Ya. Shpotyuk*ab,
A. Ingramc,
O. Shpotyukde,
C. Boussard-Pledelb,
V. Nazabalb and
B. Bureaub
aCentre for Innovation and Transfer of Natural Sciences and Engineering Knowledge, University of Rzeszow, 1, Pigonia str., 35-959 Rzeszow, Poland. E-mail: yashpotyuk@gmail.com
bLab. Verres et Céramiques UMR-CNRS 6226, University of Rennes 1, 35042 Rennes Cedex, France
cOpole University of Technology, 75, Ozimska str., 45370 Opole, Poland
dVlokh Institute of Physical Optics, 23, Dragomanov str., 79005 Lviv, Ukraine
eInstitute of Physics, Jan Dlugosz University, 13/15, Armii Krajowej al., 42200 Czestochowa, Poland
First published on 22nd February 2016
By exploring the positron–electron annihilation technique in positron lifetime measuring mode, it is shown that principal rare-earth (RE) induced structural reconfiguration in Ga-codoped TAS-235 glass (that is a glassy Te20As29Ga1Se50 alloy) is related to occupation of intrinsic free-volume voids by embedded RE ions tightly connected with Ga-based tetrahedrons via strong covalent RE-Se/Te–Ga links. A gradual decrease in the intensity of the second component of two-term decomposed lifetime spectra of annihilating positrons accompanied with a detectable increase in the defect-related positron lifetime (thus inducing essentially a depressed rate in positron trapping) is evidenced by the example of Pr3+ ions added homogeneously to Te20As29Ga1Se50 glass in the amount of 500 ppmw. Observed changes in positron lifetime spectra are explained in terms of the competitive contribution of different occupancy positions in Ga-codoped glass available for RE ions and trapped positrons.
In contrast to oxide glasses, where a large variety of experimental techniques can be employed to study RE doping (such as nuclear magnetic and electron paramagnetic resonances, neutron diffraction, fluorescence line-narrowing and decay analysis),7,8 the structural probes to be successfully applied to ChG are very restricted. In order to ensure optimum low phonon energy environment for positively charged RE-ions, the ChG should be additionally modified by local negatively charged sites, which act like cation vacancies in crystals providing a total electrical charge compensation.8 Because of anomalously high electronegativity proper to oxygen O atom,9 an intrinsic atomic arrangement in oxide glasses can be adapted respectively to create own electrical charge misbalance needed to accommodate homogeneously the embedded RE ions without their clustering (and thus to overcome a parasitic concentration quenching of fluorescence).6–8 In ChG, which are characterized by close electronegativities for constituting atoms, the RE-incorporation induced structural reconfiguration cannot be simply over-balanced by intrinsic covalent-bonded atomic environment obeying full saturation in respect to the Mott's 8-N rule.9 Charge-compensation equilibrium in such a case is achieved only extrinsically, e.g. by additional sites randomly distributed in a glass matrix possessing locally uncompensated excess of negative electrical charge. In this respect, the ChG preliminary doped with Ga or In seem most efficient,6,10–15 where charge compensation for incorporated RE ions is satisfied due to local over-coordinated environment around these atoms whatever their main valence state. Under a given rate of these codopants, which do not disturb the glass-forming ability of the hosting ChG, the RE ions can reside homogeneously without forming tightly bounded atomic clusters.8 Thus, the most efficient structural tools to probe successful RE doping in ChG should be sensitive to hierarchical atomistic transformations squeezing (Ga,In)-codoped and RE-doped sites.
That is why the phenomenon of positron–electron annihilation in positron lifetime measuring mode, e.g. positron annihilation lifetime (PAL) spectroscopy known as high-informative free-volume probing method suitable for different solids despite their structural nature,16,17 is expected to be useful to characterize RE-doping in ChG. Indeed, the positron (the positive antiparticle of electron) can be imagined as highly electropositive probe in its interaction with matter, whatever the nature of the interaction (trapping in extended defects or due to decaying of bound positron–electron states known as positronium Ps atoms in structurally-intrinsic voids).16,17 Under condition of atomic-accessible free volume in Ga/In-modified ChG, the negatively charged sites related to incorporated codopants are most preferential occupancy positions for both positrons and RE-ions. So competitive contribution from corresponding annihilation paths parameterized through histogram of elementary positron–electron annihilation events forming PAL spectrum, is expected as numerical measure of RE doping.
