Accepted Manuscript Title: Structural and optical investigations on Mn3 O4 hausmannite thin films gamma irradiated along with an enhancement of photoluminescence sensing proprety Authors: L. Ben Said, K. Juini, F. Hosni, M. Amlouk PII: DOI: Reference:
S0924-4247(17)31150-0 https://doi.org/10.1016/j.sna.2017.12.040 SNA 10527
To appear in:
Sensors and Actuators A
Received date: Revised date: Accepted date:
20-6-2017 26-11-2017 18-12-2017
Please cite this article as: Said LB, Juini K, Hosni F, Amlouk M, Structural and optical investigations on Mn3 O4 hausmannite thin films gamma irradiated along with an enhancement of photoluminescence sensing proprety, Sensors and Actuators: A Physical (2010), https://doi.org/10.1016/j.sna.2017.12.040 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Structural and optical investigations on Mn3O4 hausmannite thin films gamma irradiated along with an enhancement of photoluminescence sensing proprety
a
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L. Ben Said a,b *, K. Juini c, F. Hosni c and M. Amlouk a
Unité de physique des dispositifs a semi-conducteurs, Faculté des sciences de Tunis,
Université de Tunis El Manar, 2092 Tunis, Tunisia..
Faculté des Sciences de Bizerte, Zarzouna 702, Bizerte, Carthage University, Tunisia.
c
Laboratoire de Recherches en Energie et Matière pour le Developpement des Sciences Nucléaires
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b
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(LR16CNSTN02), 2020 Sidi Thabet Ariana, Tunisia.
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*Corresponding author:
[email protected]
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Graphical abstract
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Non-irradiated Irradiated 25 kGy Irradiated 50 kGy Irradiated 100 kGy
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wavelength (nm)
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Highlights
Hausmanite Mn3O4 thin films were exposed to γ-radiation source ranging from 0 to 100 kGy.
XRD study reveals that all the films are polycrystalline with spinel orthorhombic structure.
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The band gap energy of the films increases from 2.20 to 2.70 eV as the γ-radiation increased.
The photoluminescence intensity increases with increasing gamma doses up to 50kGy
The enhancement of photoluminescence propriety may be of interest in some sensitivity areas such as photocatalysis and gas sensors.
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Abstract:
This paper reports the results of the structural and optical study of gamma irradiated Mn 3O4
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sprayed thin films having thickness of the order of 2µm. Mn3O4 thin samples were irradiated
by different gamma-rays doses (25, 50 and 100 kGy). First, the structural features of asdeposited and γ- irradiated films were investigated by X-ray diffraction (XRD). XRD Results show that the average grain size and the degree of the crystallinity depend strongly on the
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irradiation dose. Second, the optical properties for as-deposited and exposed thin films were
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analyzed. It was found that the optical transmittance coefficient of irradiated samples
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increases. Moreover, the optical energy gap value determined by means of the absorption coefficient increases from 2.20 to 2.70 eV with increasing absorbed dose. Finally, the effect
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of such irradiation on photoluminescence (PL) properties was also studied. It is found an enhancement of the photoluminescence property of such films for gamma doses 25- 50kGy.
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This may be of interest for possible use of these films in sensitivity domains such as photocatalysis and gas sensors.
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Keywords: Mn3O4, thin film; γ- irradiation; optical properties; Structural properties; Spray pyrolysis
1. Introduction
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Devices that require relatively high optical transmittance in the visible range; comprising, organic light emitting diodes (OLEDs), flat panel displays [1, 2], gas sensor [3], electrochromic windows [4], and photovoltaic [5, 6] are being increasingly studied. Indium tin oxide (ITO) is the best known and the widely studied of TCOs for organic optoelectronic devices [7]. Nevertheless, indium has become increasingly expensive and its limited resources may cause problems to satisfy future demand. These problems have motivated the search for alternative materials. Besides the abundance and hence low cost of the major constituents of 2
Mn3O4, high optical transparency ( ≥ 73%), various valence states and p-type conductivity makes this binary material an attractive alternative of ITO. The properties of thin films depend on the method of preparation and the treatment conditions. The spray pyrolysis technique is a simple and cost- effective method to prepare different TCO materials in homogenous form, and large area films with variety of thicknesses (nm to μm). During the last three decades, modification of materials properties by irradiation gained great interest by many laboratories [8-10]. This attraction is due to the fact that ionizing radiations (such as X-
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rays, gamma rays, electron beam) are finding more and more applications in the industrial and medical fields. Passing through any metal oxide, gamma radiation cause structural defects
optical, electrical, dielectric and magnetic changing [11- 25].
