared by reuxing the solution for 17 h then reserved in the refrigerator for 12 h at 5 C. Then the nanoparticles were extracted by precipitation with the addition of acetone to the solution. This process was repeated for the supernatant, two samples are obtained are called F and G. The resulting powder was separated by centrifuging and then dried in vacuum at room temperature and ready to dissolve in many solvents including water. Crystal structure of nanoparticles was characterized by XRD. X-ray powder diffraction analysis using a Rigaku

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the excess of sulfur ions or the crystallized organics bonded to surface of the nanoparticles. In this size regime the organicinorganic interface becomes pivotal, because about 40 % of the atoms making up the nanoparticles located on its surface. The lattice parameters are evaluated from the relation, p a d h2 k2 l2 , where h, k and l are the Miller indi , which ces. The calculated lattice parameter is 5.404 A for nearly equals the standard value for ZnS (a = 5.406 A Cubic ZnS (JCPDS- ICDD No.5-0566). We have calculated the nanoparticle size from the fullwidth at half maximum (FWHM) of the XRD peaks. The average particle size of the nanoparticles can be obtained by the following relation [23]: D Kk b cos h 2

the Bragg equation, we can roughly calculate the distance between nearest neighbors from the position of the rst shoulder. This distance can be considered as the distance between the centers of the two nanoparticles, beside each other, and equal the diameter of the nanoparticles. The calculated value for the F sample is 4.01 nm which is larger than the diameter obtained from the Scherrers equation, indicating that the particles are separated from each other by a shell of organic ligands around them. It is expected that this result is due to the larger size of the nanoparticles determined by small angle diffraction relative to the size evaluted by Scherrers equation, because the Scherrers equation determines the nanocrystallite core, but the size of determined from small angle is the distance from the center of nanoparticles to the center of neighboring one. 3.2 UVVis absorption spectra Figure 3 shows the UVVis absorption spectra of samples A, B, C, D and E. The sample reuxed for 4 h (sample A) shows a relatively broad absorption with a maximum centered at 310 nm (3.997 eV) along with absorption tail. For the sample reuxed 5 h (sample B), beside the main absorption band with maximum centered at 308 nm (4.023 eV) another absorption shoulder appeared at 330 nm (3.755 eV). The intensity of this shoulder is increased with increasing reuxing time up to 11 h, as clear from the spectrum of sample C. Further increase in reuxing time up to 13 and 17 h (D and E samples), the observed absorption spectra consists of only one band at 307 nm and shoulders appeared for B, C samples are disappeared. We have tted the absorption spectra of A, D and E samples by single Gaussian peak, while, the spectra of B and C samples are tted by two Gaussian peaks as shown in
Intensity (arb. units.)

where, k is the X-ray wavelength, b is the FWHM, h is the diffraction angle, and K is the form factor (K = 0.9). The calculated sizes are 3.54 and 3.51 nm for F and G samples, respectively. The calculated average particle sizes within error about 2 % as the data of the X-ray collected with a step size 0.04. We should bear that the real error is more than this value because of the other factors affect on the broadening of the X-ray diffraction peak such as strain and instrument. We have also studied the small angle diffraction patterns for the two samples, as shown in Fig. 2. The diffraction pattern for sample F shows a shoulder at 2.2 and two diffraction peaks at 6.9 and 9.1. These diffraction peaks are caused by some short-range ordering of particles in the powder. The appearance of x-ray diffraction peaks in the small-angle region for the nanomaterial indicates that the nanoparticles have a narrow size distribution. By using

Intensity (arb. units.)

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Fig. 1 Wide angle X-ray diffractograms of ZnS nanoparticles capped with mercaptoacetic acid

Fig. 2 Small angle X-ray diffractograms of ZnS nanoparticles capped with mercaptoacetic acid

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Fig. 3. We found that the widths of the main absorption bands, nearly at 307 nm, for the B and C samples are highly decreased relative to the width of the main peak at 310 nm appeared for sample A. While for D and E samples the widths of the absorption bands, nearly at 307 nm, are larger in comparison with the same band appeared for B and C samples. In contrast the width of the absorption bands for samples D and E nearly at 307 nm is very smaller relative to width of the 310 nm band appeared for sample A. The long absorption tail and shoulders appeared for A, B and C samples can be attributed to the following: (1) growing of different size distributions and larger size of the nanoparticles, (2) the defects in the grown ZnS nanoparticles like Zn, S vacancies and Zn, S interstitial. The rst reason is canceled out as a result of the following: (a) the disappearance of the shoulder appeared for the samples reuxed for long times, (2) the decrease of the band width of the main predominant band (3) the shift of the center of the main band to higher energy by about 3 nm. Consequently, we attributed the appearance of this shoulder for the samples reuxed for short times to the various defects

