Optical Materials 34 (2012) 12311234

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Optical Materials
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Short Communication

Visible light emission from selenium color centers formed in silicate glasses
Jeon Choi a, Jong Heo b, Yong Gyu Choi c, Woon Jin Chung a,
Institute for Rare Metals and Division of Advanced Materials Engineering, Kongju National University, Cheonan, Chungnam 330-717, Republic of Korea Department of Materials Science and Engineering and Division of Advanced Nuclear, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk 790-784, Republic of Korea c Department of Materials Science and Engineering, Korea Aerospace University, Goyang, Gyeonggi 412-791, Republic of Korea
b a

a r t i c l e

i n f o

a b s t r a c t
We experimentally verify that a color center in the form of Se 2 takes shape in silicate glasses containing relatively small amount of ZnSe which are prepared via a conventional melt-quenching process. Samples also produce broad photoluminescence when excited with UV light source, suggesting potential applications in the visible range. Analyses based on X-ray diffraction patterns, high resolution transmission electron microscopy, and Raman spectroscopy support the formation of Se 2 color centers in addition to Se nanocrystals. 2012 Elsevier B.V. All rights reserved.

Article history: Received 30 November 2011 Received in revised form 30 January 2012 Accepted 30 January 2012 Available online 22 February 2012 Keywords: Se Glasses Color centers ZnSe Luminescence

Introduction Glasses capable of incorporating quantum dots (QDs) inside have been extensively studied in order to take advantage of their optical properties as they have high quantum efciency in their radiative bandgap transition and their bandgap energy is easily tunable through controlling the dot size [13]. In particular, glasses with narrow bandgap semiconductor QDs such as PbS and PbSe [3 5] exhibit broad emission bands which can cover the entire optical telecommunication window (1.21.7 lm) simply by varying the size of the QDs via thermal treatment. Recently, more attention has been paid to radiative emission in the visible wavelengths because of diverse applications such as the active layer of solar cells, light-emitting diodes and even bio-imaging of materials [69]. In this respect, after careful preparation via a solution based chemical synthesis, CdS (or Se) QDs that possess extended bandgap energy corresponding to the visible range are mostly studied for such applications. CdS (or Se) QDs can also be incorporated into the glass matrix via conventional melt-quenching method followed by proper thermal treatment [1013]. Xu et al. observed bandgap adjustment of CdSe QDs within the visible range in silicate glasses [13]. They precipitated CdSe QDs from silicate glass containing CdO and ZnSe, but the role of ZnSe for the formation of CdSe QDs was
Corresponding author. Address: Division of Advanced Materials Engineering, Kongju National University, 275 Budae-dong, Seobuk-gu, Cheonan, Chungnam 330717, Republic of Korea. Tel.: +82 41 521 9377; fax: +82 41 568 5776. E-mail address: wjin@kongju.ac.kr (W.J. Chung).
0925-3467/$ - see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.optmat.2012.01.037

not clearly provided. The solgel process [6,1417] can be used for making ZnSe QDs within glasses, thus providing visible emissions near green wavelengths. Chalcogen elements, however, can also give the visible emission in the form of color centers such as S 2 or Se2 without forming semiconductor QDs when they are incorporated successfully in the inorganic host materials [1820]. Electronic transitions between the molecular orbital states of these radicals are responsible for the absorption and corresponding photoluminescence [1820]. It is worth mentioning that these chalcogen color centers have mostly been accommodated in inorganic crystals based on halides or sodalite structures. As long as a glass matrix is concerned, so far the formation of these color centers has hardly been reported, so that a successful demonstration of the color centers in glass matrix can be a good option for their practical applications. In this study, we prepared silicate glasses with ZnSe in an effort to form such chalcogen based color centers via conventional meltquenching method. We conspicuously observed change in the color and photoluminescence of the glass samples, which were attrib uted to the Se 2 color centers. The formation of Se2 color centers and nanocrystals within the silicate glasses is identied. As ZnSe was added to promote the Se 2 color centers, the formation of ZnSe QDs is highly probable and their possible effects on the structural and optical properties were also discussed. The silicate glass with the composition of 65SiO2A25Na2OA 5BaOA5ZnO (in mol%) was chosen to which ZnSe was added by 0.5, 1, 3 and 5 mol%. In order to compare the effects of ZnSe, a glass sample with additional 5 mol% of Se was also prepared. High purity