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such as, distortions, grain boundaries and oxygen vacancies modifications involving thus
Recently, several attempts have been achieved to investigate the effect of gamma radiation especially on thin films structures of different metal oxides [26 - 34]. Nevertheless, there are
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some discrepancies in the literature where, on one hand a considerable enhancement of the
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material properties is reported and on the other hand only a small effect is observed. Indeed, the effect of ionizing radiations depends on both the radiation dose and the parameters of the
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films including its thickness. In this work, the results reveal that the irradiation of Mn3O4 thin
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film to γ-rays produces changes in the micro structural properties which in turn affect the optical properties of the material. However, there is lack of information on the effect of
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gamma irradiation on the structural and optical properties of pure Mn3O4 thin films grown on glass substrate. The present study was carried out to investigate the effect of γ-rays radiation
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on the structural and optical properties of Mn3O4 thin films prepared by the spray pyrolysis technique. A special emphasis has been focused on the photoluminescence property gamma of
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irradiated Mn3O4 thin films.
2. Thin films preparation
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The spray pyrolysis is a humid and a cost-effective technique where the endothermic thermal decomposition is taken place at the hot surface of the substrate to give the target. Mn3O4 thin films were prepared from an aqueous solution containing magnesium chloride (MnCl2-6H2O) sprayed at a rate of 4 ml / min. The substrate temperature was maintained at 350°C using a digital temperature controller with a k-type thermocouple. The distance between nozzle and substrate was about 27 cm. The filtered compressed nitrogen air was used as a gas carrier. The 3
total deposition time was of the order of 20 min. After the deposition, the films were dried at room temperature. The thickness of the samples was estimated from environmental scanning electron microscope FEI Quanta 200 model and found to be around 2µm. 3. Characterization techniques The irradiation of Mn3O4 thin films was carried out using the Tunisian Cobalt-60 irradiation
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facility at the dose rate 80 Gy/min. The irradiation doses applied in this study were 25, 50 and 100 kGy at an ambient temperature of 25°C (±0.5 °C) [35, 36]. After irradiation, the structure of as-deposited and irradiated films were analyzed by X-ray diffraction using a Siemens
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D500 diffractometer with monochromatic CuKa radiation (l = 1.5406 Å) in the span of the
angle between 10° and 70° with a step of 0.05° at room temperature. On the other hand, the transmittance spectra of un-irradiated and irradiated films were measured through the
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wavelength range 250- 2500 nm using SHIMADZU UV 3100 UV–VIS spectrophotometer. Finally, PL spectra were performed at room temperature by means of a Perkin-ElmerLS55
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Fluorescence spectrometer with an excitation wavelength of 275 nm.