In this research, the method of PAL spectroscopy will be first employed to study structural changes in Ga-modified TAS-235 glass (the known glassy-like Te20As30Se50 alloy widely used in IR chalcogenide photonics) caused by doping with Pr3+ ions.18–21
The PAL measurements were performed using a fast–fast coincidence system of 230 ps resolution (the full width at half maximum of single Gaussian determined by measuring 60Co isotope) based on two Photonis XP2020/Q photomultiplier tubes coupled to BaF2 scintillator 25.4A10/2M-Q-BaF-X-N detectors (Scionix, Bunnik, Holland) and ORTEC® electronics (ORTEC, Oak Ridge, TN, USA). The reliable PAL spectra were detected in a normal-measurement statistics (∼1 M coincidences) under stabilized temperature (22 °C) and relative humidity (35%). The channel width of 6.15 ps allows a total number of channels to be 8000. The radioactive 22Na isotope of relatively low ∼50 kBq activity prepared from aqueous solution of 22NaCl wrapped by Kapton® foil (DuPont™, Circleville, OH, USA) of 12 μm thickness was used as positron source sandwiched between two identical tested samples.
The raw PAL spectra were processed with LT 9.0 program.23 Accepting unchanged contribution intensity from a source with two inputs (with 372 ps and ∼2 ns lifetimes), these spectra were adequately decomposed into two components with τ1,2 lifetimes and normalized I1,2 intensities (I1 + I2 = 1). Under above spectrometer resolution, this allows an error-bar for such arranged measuring protocol not worse than ±0.005 ns in lifetimes and ±0.01 in intensities. Introducing third component in the envelope of fitting curves did not improve goodness of fitting significantly. So Ps formation is not proper for studied ChG in full agreement with previous results.21 The positron trapping modes, e.g. average positron lifetime τav., lifetime in defect-free bulk τb, trapping rate in defects κd and fraction of trapped positrons η were calculated exploring a formalism of known two-state positron trapping model.16,17,21,24–26 In addition, the (τ2 − τb) difference was accepted as a size measure for extended free-volume defects where positrons were trapped, as well as the τ2/τb ratio was taken as direct signature of nature of these trapping defects in terms of equivalent number of monovacancies.16
The PAL spectra of both parent and Pr3+-doped Te20As29Ga1Se50 glass reconstructed from x2-component fitting at the general background of standard source contribution are respectively depicted on Fig. 1a and b. The limited values of statistical scatter of variance tightly grouped around 0-axis testify that PAL measurements are adequately described within this fitting procedure. So the decaying behavior of PAL spectra on Fig. 1 can be reflected by sum of two exponents with different time constants inversed to positron lifetimes.16 The best-fit positron trapping modes for these samples along with experimental data for TAS-235 glass calculated within two-state model are given in Table 1.
Sample, state | Fitting parameters | Positron trapping modes | |||||||
---|---|---|---|---|---|---|---|---|---|
τ1 ns | τ2 ns | I2 a.u. | τav. ns | τb ns | κd ns−1 | τ2 − τb ns | τ2/τb | η | |
Te20As30Se50 | 0.202 | 0.360 | 0.400 | 0.264 | 0.244 | 0.86 | 0.12 | 1.47 | 0.17 |
Z = 2.30; ρ = 4.888 g cm−3 | |||||||||
Te20As29Ga1Se50 | 0.208 | 0.358 | 0.370 | 0.263 | 0.246 | 0.75 | 0.11 | 1.44 | 0.16 |
Z = 2.30; ρ = 4.912 g cm−3 | |||||||||
Te20As29Ga1Se50 + 500 ppm Pr3+ | 0.213 | 0.363 | 0.330 | 0.262 | 0.246 | 0.64 | 0.12 | 1.47 | 0.14 |
Z = 2.30; ρ = 4.910 g cm−3 |