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in ZnS nanoparticles. We will discuss in detail these defects by the photoluminescence and photoluminescence excitation spectroscopies. We have studied the absorption of the precipitated samples dispersed in aqueous solution. Figure 5 shows the absorption spectra of F and G samples. The absorption band of G sample has a small width and little shifted to higher energy relative to F sample, which indicate a small size distribution of G sample with respect to F sample. On the other hand, the absorption band of F and G samples shift to higher energy with respect to A, B C, D and E samples. We attributed this shift to the following reasons (1) The difference in the dielectric constants between DMF and the water, (2) The improvement of the lattice structure during the precipitation method due to the elevation of temperature. The absorption spectra of E and F samples have one absorption maximum centered at 294 (nm) (4.21 eV) and 292 nm (4.24 eV), respectively, these absorption bands are attributed to E1s1s absorption energy. The E1s1s for E and F samples are blue shifted from n = 1 exciton of the cubic bulk ZnS by 0.3978 and 0.441 eV, respectively. The energy of n = 1 exciton of bulk ZnS is 3.8022 eV [24]. The blue shift of E1s1s is due to the quantum size effect. According to the difference between the E1s1s and the energy of the bulk band gap of ZnS, we have calculated the size of the nanoparticles using effective mass approximation with innite connement potential. The calculations are based on the proposed following relationship for the particle size dependent energy gap [25]: a 2 aB B E1s1s Eg bulk p2 R 0:248R R y 1:786 y a a y 3 where, E1s1s is the energy gap of the ZnS nanoparticles, Eg is the bulk band gap energy of ZnS (3.66 eV), a is the nanoparticles radius, aB is the exciton Bohr radius (aB = 2.5 nm), and R y is the exciton Rydberg energy (Ry 34:7 meV). The calculated nanoparticles sizes in diameter for F and G samples are 3.64 and 3.56 nm, respectively. The calculated sizes are slightly more than the obtained result from X-ray analysis. On the other hand, we have calculated the sizes of the nanoparticles according the published formula between the position of the wavelength of the rst absorption maximum and the diameter of the nanoparticles as follows [26, 27]:

C
308 nm

B
310 nm

A
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0:13 k1s1s 186:7dnanoparticle

Wavelength (nm)

Fig. 3 UV-vis absorption spectra for the samples reuxed at different times (circles) and the solid lines is the Gaussian tting for the absorption spectra. The A, B, C, D and E samples are reuxed for 4, 5, 11, 13 and 17 h, respectively

where, k1s1s is the wavelength of the rst absorption maximum and d is the diameter in angstrom of ZnS nanoparticles. The calculated nanoparticles diameters for F and G samples are 3.37 and 3.12 nm, respectively, which are slightly smaller than that obtained from X-ray analysis.

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On the other hand, we have determined the size distributions of G sample form the absorption spectrum. First the absorption spectrum was replotted versus the energy. Then, we have tted the absorption spectra with a Gaussian function as shown in the inset of Fig. 4. The Gaussian function formula as follows: " # AB 2 AB EAB E exp 5 ABpeak 2DEAB 2 ; DEAB is AB is the mean energy corresponding to R where E the variance. AB is the absorbance of the sample; it cor. The responds to a nanocrystal of certain mean radius R absorption is normalized with respect to the maximum height ABpeak of the main exciton peak. Realizing that the absorbance AB is proportional to the nanocrystals number, the size distribution can be determined from Eq. (5). According to these calculations our samples generally have standard deviations, less than 11 %. 3.3 Photoluminescence We have studied the photoluminescence and photoluminescence excitation to investigate the sources of the different emission states. Figure 5ad show the photoluminescence at different excitation energies for C sample. Figure 6a shows the photoluminescence at different excitation wavelengths from 280 to 300 nm with 10 nm steps. The photoluminescence spectra consists of a shoulder which cover the range from 350 to 385 nm with predominant emission peak nearly centered at 408 nm. The shoulder covers the range of the emission states of the sulfur and zinc interstitial ions. While

292 nm 294 (nm)