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4. Results and Discussion 4.1. XRD analysis
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Fig. 1 shows typical XRD patterns of the manganese oxide thin films subjected to different gamma radiation doses. It can be seen that all these XRD patterns reveal that the films have a polycrystalline structure and possess a prominent diffraction peak due to the reflection from
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(101) plane corresponding to 2θ-value of about 18°, revealing the fact that the preferred orientation along (101) was common at all gamma radiation doses. In order to determine the
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change in crystal structure in Mn3O4 films after irradiation, the variation in the peak intensity which is directly tributary to the degree of crystallinity state as well as the full-widths at halfmaximum (FWHM) which reveals the evolution of the grain size have been examined. (101)
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diffraction peak intensity increases with gamma radiation dose up to 50 kGy leading to an improvement in the crystallinity of the samples and decreases slightly thereafter. It is reported that there is an improvement of the crystallization in indium oxide thin films with
gamma radiation dose up to a certain dose [28]. Also, Abhirami et al. [31 ] found a sharp increase in the intensity of some peaks of SnO2 up to 100 kGy. Moreover, the enhancement in the peak intensity in the thin films of the mixture of In2O3 and SiO oxides was also reported elsewhere [37, 38]. 4
In contrast, the decrease in the intensity of (101) preferential orientation may indicate a slight increase of the surface roughness after irradiation generated by a meaningful increase of staking defects such as distortion and dislocation and so on. On the other hand, the FWHM of this diffraction peak increases with gamma radiation dose up to the critical dose of 25 kGy and decreases thereafter leading to a decrease in the crystallite size (calculated using Debye– Scherrer's equation) down to 43.7 nm for 25 kGy irradiated Mn3O4 and then followed by a slight increase again to 53.4 nm for both 50 and 100 kGy doses. Al-hamdani et al. [39] found
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that the grain size of ZnO thin films decreases with the dose. Moreover, Ramadan et al. [40]
obtained the same behavior regarding NiO thin films. They attributed such results to the
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fragmentation of large grains by irradiation at fairly high doses, ie, irradiation-induced voids. Contrary to Ramadan et al., Baydogan et al. reported that the decrease in both the roughness
and the grain size could be due to the number of voids decrease excessive owing to the combination of the voids with each other after irradiation method [41]. In other side, the
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increase of gamma-irradiation does until 50 kGy doesn’t show any development of new
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peaks. However, when the gamma radiation dose achieves 100 kGy development of new peaks is occurred. Indeed, (021) and (120) new planes appear: the first corresponds to Mn3O4
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phase according to standard powder diffraction data of (JCPDS 01-086-2337) and the second
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may be attributed to the beginning of the formation of Mn3O4 Manganoxide secondary phase matching (JCPDS Manganoxide (NR) card). This phenomenon could arise as a result of
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densification that occurred due to localized heating happened during γ -ray exposure. XRD is also an effective tool to estimate the unit cell parameters of materials. As could be seen from Table.1, a drastic increase was observed in the lattice parameter ‘a’ for irradiated sample at
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dose of 100 kGy. This increase may be attributed to the conversion of smaller size Mn3+ ions to larger size Mn2+ ions as an ionizing effect of gamma radiation. This being, the c/a ratio that
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reflects the expand of Jahn-Teller distortion of octahedral symmetry caused by Mn3+ ions, has therefore decreased dramatically, probably assigned to local structure distortion due to the gain of oxygen by Mn ions (following the ionization of Mn3+ into Mn2+), which produces the
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stress field in the bulk sample. The structural parameters of Mn3O4 thin films, calculated from the XRD data are gathered in Table.1.
4.2. Optical study 4.2.1. Absorption spectra 5
The variations of the absorption coefficient of Mn3O4 thin films with incident photon energy for as deposited and gamma-irradiated samples are shown in Fig. 2. The absorption coefficients were calculated from the transmittance and reflectance spectra of Mn3O4 thin films. From Fig. 2, the absorption coefficient decreases with irradiation dose. In the same line, it is noted that the absorption edge blue shifts towards higher energies with the irradiation dose. This may be due to the fact that as the dose increases, the resulting structural changes, such as bond angle and length variations, lead indeed to a decrease in the absorption edge
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region [42].