It is obvious that Ga-codoping does not cause increase in defect-specific positron lifetime τ2 (like under crystallization),21 but rather leads to an opposite and very slight decaying tendency (decrease from 0.360 ns in TAS-235 glass to 0.358 ns in Ga-codoped Te20As29Ga1Se50 glass). In contrast, the intensity of second component I2 is subjected to more pronounced changes, e.g. rough dropping, thus resulting in gradual decrease in positron trapping rate in defects κd and, correspondingly, the fraction of trapped positrons η (Table 1). It means that Ga-codoping does not approach fragmentation of free-volume voids in TAS-235 glass as it occurs in crystallized Te20As28Ga2Se50 alloy.21
Then, it is found that doping of Te20As29Ga1Se50 glass with 500 ppmw of Pr3+ further depresses the process of positron trapping (in part, the κd and η values are respectively reduced to 0.64 ns−1 and 0.14), this tendency being realized via more essential increase in defect-related positron lifetime τ2 (from 0.358 ns to 0.363 ns) accompanied by strong decrease in I2 intensity (from 0.370 to 0.330). Noteworthy, neither defect-free bulk positron lifetime τb, nor average positron lifetime τav. are subjected to detectable changes (within an error-bar of PAL measurements) in these successive Ga-codoping and Pr3+-doping processes. Let's clarify physical meaning of these structural reconfiguration processes grounded on previous results for similar chalcogenide glass-forming systems.20–22,26–30
Thus, it is well justified that among huge diversity of expected positron trapping sites possible in different ChG matrices, the preferential process of positron capturing is defined by extended free-volume defects in the nearest vicinity of chalcogen atoms neighboring with main glass-forming structural units (network-composing polyhedrons).26–30 In view of extra-low two-fold coordination and strong directionality of covalent bonding, the chalcogen atoms form low-electron density spaces, termed also as bond free solid angles (BFSA) by Kastner.31 Such BFSA undoubtedly contribute to neighboring geometrical free-volume spaces, ensuring them to possess an effective negative electrical charge due to proximity with more electronegative chalcogen atom (Ch = S, Se, Te) linked with more electropositive cation-type neighbor (As). The Ch atoms form an outer wall for innermost free-volume voids, which can be identified in view of their preferential electric state as counterparts of cation vacancies in crystals. Therefore, the most efficient positron traps in ChG can be imagined as geometrical voids within cycle-type formations of Ch-interlinked polyhedrons, such as As(Se/Te)3/2 pyramids, surrounded preferentially by Se- and/or Te-based BFSA. These voids are composed of atomic-accessible geometrical cores arrested by surrounding atomic-inaccessible shells formed by Se- and/or Te-based BFSA.
Specifically, in the case of chalcogen-rich TAS-235 glass (as compared with stoichiometric ChG built of corner-shared As(Se/Te)3/2 pyramids),18–21 an essential contribution of –Se–Se– bridges between pyramids somewhat depresses the positron trapping like in Se-rich glassy As–Se.28 But just these homonuclear links can be affected by small Ga additions, as it follows from energetic balance of covalent chemical bonding in quaternary Ga–As–Se–Te system (see Table 2), composed by assuming the homonuclear Ga–Ga, As–As, Se–Se and Te–Te bond energies as 34.1 kcal mol−1, 32.1 kcal mol−1, 44.0 kcal mol−1 and 33.0 kcal mol−1, respectively,32–34 and calculating the heteronuclear bond energies in respect to known Pauling method.32 Thus, in view of this analysis and in excellent agreement with previous structure study,20 it follows that GaSe4/2 tetrahedrons (not GaTe4/2) mostly appear in TAS-235 glass under Ga codoping instead of homonuclear Ch–Ch (e.g. Se–Se, Se–Te and/or Te–Te) links. So corner-sharing polyhedrons directly linked through common Ch atom become dominating building blocks in Te20As29Ga1Se50 glass, respectively modifying an arrangement of free-volume voids.
