Raman and EPR Characterization of Diluted Magnetic Semiconductor

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C: Physical Processes in Nanomaterials and Nanostructures

Raman and EPR Characterization of Diluted Magnetic Semiconductor Sb2-xMnxS3 Nanocrystals Grown in Glass Matrix Ricardo S. Silva, Eder Vinicius Guimarães, Nilo F. Cano, Robson Humberto Rosa, Hanna Degani Mikhail, Anielle Christine Almeida Silva, and Noelio Oliveira Dantas J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b10539 • Publication Date (Web): 14 Feb 2019 Downloaded from http://pubs.acs.org on February 19, 2019

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The Journal of Physical Chemistry

Raman and EPR Characterization of Diluted Magnetic Semiconductor Sb2-xMnxS3 Nanocrystals Grown in Glass Matrix R. S. Silva1*, E. V. Guimarães1, N. F. Cano2, R. H. Rosa3, H. D. Mikhail4, A. C. A. Silva5, N. O. Dantas5 1Instituto

de Ciências Exatas, Naturais e Educação (ICENE), Departamento de

Física, Universidade Federal do Triângulo Mineiro, 38025–180, Uberaba, Minas Gerais, Brazil. 2Instituto

do Mar, Universidade Federal de São Paulo, 11070–100, Santos, São

Paulo, Brazil. 3Instituto

Federal do Triângulo Mineiro, 38064-790, Uberaba, Minas Gerais, Brazil.

4Instituto

de Ciências Tecnológicas e Exatas (ICTE), Departamento de Engenharia

Mecânica, Universidade Federal do Triângulo Mineiro, 38064–200, Uberaba, Minas Gerais, Brazil. 5Laboratory

of New Nanostructured and Functional Materials, Institute of Physics,

Federal University of Alagoas, 57072-900, Maceió, Alagoas, Brazil. *[email protected] (R. S. Silva) Abstract Structural and magnetic property change for different Mn-concentrations in diluted magnetic semiconductor Sb2-xMnxS3 nanocrystals grown in a glass host matrix were investigated. Transmission electron microscopy images and energy dispersive X-ray analyses and Raman spectra with Modified Model confirm the size and composition of nanocrystals. Electron paramagnetic resonance shows six hyperfine lines of the electron states, which are attributed to the interaction between the electron spin (S = 5/2) and the nuclear spin (I = 5/2) of Mn2+ ions (3d5) located in the crystal field of Sb2S3 semiconductor. Also, a change in Mn-Mn interactions is observed as Mnconcentration increases. The blueshift of Raman band around 188 cm-1 with increasing Mn concentration gives strong indications of the substitution of Mn2+ ions

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for Sb+3 ions in the crystalline structure of Sb2S3. In addition, the band around 217 cm-1 remains constant for Mn-concentrations of 0.00 to 0.10. However, for x = 0.20, a displacement of 210 cm-1 occurs, which indicates an interstitial incorporation of Mn ions in the Sb2S3 structure at high Mn-concentrations. A Raman high frequency "shoulder” (HFS) mode at 339 cm-1 is observed. Therefore, in this work, Sb2-xMnxS3 nanocrystals were grown successfully. 1. Introduction Advances made in the doping of transition metal (TM) ions, in the semiconductor crystal lattice, is relevant for developing diluted magnetic semiconductor (DMS) nanocrystals (NCs) and for permitting the formation of the new materials with interesting optical, magnetic and electronic properties. These new properties acquired in diluted magnetic semiconductor nanostructures are attributed to exchange interactions between semiconductor sp-bands and d-levels introduced by TM-ions.1-4 Mn-doped semiconductor nanocrystals allow for the study of spin dynamics together with the effects of quantum confinement properties. The charge of the optical and magnetic properties by varying the Mn-concentration and the size were reported for various types of nanocrystals, such as: Bi2-xMnxS3,5,6 Bi2xMnxTe3,7 Cd1-xMnxS,8 Cd1-xMnxSe,9 Pb1-xMnxS,10 Pb1-xMnxSe11,12 and Zn1-xMnxO.13 DMS nanostructured materials can be utilized in a range of technological applications such as in light-emitting diodes,14,15 solar cell photovoltaics,7 photonic and magnetic devices,16 and fluorescent biomarkers.17, 18 The investigation by Raman spectroscopy has been extensively used in the study of vibrational modes in diluted magnetic semiconductor nanostructures systems. There are changes in the phonons’ modes of vibration due to the effects of quantum confinement on nanocrystals that are different from the bulk material.19-21 As an example, the Raman bands in Bi2S3 nanocrystals are asymmetrically broad and with peak intensities different from the bulk material.22 In semiconductor nanocrystals embedded in an amorphous matrix, the effects of quantum confinement and network contraction are size dependent and are not observed for the corresponding bulk material.23-25 In addition, it is possible to confirm doping