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4.2.2. Optical band gap energy
Spectral dependencies of absorption coefficients for typical semiconductors in the high
α (hν) = A (hν – Eg)1/2
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absorption region are described by the following relation:
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(1)
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This formula is often called the Tauc law, where A is a constant; α is the absorption
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coefficient; Eg is the optical band gap energy. This kind of spectral behavior is fairly easy to understand assuming parabolic dependencies for the density of valence and conduction band
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states. As shown in Fig. 3, the direct allowed optical band gap was evaluated from the linear plots of (αhν)2 as a function of energy for different doses. The intersections of these curves with the abscissa axe give the optical band gap energy values. It is found that Eg value
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increases from 2.2 eV for as deposited Mn3O4 thin film to 2.7 eV for sample irradiated at 100 kGy. Further results are summarized in Table 2. The optical band gap energy variation with
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increasing dose may be related to bond breaking, bond angle variations as well as bond rearrangement of atoms which take place upon irradiation of Mn3O4 irradiated thin film leading to a noteworthy change in local structure order and therefore a change in the density
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of localized states. As described above, Mn3O4 thin films have a layer structure. Under irradiation process, these films exhibit some atomic rearrangements. The defects such as dangling bonds could be removed leading to a change of the atomic distances and bond angles. The removal of these defects induces a decrease of the density of localized states in the band gap. This causes indeed a decrease in the transition probabilities from the band tails and thus the optical energy gap increases according to a previous work [42].
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4.2.3. Urbach Energy In addition to the band gap energy, it is possible to determine from the optical absorption spectra recorded for as-deposited films as well as for irradiated ones, the energy width of the band tails of localized states. In fact, the presence of sharp band edges in crystals and thin films materials results in a sharp increase in the absorption coefficient when the photon energies exceed the optical band gap. In amorphous compouds (also in some crystals), the
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presence of energy band tails results in significant absorption even at photon energies below the optical band gap [43]. Typical spectral dependencies for energies at the absorption edge
are shown in Fig. 4. This absorption below the edge is described by an exponential
α = α0 exp (hν /EU)
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dependence:
(2)
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Which is usually called the Urbach empirical law, where α0 is a constant and EU is the Urbach
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energy which indicates the width of the band tails of the localized states. The energy width of
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the band tails of localized states has been found to decrease with gamma radiation dose which resulted in an increase in the band gap energy. It is well known that Urbach energy EU can
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characterize the degree of the absorption edge smearing due to the crystalline lattice disordering caused by different factors: structural disordering that could be intrinsic (intrinsic
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structural defects, e.g. dislocations or vacancies) as well as induced by external factors (doping effect, deviation from the stoichiometry , ion implantation, hydrogenation, ….),
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temperature disordering which is principally caused by the lattice thermal vibrations and compositional disordering caused by atomic substitution in mixed crystals [45]. In this work.
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an increase in the band gap energy value is noted due to a heat input induced by gamma irradiation probably resulting in the decrease of Urbach energy (see Table. 2). 4.2.4. Reflectance and transmittance spectra
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The reflectance R(λ) and transmittance T(λ) optical measurements recorded
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spectrophotometer were transformed to absolute values performing an adjustment to eliminate the absorbance and reflectance of the glass substrate. Fig. 5 reveals typical visible and nearinfrared of T(λ) and R(λ) for as-deposited and γ-irradiated (25, 50 and 100 kGy) Mn3O4 thin films. An inspection of these figures underlines an increase of transmittance with γ-irradiation dose. In the absorption region situated in 350nm to 600nm domain, the transmittance spectra 7
of the irradiated films are shifted to shorter-wavelength (blue shift). Such shifts are related to variation in the optical band gap of irradiated films which was confirmed in the previous sections. As it could be seen, in the transparent region located at 600 - 2000 nm region, the transmittance of the irradiated films showed an increase from ~73% of as-deposited film to ~80% of irradiated one at 100 kGy as shown in Table.2. This increase may be due to two possible raisons: (i) the first is tributary to the decrease in the metal to oxygen ratio (Mn/O) causing a decrease in the carrier density parameter and (ii) the second is related to the
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presence of intra band transitions at localized states situated in the band gap. However, the
presence of both phenomena remains also plausible. These results are consistent with results obtained elsewhere [30, 42, 45]. The effect of gamma radiation on optical transmission can be
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more investigated by plotting the relative change of transmission ∆T/T0 against the incident
photon energy in the transmission edge region of the optical spectra, with T and T0 are the transmission after and before irradiation respectively [42]. As seen in Fig. 6, a peak in the
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relative change of transmission is depicted at 2.5 eV. This energy value marks the beginning
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of the transmission edge as well as the end of the absorption one. Moreover, the peaks
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regarding the values of the relative change of transmission ∆T/T0, were plotted in terms of gamma irradiation dose. The results are displayed in Fig.7. The corresponding peak values are
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found to increase with the radiation dose, confirming that the shift in the absorption (transmission) edge is especially accompanied by a possible increase in transmission
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coefficient and a decrease in absorption due to the process of γ –irradiation.