Bond | E, kcal mol−1 | Bond | E, kcal mol−1 |
---|---|---|---|
Ga–Ga | 34.1 | As–Se | 41.7 |
As–As | 32.1 | As–Te | 32.7 |
Se–Se | 44.0 | Ga–Se | 55.2 |
Te–Te | 33.0 | Ga–As | 37.2 |
Se–Te | 44.2 | Ga–Te | 36.1 |
Following to well-known graphical presentation of idealized structure of RE-doped Ge–As–S glass given by Aitken,12 this specificity of free-volume arrangement in TAS-235 glass can be presented as shown on Fig. 2a. The pyramidal AsSe3/2, AsTe3/2 and mixed As(Se/Te)3/2 units interlinked directly through common Ch atom (–Se– and/or –Te– bridges) or through two Ch atoms (e.g. –Se–Se–, –Se–Te– and/or –Te–Te– bridges) create characteristic cycle-type arrangement with some amount of positron trapping sites in the form of agglomerated inner free-volume voids. Under transition to Ga-codoped Te20As29Ga1Se50 glass, the Ga-based GaSe4/2 polyhedrons with energetically favorable Ga–Se bonds (Table 2) appear in the network of interlinked As(Se/Te)3/2 pyramids (Fig. 2b). In preferential Ch environment (as in TAS-235 glass), the Ga behaves as typical metal tending to be four-fold coordinated by Ch atoms to form mostly GaSe4/2 tetrahedrons (despite its main valence state +3), as it was well argued in previous research.20 From charge compensation standpoint, it means that some excess of negative electrical charge is stabilized in a vicinity of these tetrahedrons. Created deficit in Ch is counterbalanced by disappearing of some –Se–Se–, –Se–Te– and –Te–Te– bridges at the cost of direct corner-shared links between polyhedrons. Under small amount of Ga added (not too far to disturbed preferential ring statistics in a glassy network), these structural reconfiguration processes do not change essentially the volume of existing positron traps (at least, near average atomic coordination 2.3 character for TAS-235, where rather smooth compositional dependence of defect-related positron lifetime τ2 is expected for glassy As–Se).26,28,35 Disappearing of some two-atomic –Ch–Ch– bridges along with formation of GaSe4/2 tetrahedrons makes cycle-type formations in glassy Te20As29Ga1Se50 narrower (Fig. 2b), and free-volume voids arrested by interlinked polyhedrons become respectively smaller resulting in slightly reduced defect-related positron lifetime τ2 (Table 1). So network of Ga-codoped glass becomes denser. Indeed, as it follows from Archimedes displacement measurements (in a distilled water with ±0.005 g cm−3 error-bar), the atomic density of glassy Te20As29Ga1Se50 reaches 4.912 g cm−3 instead of 4.888 g cm−3 for TAS-235 glass (thus giving in recalculation to molar volume, correspondingly, 17.80 cm3 mol−1 and 17.90 cm3 mol−1).21
Such densification of atomic structure of Te20As29Ga1Se50 glass shifts balance between available positron annihilation paths from defect-specific trapping towards defect-free bulk trapping. Under such condition, the intensity of second component I2 is not further a good parameter, describing realistic concentration of positron traps (since positron trapping now is essentially disturbed by increased probability of annihilation from bulk defect-free states). Even under unchanged defect-free bulk positron lifetime τb, which can be caused by counterbalanced inputs from changes in positron annihilation channels, this effect leads to depressed trapping rate in defects κd and fraction of trapped positrons η, as it is demonstrated in Table 1.
Effect of RE-doping on PAL modes in such modified structure of Ga-codoped Te20As29Ga1Se50 glass can be explained in terms of competitive contribution of changed occupancy positions available for RE ions and trapped positrons. Such free-volume sites possessing simultaneously an effective negative electrical charge are placed in a vicinity of Ga-based tetrahedrons as schematically illustrated in Fig. 2b. The Pr3+ ions are stabilized in the network of Te20As29Ga1Se50 glass due to strong covalent bridging Pr3+–Se/Te–Ga links,7,8,12 thus eliminating corresponding void as potential positron trapping center (Fig. 2c). Thereby, the depressed positron trapping in Te20As29Ga1Se50 glass doped with 500 ppmw of Pr3+ (as it demonstrated by positron trapping modes gathered in Table 1) results from changed occupancy of these Ga-related free-volume positron traps.
As to the concentration of these extended positron trapping sites, it can be roughly estimated by accepting their analogy with negatively charged vacancies in elemental and compound semiconductors giving trapping coefficient at the level of 1015 atom per s.36,37 With atomic densities and experimental trapping rates character for different glasses in Table 1, it gives defect concentration near 5 × 1016 cm−3. Of course, these defects can be affected by RE additions even at such low level as a few tens of ppmw, provided the same sites are responsible for RE occupation and positron trapping. Undoubtedly, just this specificity is most essential in application of PAL spectroscopy to study RE doping effects in ChG, especially in a view that conventional atomic structure sensitive probes (X-ray, electron or neutron diffraction) are ineffective because of under-margin level of added ions, which is typically beyond reliably detectable limits of these methods.7,8 Noteworthy unchanged (τ2 − τb) difference and τ2/τb ratio (see Table 1) testify also in a favor of the same nature for positron traps in all studied ChG.
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