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processes and formation of other crystals, by the displacement of Raman bands and the appearance of characteristic bands, respectively.26,

27

Based on the Raman

spectra, and using the modified phonon confinement model, it is possible to determine the size of the nanocrystal, as well as the formation of structures core/shell.27, 47, 48 In this context, Sb2S3 nanocrystals were synthesized in a glass matrix, doped with different Mn x-concentrations and investigated by techniques of Transmission Electronic Microscopy/Energy Dispersive X-ray spectroscopy (TEM/EDX), Electron Paramagnetic Resonance (EPR) and Raman Spectroscopy. The Sb2S3 is a semiconductor of orthorhombic crystalline structures from the V-VI family, which has a direct band gap of about 1.5 at 1.9 eV, 29-31 with an exciton Bohr of 0.9 nm.32 These materials are used for application in solar cells

33, 34

and photodetectors.35, 36 The

orthorhombic unit cell of Sb2S3 contains 20 atoms, in which 60 Raman modes are identified at the 𝛤 point of the Brillouin zone. The optical phonon modes are identified as: 30 active Raman modes, 22 infrared (IR) active modes and 5 silent modes. For the acoustic phonons, 3 modes have been identified.37-40 The doping with Mn magnetic ions in Sb2S3 semiconductors provides a change in the structural and magnetic properties attributed to the substitution of Sb3+ ions with Mn2+ forming the DMS Sb2-xMnxS3 NCs that gift new properties different from the pure Sb2S3 semiconductor. DMS Sb2-xMnxS3 NCs embedded in host glass is a new type of material with interesting physical and chemical properties which have great potential for development in the future of nanodevices for applications technological. 2. Experimental Details Mn-doped Sb2S3 NCs were grown in the host glass, named SNAB, with the chemistry composition: 40SiO2. 30Na2CO3. 1Al2O3. 29B2O3 (%mol). The samples were prepared by adding the nominal quantities 2[Sb2O3 + S] (wt% of SNAB) plus x[Mn] (wt% of Sb), with x = 0.00, 0.05, 0.10, and 0.20. The chemical reagents used in the synthesis process were procured from the Sigma-Aldrich company with a standard purity of: SiO2 (99.9%), Na2CO3 (99,5%), Al2O3 (99.9%), B2O3 (99.98%), Sb2O3 (99%), Mn (99.9%) and S (99.5%). The preparation of the samples consist



of three steps: In the first step the powders are mixed in an alumina crucible and melted at 1300°C for 1 hour. In the second step, the resulting melted mixture is cooled rapidly to room temperature for the formation of the glass matrix. In the third step, a heat treatment at 550°C for 10 hours is performed, which allows the diffusion of the Sb3+, Mn2+ and S2- ions. This step will give rise to the DMS Sb2-xMnxS3 nanocrystals. One hundred milligrams of powdered sample were used for each measurement. TEM images and energy dispersive X-ray spectroscopy (EDX) were taken using a JEM-2100 (JEOL, 200 kV) in order to investigate the formation and size of the Sb2−xMnxS3 NCs. Samples for the TEM and EDX measurements were deposited on a Cu grid. In order to investigate the modifications of the electronic states induced by Mn2+ ion incorporation, we performed, at room temperature, EPR measurements using a Bruker EMX EPR spectrometer operating at X-band frequency with a 100 kHz modulation frequency. The Raman system used to record the spectra was a commercial triple spectrometer (Jobin Yvon Model T64000) equipped with a charge-coupled device (CCD) detector. The 514 nm line from an argon-ion laser was used to excite the samples. An objective of 50X was used to focus the laser beam down to a spot of 1.5 μm in diameter. Therefore, the laser power and the power density hitting the sample were 10 mW and 3 × 105 W/cm2, respectively. 3. Results and Discussion The formation of the Sb2-xMnxS3 NCs was confirmed by Transmission Electron Microscopy (TEM) images. Figure 1(a) shows the presence of Sb2S3 NCs (x = 0.00) embedded in the host glass. A Sb2S3 nanocrystal image, with an average size of 8.0 nm, is amplified and exhibited in figure 1(b). An interplanar spacing value of 0.276 nm, attributed to the (221) crystalline plane of the Sb2S3 host semiconductor, is attained. Histogram of nanocrystals size distribution, to x = 0.00, with average diameter D = 7.55 nm and dispersion σ = 0.41 nm are shown in Figure 1(c). In Figure 1(d), the EDX analysis of the area circled in Figure 1(a) shows the presence of the Sb and S elements that originate the Sb2S3 NCs embedded in the host glass. TEM images of the Sb2-xMnxS3 NCs, for the xMn-concentration of 0.10,