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4.2.5. Photoluminescence investigation Fig. 8 (a) displays the room-temperature photoluminescence spectra of non-irradiated and γ-
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irradiated Mn3O4 films obtained with an excitation wavelength of 275 nm. Four PL emission peaks located at 399 nm, 416 nm, 449 nm, 498 nm and 539 nm are observed (Fig. 8 (b)). UV emission bands situated at 399 nm, 416 nm and 449 nm correspond to the recombination and
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emission of free excitons through an exciton–exciton collision process near band edges of the well crystallized crystals. A prominent blue emission peak at 498 nm and a green emission observed at 539 nm can be explained by the oxygen vacancy-related defect emission [46]. The peak position was unchanged with increasing the irradiation dose while new emission peaks located at 579 nm, 584 nm and 591nm appeared for irradiated sample at 25 kGy dose. These peaks correspond to the yellow PL emission that can be attributed to d–d transitions involving Mn3+ ions [47]. So, the PL emission behavior in the yellow–violet luminescent region 8
demonstrates the promise applications in ultraviolet and visible light emission devices. The luminescence intensity increased with increasing the irradiation dose up to 50 kGy. The increase in PL intensity with the irradiation dose can be understood by the fact that more and more traps are getting filled with the increase of irradiation dose and subsequently these traps release the charge carriers on thermal stimulation to at last recombine with their counterparts, as reported elsewhere [48]. Nevertheless, a decrease in PL signal intensity is observed when the radiation dose is equal to100 kGy. For this dose, the irradiation process leads to a bond
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breaking around the luminescent atom inducing a mismatching between the luminescent and
non-luminescent atoms like Mn and O [49]. Thus, the concentration of these disruptions in
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bonding induced defects and distortion and then decreases effectively the luminescence property [50-52]. This study regarding the enhancement of PL property for irradiated sample at 25-50kGy attests the possible use of such films as optoelectronic sensors.
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5. Conclusion
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This work covers the effect of gamma irradiation of Mn3O4 sprayed thin films. This
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irradiation highlights interesting changes regarding the microstructural and optical properties by means of four doses of such binary oxide hausmannite material. Special emphasis is put on
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the PL findings. With the focus mainly on efficiency, the aspect of reactivity against gamma irradiation of such oxide films has been addressed. Further studies are in to pave the way for
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possible application of such irradiated films in sensitivity devices (gas and bio-sensors, etc.). Indeed, this sensitivity seems to us quite important. Similarly, in our laboratory we found
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encouraging results in photocatalysis tests under visible light [53].
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BEN SAID LILIA Born: February 17, 1987- Bizerte, Tunisia Identity Card: 08933982 Civil Status: Married, two children Current Position: Third year PhD student in Physics
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Registration: Faculty of Sciences of Bizerte, Carthage University, 7021 Jarzouna, Bizerte, Tunisia
Sciences de Tunis,Campus Universitaire 2092 Tunis, Tunisia.
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Research Laboratory : Unité de Physique des Dispositifs à Semi-conducteurs, Faculté des
Address : 2 Rue Abbass Mahmoud El Akkad Cité Bougatfa II Bizerte Tunisia.
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e-mail:
[email protected]
Academic background
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Phone : +216 72 533384, Mobile :+216 58174883
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2012 : “Master’s degree in materials: properties and analysis ” at Faculty of Science-Bizerte, Tunisia.
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2010 : Maitrise in Applied Physics at Faculty of Science-Bizerte.
CC E
2006 : Bachelor’s degree, Mathematics, Bizerte, Tunisia.
II-
Professional experience
A
2013-2014: Temporary teaching in physics during the first semester.