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(>99.9%) raw materials were weighed and thoroughly mixed. Batches were melted in an alumina crucible at 1350 C for 1 h under ambient atmosphere. The melts were quenched on a brass mold and subsequently annealed at 350 C for 1 h to eliminate thermal stress. Without any further heat treatments, the resulting homogeneous glasses were then cut into shapes and optically polished for further investigations. A UV/VIS/NIR spectrophotometer (PerkinElmer, Lambda 750) and uorescence spectrometer (Perkin Elmer, LS55) recorded absorption and photoluminescence spectra of the samples, respectively. An X-ray diffractometer (Rigaku, D/MAX-2500U) and eld-emission TEM (JEOL, JEM-2100F) were used to identify the crystalline phase. Structural change was monitored by using a Raman spectrometer (HORIBA JobinYvon Ltd., SPEX 1403) with 514 nm excitation and X-ray photoelectron spectrometer (Thermo Scientic, Multilab ESCA2000). All measurements were performed at room temperature. UV/VIS absorption spectra of the silicate glasses with varying ZnSe content are shown in Fig. 1. The inset gure represents the visible PL spectra of the glasses when excited at 266 nm. As shown in the gure, the absorption peak at $365 nm increased as ZnSe was added to the glasses, and the color of the glasses also darkened to orangebrown. It should be noted that the glass with 5 mol% Se was transparent and gave no absorption peak at the corresponding region. The addition of ZnSe thus exerts an important effect on the optical properties of the glasses. Low vaporization temperature of elemental selenium, however, might have also prevented the formation of such absorption centers in the sample with just Se. Considering the bandgap energy of ZnSe (E0 $ 2.82 eV or equivalently $440 nm at 10 K), the absorption peak could be regarded as the rst excitonic transition of ZnSe QDs if successfully formed. Distinct absorption peak due to the excitonic transitions are well observed in other semiconductor QDs such as PbSe, PbS, CdSe and CdS within glass matrices [35,1013]. As shown in the inset gure, the UV-excited PL spectra have a broad emission band centered at $550 nm and show a marginal red-shift as ZnSe increases. The broad visible emission centered at the green to yellow wavelengths suggests the potential of the present glass as a phosphoric material in the visible range. The emission from the present glasses was similar to those observed previously from the glasses with ZnSe QDs which showed emission peak above 2.42.5 eV [15,17]. However, it should be mentioned that the emission from the intrinsic transition of ZnSe QDs around 2.5 eV was dramatically lower and hard to observe at room temperature in borosilicate glasses, especially these with high content (up to 0.6 mol%) of ZnSe QDs [1416]. The formation of QD clusters and delocalization of the excitons were responsible for the

phenomena [15]. As such, the emissions are not explained just in terms of ZnSe QDs, and a proper alternative rationale is thus required for the stable emission of the present glasses with high content of ZnSe as a starting material at room temperature. Emission spectra similar to those observed from the current glass samples also can be found in halide or sodalite crystal structures embedding Se 2 or Se2 di-radical color centers [18,19]. An absorption band near $365 nm can also be found in those crystals, supporting the possible origin of the absorption and emission spectra of the present glasses. The absorption near $3.6 eV in KI crystal was attributed to the 2Pg ? 2Du transition of Se 2 [20] while Schlaich et al. ascribed the absorption near $28,000 cm1 ($357 nm) to the photo-chemically formed Se2 di-radical from Se 2 within the Na8[Al6Si6O24]Cl2 sodalite structure. The formation of Se 2 thus seems to be responsible for the optical properties. However, it should be noted that the present glass did not yield another com1 mon Se [19]. The signicant dif2 absorption band at $20,000 cm ference in crystallographic environment of the crystals and glass could modify the excited states of Se 2 , accounting for the behavior. Presence of any possible crystalline phases was examined with X-ray diffraction (XRD) as depicted in Fig. 2. A characteristic diffuse pattern of the glassy phase was observed for all the samples prepared. This indicates the formation of homogeneous glassy phase or possibly nano-crystalline phases with a few-nm scale. A small peak evolved at 2h $ 32 from the glass with 5 mol% of ZnSe implies such a possibility of nanocrystal formation. Here, it is interesting to nd that the peak does not match the ZnSe crystal as observed elsewhere [16] but coincides with the strongest (1 0 1) peak of elemental selenium (JCPDS #85-0568). High resolution TEM inspected the glass with 3 mol% of ZnSe in order to identify the possible formation of nanocrystals. As shown in Fig. 3, nanocrystals of $7 nm in size were well resolved within the silicate glass matrix. The glass with 5 mol% Se was also inspected by using HR-TEM but no original crystalline phase was found. The estimated d-spacing ($2.839 ) of the observed nanocrystals was compared to the possible compounds including ZnSe and Se crystals. The (2 0 0) of ZnSe (JCPDS #02-0479, int-f = 10) and the (1 0 1) of Se (JCPDS #85-0568, int-f = 999) were indexed to match the value. Considering the intensity factor of two planes in association with the XRD result, it is plausible to assume that the nanocrystals currently formed in our samples is elemental Se rather than ZnSe QDs. Nano-crystalline Se can also affect optical properties; Se nanocrystals formed by solution based or electrochemical synthesis [21,22] showed plasmon resonance absorption around 250 nm or absorption near $2.4 eV, proving little relationship of the Se nanocrystals to the absorption band at $365 nm of the present system.