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are shown in Figure 1(e). The magnification of the selected nanocrystal with a size of around 8.0 nm and an interplanar spacing of 0.312 nm, which is characteristic of the (230) crystalline plane of the Sb2S3 semiconductor, is shown in Figure 1 (f). Figure 1(g) shows, for the x = 0.10 sample, the histogram of nanocrystal size distribution with average diameter D = 7.88 nm and dispersion σ= 0.73 nm. For the assembly of the histograms in Figures 1 (c) and 1 (g), 20 nanocrystals from Figures 1 (a) and (e) were selected. For the TEM images in Figure 1 (e), according to the Raman spectroscopy data (Figure 3), for which x = 0.10, there may be the formation of MnS,50, 51 in addition to the presence of Bi2-xMnxS3 NCs, in which the dispersion of σx=0.10 is greater than σx=0.00. In Figure 1(h), EDX analyses of the area circled are shown, indicating a characteristic peak of Mn at 5.894 KeV, in addition to the elements Sb and S. This provides strong evidence of the incorporation of Mn2+-ions in substitution of the Sb3+ions, forming the Sb2-xMnxS3 NCs. A variation of the concentration ratio between Sb and S is observed in the EDX measurements displayed in Figures 1(d) and 1(h). This variation gives evidence of the change in concentration in the analyzed samples. Variation of intensity in EDX spectra is also observed in 5% Ir-doped SrTiO3 film.41 The average diameter and size dispersion of TEM images were analyzed with the Image J software.42 The energy level splitting of Mn2+-doped Sb2−xMnxS3 NC, for x = 0 to 20%, was investigated by EPR spectroscopy and the observed spectrum is shown in Figure 2(a). The observation of six hyperfine lines is attributed to the allowed transitions M S  1 and M I  0 between MS = 1/2 ↔ − 1/2 electronic states, when they are placed in a characteristic crystal field of Sb2S3 NC, and are due to the interaction between the electron spin (S = 5/2), the nuclear spin (I = 5/2) of Mn2+ ions (3d5) and are due to transitions with M S  1 and M I  0 .43 Based on these investigations, the signal with six well-defined EPR lines is assigned to the allowed Mn2+ transitions with the ion substitutionally incorporated in the Sb3+ sites of the Sb2S3 NC orthorhombic crystal structure. This structure is shown in Figure 2(b). An overlap between the hyperfine signal of isolated Mn2+ ions, together with the signal due to Mn-Mn interactions, becomes more evident as the Mn-concentration



increases.44,

45

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The average Mn-Mn distance was estimated from the Mn

concentration in nanocrystals using the following simplified model. Considering that the unit cell volume Vc of the nanocrystals is approximately the same as the bulk one (486.015 x 10-3 nm3),46 then the number of unit cells in a nanocrystal with volume VNC is n = VNC/VC. The Mn concentration is given by xMn = nMn/(8n), where nMn is the number of Mn atoms in the nanocrystals and the numerical factor accounts for the 8 Sb sites per cell. Therefore, the mean volume occupied by each Mn atom is VNC/nMn = Vc/(8xMn). Admitting a homogeneous substitutional Mn distribution among the Sb sites (8 per unit cell), it follows that the average Mn-Mn distance estimated is dMn-Mn ≈ ½(Vc/xMn)1/3. The background signal intensity, attributed to Mn-Mn ions, increases in function of xMn -concentration (as observed Figure 2(a)) as the Mn-Mn separation distance reduces. In Figure 2(d), for samples with x > 0.00, background signal in the EPR spectra has been subtracted making the processes of interaction more evident. In Figure 2(d), five peak-to-peak separations of the hyperfine structure are observed and the separations are 6.39, 7.68, 8.27, 9.05 and 9.57 mT with an average value of 8.19 mT. Raman spectra of Sb2−xMnxS3 nanocrystals, for Mn-concentration of 0.00, 0.05, 0.10 and 0.20, are shown in Figure 3. The Raman spectra show the characteristic active modes Ag1, B1g, Ag2, Ag3 and B2g of the Sb2S3 semiconductor, and the frequency modes from Figure 3 are collected in Table 1. 37-40 Table 01 - Raman modes identified in Figure 3 from the fitting procedure for the Sb2-xMnxS3 nanocrystals doped with different Mn-concentrations. Raman modes

𝐴1𝑔 𝐵1𝑔

Raman shift (cm−1) for Sb2-xMnxS3 nanocrystals 0.00 0.05 0.10 0.20 188 194 194 194 217