III-
Publications
13
« Pure and zirconium-doped manganese (II,III) oxide: Investigations on
structural
and
conduction-related
properties
within
the
Lattice
Compatibility Theory scope» Accepted L. Ben Said, T.Larbi a,A. Yumak,K. Boubaker, M.Amlouk
Mn3 O4 thin films along with ethanol sensing» Accepted
SC R
L. Ben Said, A. Inoubli, B. Bouricha, M. Amlouk
IP T
« High Zr doping effects on the microstructural and optical properties of
«Ethanol sensing properties and photocatalytic degradation of methylene
A
N
U
blue by Mn3O4, NiMn2O4 and alloys of Ni-manganates thin films» Accepted
M
T. Larbi, L. Ben said, A. Ben daly, B. ouni, A. Labidi, M. Amlouk
ED
«A study of optothermal and AC impedance properties of Cr-doped Mn3O4
sprayed thin films» Accepted
CC E
PT
T. Larbi, A. Amara , L. Ben Said , B. Ouni, M. Haj Lakhdar, M. Amlouk
«Electric Conduction Mechanisms Study within Zr Doped Mn3O4 Hausmannite Thin
A
Films through an Oxidation Process in Air» Accepted L. Ben Said, A. Inoubli, R. Boughalmi , and M. Amlouk
14
Lilia Ben Said University of El Manar Tunis Tunisia Faculty of Sciences of Bizerte Carthage University Tunisia
A
CC E
PT
ED
M
A
N
U
SC R
IP T
Lilia Ben Said (1987) is a PhD student in the unity of physics of semiconductor devices (UPDS) of the Faculty of Sciences of Tunis Tunisia. Her researches are focused on the binary thin films of semiconductor based on development and implementation of metal oxide materials specifically thin Mn3O4 films doped Zirconium deposited by spray pyrolysis technique and their application to environmental devises for gas sensors and catalysis. She is author of 6 scientific articles published in renowned international journals. Also, she participated in the international conferences on the physics of nano-materials. She made temporary teaching in physics during the first semester in 2013-2014 university year.
15
Fig. 1: The typical X-ray diffraction (XRD) patterns of Mn3O4 thin films irradiated by γ-ray with various irradiation doses. Fig. 2: The variation of the absorption coefficient with photon energy for un-irradiated and irradiated samples.
IP T
Fig. 3: The variation of (αhν)2 with the incident photon energy for un-irradiated and γ- irradiated samples. Fig. 4: Variation of ln(α) with energy of un-irradiated and γ-irradiated Mn3O4 thin films.
SC R
Fig. 5: Transmittance and reflectance spectra of un-irradiated and γ-irradiated Mn3O4 thin films. Fig. 6: The variation of the relative transmission, ∆T/T0 = (T-T0)/T0, with photon energy for γ-irradiated samples.
U
Fig. 7: The variation of peak position in Fig. 6, with irradiation dose.
A
CC E
PT
ED
M
A
N
Fig. 8: (a) The room temperature PL spectra of the un-irradiated and γ-irradiated Mn3O4 thin films. (b) Deconvolution spectrum of the un-irradiated Mn3O4 .
16
Intensity (a.u)
SC R
IP T
120
021
Irradiated 100 kGy
PT
M
112 200 103 121 211 202 004
ED 20
30
40
50
60
400
303
105
Non- irradiated
70
2 (degree)
CC E
10
Irradiated 25 kGy
224
101
A
N
U
Irradiated 50 kGy
A
Fig. 1: The typical X-ray diffraction (XRD) patterns of Mn3O4 thin films irradiated by γ-ray with various irradiation doses.
17
IP T
6 5
SC R
Non-irradiated Irradiated 25 kGy Irradiated 50 kGy Irradiated 100 kGy
U
3
6
-1
(10 cm )
4
A
N
2
M
1
-1
0,5
1,0
1,5
2,0
2,5
3,0
3,5
h (eV)
PT
0,0
ED
0
A
CC E
Fig. 2: The variation of the absorption coefficient with photon energy for un-irradiated and irradiated samples.