Fig. 1. UV/VIS absorption spectra of the silicate glasses with ZnSe contents (x) of 0.5, 1, 3 and 5 mol%. The inset gure shows the normalized photo-luminescence of those glasses when excited at 266 nm.

Fig. 2. X-ray diffraction pattern of the silicate glasses with ZnSe contents (x) of 0.5, 1, 3 and 5 mol%.

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Fig. 3. TEM image of the silicate glass with 3 mol% ZnSe. The inset gure represents the diffraction pattern of the nano-crystals.

However, the formation of nanocrystals and their identication require further investigations. The presence of Se-related structures was investigated by Raman spectroscopy. A glass without ZnSe was prepared and also examined for comparison purpose. As shown in Fig. 4, strong Stokes shifted peaks at $323, 644, 965, 1287 cm1 developed as ZnSe content increased. A small peak at $267 cm1 also evolved with ZnSe content. ZnSe QDs normally produce characteristic transverse optical (TO) and longitudinal optical (LO) phonon modes at $205 and 250 cm1, respectively [16,17,23]. The intense Raman shifted peaks observed in Fig. 4 thus indicate negligible relationship to the ZnSe QDs. Instead, characteristic intense Raman peaks at $330 cm1 and its overtones, however, have been observed from the Se 2 containing crystal structures [19,24] which coincide well with the present results. A relatively small Raman peak at $260 cm1 was also observed in the Se 2 containing materials and assigned to the characteristic vibration mode of the Se chain. These results, therefore, clearly indicate the formation of Se 2 and possible formation of SeSe chains within the silicate glasses. The development of Raman peaks due to Se 2 as a function

of the ZnSe amount can also elucidate the origin of the absorption band at $365 nm as discussed earlier. In an effort to determine the formation mechanism of Se 2 and examine the structural role of ZnSe precursor, X-ray photoelectron spectroscopy of O 1s electrons within the glasses was performed and deconvoluted as reported for silicate glasses [25]. As depicted in the inset gure of Fig. 4, the fraction of non-bridging oxygen (NBO) was increased as ZnSe content increased. This suggests that ZnSe breaks the SiAOASi network within the glass, producing NBOs. As ZnSe provides selenium in lieu of oxygen, unlike ZnO, it seems reasonable to assume the formation of SiASe to break the silicate network. Additional bonding of Se-ion thus can form the Se 2 within the glass structure. If the glass contains Se nanocrystals, Se 2 can also result from the selenium defects at the surface of nanocrystals. The formation mechanism of Se 2 and Se nanocrystals are not clear at the moment, and further investigations are in progress. The formation of Se-related structures when the glass was synthesized with ZnSe, however, can provide a Se-rich local environment to other cations within the glass. We believe that other Se-based QDs such as CdSe or PbSe would also be formed within glass networks, when those glasses are prepared with ZnSe together with CdO or PbO as starting materials [13,26]. In summary, we observed the visible absorption and photoluminescence emission from silicate glasses with additional ZnSe. A broad emission centered at $550 nm proved potential for applications at the visible wavelengths such as UV-converting or color changing materials for light emitting diodes, displays or bio-imaging applications where other QDs are currently used. Formation of ZnSe QDs was considered but evidence supporting its presence was hardly found. Instead, the optical properties were attributed to the Se 2 color centers which have not been commonly reported in glass matrices. All the experimental characterization carried out in this study, i.e., XRD, HR-TEM and Raman spectroscopy, proved the presence of Se 2 color centers as well as Se nanocrystals. Here, the precursor ZnSe played a crucial role for the formation which requires further investigation. Acknowledgements This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (20100002406). The authors also thank Dr. Jung Ho Yoo, National Nanofab Center for his kind assistance on TEM measurements. Jong Heo is supported by Basic Science Research (2010-0022407), Priority Research Centers (2010-0029711) and World Class University (WCU) (R31-30005) Programs through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology. References
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