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Fig. 4 UV-vis absorption spectra for F and G samples dispersed in aqueous solution. The inset is the Gaussian tting according Eq. (5) of the spectrum of G sample

the predominant emission peak centered at 408 nm cover the range of zinc and sulfur vacancies. Figure 5b shows the photoluminescence at different excitation wavelengths from 310 to 330 with 5 nm steps. This range of excitations covers the position of the shoulder appeared from the absorption study. The emission consists of a shoulder at 360 nm and a predominant peak centered at 407 nm. The shoulder appeared at 360 nm is shifted to lower energy with increasing excitation wavelength up to 372 nm. This result indicates that there are two emission states with different energies in this range. These two emission states at 360 and 373 nm are attributed to sulfur and zinc interstitial ions, respectively. Figure 5c shows the emission at different excitation wavelengths from 335 to 350 nm with 5 nm steps. The emission consists of the shoulder at 375 nm which attributed to interstitial zinc ions along with the predominant peak centered at 408 nm which may be mainly due to Zn vacancies. Figure 5d shows the photoluminescence at different excitation wavelengths from 355 to 375 with 5 nm steps. The emission shows only one predominant peak centered at 410 nm for the samples excited at 355 and 360 nm. With increasing excitation wavelength the emission intensity decreased and shifted to 415 nm. We attributed the emission peak centered at 415 nm to sulfur vacancies. The low intensity of this peak in our sample due to the used of a high ratio of sulfur source in the preparation of the nanoparticles. These results indicate that this sample which reuxed for short times at low temperatures in DMF solvents have a number of defects which effect on the luminescence. The emissions caused by the defects are predominant and the band edge emissions are weak. These defects are as follows: zinc vacancies and interstitial sulfur act as an acceptor state and sulfur vacancies and interstitial zinc act as donor states. We have studied the photoluminescence for E sample. Figure 6a shows the photoluminescence for the E sample at excitation with wavelength 305 nm which equals the rst absorption maximum E1s1s for this sample. Clearly, the photoluminescence consists of a sharp peak at 346 nm and another peak at 369 nm along with a broad peak covering the range from 377 to 528 nm and centered at 401 nm. The peaks at 346 and 401 nm are attributed to near band edge emission and zinc vacancies, respectively. While, the peak appeared at 369 nm are attributed to interstitial sulfur, the discreteness of this peak is due to the using of high ratio of sulfur source during the preparation. The emission of sample E due to the excitation at 325 nm mainly consists of two peaks at 362 and 410 nm as shown in Fig. 6b. This result indicates that the interstitial sulfur plays an important role in the emission of these samples. Figure 7 shows the emission spectra for sample F excited at 300 and 305 nm. The photoluminescence of the

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(a)
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Fig. 5 a Photoluminescence spectra of C sample at different excitation wavelengths from 280 to 300 in 10 nm steps. b Photoluminescence spectra of C sample at different excitation wavelengths from 305 to 330 nm in 5 nm steps. c Photoluminescence spectra of C

sample at different excitation wavelengths from 335 to 350 nm in 5 nm steps. d Photoluminescence spectra of C sample at different excitation wavelengths from 355 to 370 nm in 5 nm steps

sample excited at 300 nm consists of two peaks one sharp at 327 nm and the other broad emission peak centered at 362 nm. These two peaks are attributed to band edge emission and shallow traps due to interstitial sulfur, respectively. Whereas, for the sample excited at 305 nm the emission maximum of the high energy peak is slightly shifted toward lower energy. Clearly, for the two excitation energies the intensity of the peak due to sulfur vacancies is greatly diminished and the intensity of the higher energy emission band is greatly increased. In addition, the full width at half maximum of the band edge emission is relatively small, about 35 nm. These results indicate that the use of high ratio of sulfur in the preparation of ZnS can cancel out the emission due to sulfur vacancies and lead to an improvement of the band edge emission. To best our knowledge, up to now there is no published work about the preparation of band edge emission of ZnS nanoparticles with thiourea as a source of sulfur. Also, we have studied the emission spectra of the G sample. Figure 8 shows the emission spectra of G sample at the excitation wavelengths 300 and 305 nm. Clearly, there is an observable difference between this sample and F

sample. Also the band edge emission with high intensity and small half width is appeared but the intensity of the emission due to sulfur deciency is slightly increased again. We attributed the increase of sulfur deciency for this sample to the long reuxing time of this sample during the precipitation method which may cause evaporation of sulfur. 3.4 Photoluminescence excitation To completely study the energy levels scheme of the prepared samples we have studied the photoluminescence excitation. Figure 9 shows the photoluminescence excitation of sample C which has shoulder at 330 nm in the absorption spectrum. Clearly, three excitations appeared with wavelengths at 322 nm (3.85 eV), 345 nm (3.59 eV) and 360 nm (3.44 eV). The excitation intensities for the bands at 345 and 360 nm have high intensity relative to the excitations near the band edge. This result indicates that the effect of trapping centers is predominant for this sample. For F sample which has high intensity band edge emission,