18
0,5
2
(h) (10 m eV )
0,4
IP T
Non-irradiated Irradiated 25 kGy Irradiated 50 kGy Irradiated 100 kGy
0,2
U
2
14
SC R
-2
0,3
N
0,1
2,0
2,5
3,0
M
1,5
A
0,0
ED
h (eV)
A
CC E
PT
Fig. 3: The variation of (αhν)2 with the incident photon energy for un-irradiated and γ- irradiated samples.
19
3,5
16
12
IP T
15,0
14,5
14,0
13,5
10
13,0
12,5 2,2
2,3
SC R
Ln ()
14
2,4
2,5
2,6
2,7
Non-irradiated Irradiated 25 kGy Irradiated 50 kGy Irradiated 100 kGy
U
8
1,0
1,5
N
6 2,0
2,5
3,0
3,5
4,0
M
A
h (eV)
A
CC E
PT
ED
Fig. 4: Variation of ln(α) with energy of un-irradiated and γ-irradiated Mn3O4 thin films.
20
IP T
100
100
(a)
90
SC R
90 80
80
60
U
Non-irradiated Irradiated 25 kGy Irradiated 50 kGy Irradiated 100 kGy
50 40
0
1000
10 0
1500
2000
2500
(nm)
PT
500
ED
10
40
20
M
20
50
30
A
30
60
Reflectance
70
N
Transmittance
70
A
CC E
Fig. 5: Transmittance and reflectance spectra of un-irradiated and γ-irradiated Mn3O4 thin films.
21
IP T SC R U
90 80
N
70
A
50
M
/0
60
40
ED
30
0
PT
20 10
25 kGy 50 kGy 100 kGy
CC E
1,8
2,0
2,2
2,4
2,6
2,8
3,0
3,2
3,4
h (eV)
A
Fig. 6: The variation of the relative transmission, ∆T/T0 = (T-T0)/T0, with photon energy for γ-irradiated samples.
22
IP T SC R
80
U N
40
A
/0
60
M
20
0
ED
0
20
40
60
80
CC E
PT
Gamma radiation dose (kGy)
A
Fig. 7: The variation of peak position in Fig. 6, with irradiation dose.
23
100
70
Non-irradiated Irradiated 25 kGy Irradiated 50 kGy Irradiated 100 kGy
579 nm 584 nm 16
591 nm
12
40
4 575
SC R
8
580
585
30
20
590
595
600
U
PL Intensity (u.a)
50
20
IP T
60
(a)
A
N
10
0 300
400
500
M
200
600
700
800
ED
wavelength (nm) 498 nm
(b) 539 nm
30
CC E
PL Intensity (u.a)
PT
40
20
449 nm
416 nm 399 nm
A
10
0 300
400
500
600
700
800
wavelength (nm)
Fig. 8: (a) The room temperature PL spectra of the un-irradiated and γ-irradiated Mn3O4 thin films. (b) Deconvolution spectrum of the un-irradiated Mn3O4 .
24
Table1: Structural and micro-structural parameters of Mn3O4 thin film, exposed to various levels of the gamma radiation dose.
c/a
Un-irradiated
5.737
9.459
1.648
311.3
68.70
Irradiated 25 kGy
5.753
9.445
1.641
312.6
43.70
Irradiated 50 kGy
5.754
9.456
1.643
313
53.45
Irradiated 100 kGy 6.060
9.448
1.559
347
3.32
IP T
c (Å)
Microstrain Dislocation (10-3) density (1012 lines/m2)
SC R
a (Å)
Average crystallite Cell volume size (Å3) (nm)
211
5.05
522
U
Cell parameters
4.14
349
53.45
3.50
349
A
CC E
PT
ED
M
A
N
Samples
25
Table2: Variation of optical parameters of Mn3O4 films with various gamma irradiation doses.
Transmittance (%)
EgTauc (eV)
EU (meV)
Un-irradiated
73
2.200
575
Irradiated 25 kGy
78
2.380
353
Irradiated 50 kGy
77
2.390
357
Irradiated 100 kGy
80
U
SC R
IP T
Samples
A
CC E
PT
ED
M
A
N
2.700
26
341