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Fig. 7 Photoluminescence spectra of F sample at the excitation wavelengths 300 and 305 nm

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Fig. 6 a Photoluminescence spectra of E sample at the excitation wavelength = 305 nm. b Photoluminescence spectra of E sample at the excitation wavelength = 325 nm

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Fig. 8 Photoluminescence spectra of F sample at the excitation wavelengths 300 and 305 nm

the photoluminescence excitation shows new three bands at 293 nm (4.229 eV), 296.9 nm (4.173 eV) and 300 nm (4.13 eV) as shown in Fig. 10. Also the bands at 323 nm, 340 nm and 360 nm appeared but with less intensity. This means that this sample has a less number of trapping centers and conrms the results of photoluminescence study. On the other hand, the calculated difference between the excitation state at 4.173 eV and at 4.13 eV is equal 0.043 eV which equals to the exciton binding energy of ZnS. Zinc sulde is a large band gap material with a relatively small static dielectric constant and relatively large effective mass with exciton binding energy at about 43.7 meV. Consequently, the bound exciton in ZnS is stable at room temperature which gives us the possibility of detecting the bound exciton

transition by smoothly changing the emission wavelength in photoluminescence excitation measurement. Another important result is the difference between the excitation state at 4.229 eV and at 4.13 eV which equal 0.07 eV, equivalent to the spinorbitsplit off energy for ZnS [28]. We have determined the Huang Rhys factor (Coupling constant) S from the difference between the excitation and emission bands and also from of the line broadening of band edge emission. Figure 11 shows the photoluminescence from F sample excited at 300 nm wavelength along with the photoluminescence excitation for emission at 327 nm. We have calculated the coupling constant from the displacement between

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Intensity (arb. units.)

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Fig. 9 Photoluminescence excitation of C sample for different emissions

Fig. 11 Photoluminescence of F sample excited at 300 nm wavelength along with the photoluminescence excitation for emission at 327 nm

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DFWHM is full width at half maximum. The calculated coupling constant S is 2.73 which agrees well with the reported value for cubic ZnS [31].

4 Conclusions We have synthesized ZnS nanoparticles capped with a bifunctionl organic molecule in DMF solvents and using a high ratio of sulfur source. The synthesized ZnS nanoparticles have a cubic structure with a nanoparticles size about 3.5 nm as revealed by X-ray analysis and UVvis absorption spectroscopy. We have investigated the synthesis of ZnS nanoparticles with different reuxing times. The absorption spectroscopy showed the appearance of shallow levels due to interstitial sulfur and zinc ions for the samples reuxed less than 13 h. Whereas, these shallow levels disappeared for the samples reuxed for long times. The photoluminescence spectroscopy revealed that the trapping centers are predominant for the samples reuxed for short times while the samples reuxing for long times the band edge emissions are predominant. On the other hand, the photoluminescence excitation dened the ne structure of the excitation levels. Also, the bound exciton and spinorbitsplit off transition energies are determined from the photoluminescence excitations.
Acknowledgments Thanks are due to the Deanship of Scientic Research (DSR) at King Abdulaziz University, Jeddah, Saudi Arabia, for facilitating and support for the research group Advances in composites, Synthesis and applications, such work is as a result of DSR project fund #(Gr34/4). This work is as a result of international collaboration of the group with Prof. F. Yakuphanoglu.

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Fig. 10 Photoluminescence excitation of E sample for different emissions

centers of the band edge emission and the center of photoluminescence excitation band (Stokes shift) as follows [29]: DStocks 2S hxLO 6

where  hxLO is the phonon energy of ZnS (43.7 meV). The calculated S value from the Stokes shift is 3.7. The value of S is in a good agreement with the reported value from the temperature dependence of the band gap of ZnS epilayers grown on GaAs substrates [30]. On the other hand, the full width at half maximum is related to coupling constant S as follows: p DFWHM 2 7 hxLO s

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