217

217

210

𝐴2𝑔

280

279

277

276

𝐴3𝑔

--------

313

310

308

𝐵2𝑔

317

320

319

316

HFS Mn-S

339 --------

337 --------

339 250

335 228; 288


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In order to calculate the average size of the Sb2S3 nanocrystals and Mn doping concentration, the modified phonon confinement model was applied in the Raman spectra.47 The modified phonon confinement model can be applied in the Raman spectra of quantum dots CdSe, core/shell CdSe/CdS and quantum dots in a glass matrix.27, 48 The following values were obtained for samples: 7.88 nm (Sb2S3: 0.00Mn), 7.86 nm (Sb2S3: 0.05Mn), 7.84nm (Sb2S3: 0.10Mn) and 7.80nm (Sb2S3: 0.20Mn). These results are in excellent agreement with the TEM images, demonstrating that the average size of the nanocrystals is around 8.0 nm and that no changes in size occur with the incorporation of Mn in the synthesis. In Figure 3, the well-defined bands indicate that the samples show good crystallographic quality.49 The band around 188 cm-1 corresponds to the S-Sb-S bond. It is observed that this band undergoes a blueshift with increasing Mn concentration.50 This result gives strong indications of the substitution of Mn2+ ions for Sb+3 ions in the crystalline structure of Sb2S3 due to the decrease of the atomic mass, thus causing an increase in the frequency of vibration. This band narrowing effect is related to the decrease in the disorder degree. 49 The band around 280 cm-1 is associated with the Sb-S bond and redshift with increasing Mn concentration.37 The redshift is justified by the interstitial incorporation of Mn ions in the Sb2S3 structure. The band around 217 cm-1 remains constant from concentrations 0.00 to 0.10. However, in the concentration of 0.20, a displacement to 210 cm-1 occurs. This result reinforces the high interstitial incorporation of Mn ions in the Sb2S3 structure. It is observed in Raman spectra that with the x= 0.10 of Mn doping, an appearance of a band around 320 cm-1, a vibrational mode of B2g, and redshifts with the increase of Mn concentration. This result gives strong evidence of the symmetry breaking and the incorporation of Mn ions into the crystalline arrangement of Sb2S3. The bands located around 250 cm-1, 228 cm-1 and 288 cm-1 for samples doped with 0.10 Mn and 0.20 Mn, respectively, are characteristic of MnS. This result indicates that, at these concentrations, Mn saturation occurs in the Sb2S3 structure, and therefore, the formation of MnS also occurred.50, 51 Raman mode Ag3, not observed in the Sb2S3 NCs embedded in the SNAB glass matrix, becomes evident at x > 0.00



and its intensity increases with the variation of x from 0.05 to 0.20. This fact can be attributed to the decrease of the structural defects caused by the Sb3+ ion vacancy, which is occupied by Mn2+ ions during the ionic diffusion process at 550 °C, as reported for Mn doped in nanostructures system.26, 54-56 The high frequency "shoulder" (HFS) at 339 cm-1 was not reported in the literature for Sb2-xMnxS3 NCs. However, similar HFS phonons have already been identified in the Raman spectra of CdSe nanoparticles,52 CdTe53 and Cd1-xMnxS NCs,26 originating from the participation of acoustic phonons in the scattering process. These phenomena observed in the Raman spectra are allotted to the improvement of the crystallographic quality of the Sb2-xMnxS3 NC nanocrystals. Of course, further experimental and theoretical investigations are necessary for the study of the optical and acoustic phonon mechanism processes in DMS NCs. 4. Conclusion We report the successful synthesis of DMS Sb2-xMnxS3 NCs, with an average diameter of 8.0 nm and crystallized in orthorhombic structures embedded in a glass host matrix. These results confirmed the incorporation of Mn2+ in the Sb2S3 NCs. The study of DMS Sb2-xMnxS3 NCs performed by experimental techniques (transmission electron microscopy ˗ TEM, energy dispersive X-ray (EDX), electron paramagnetic resonance (EPR) and Raman spectroscopy) revealed the possible control of the magnetic and structural properties. EPR spectra also demonstrated the incorporation of Mn2+ ions in the crystalline structure of Sb2S3 NCs, with the observation of six hyperfine lines and an increase of Mn–Mn interactions proportional at xMn-concentration. Structural investigation by Raman spectroscopy shows the influence of the xMn-concentration of Sb2-xMnxS3 NCs. The Mn doping process in semiconductor Sb2S3 NCs has made the change of the vibrational modes in DMS Sb2-xMnxS3 NCs possible. The formation of MnS NCs is also evidenced to x = 0.10 and 0.20 with the presence of 228, 250 and 288 cm-1 bands. DMS Sb2-xMnxS3 NCs with an average size of around 8.0 nm calculated by the modified phonon confinement model applied in the Raman spectra are according to the data obtained by TEM images. This data, in turn, provides strong evidence of sp-d exchange


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interactions between the Mn2+ magnetic ions and the Sb2S3 semiconductor NCs. We believe that this work can be used to inspire new research and the development of new technological devices. Acknowledgements The authors gratefully acknowledge financial support from the following Brazilian agencies: MCT/CNPq, Capes, Fapemig, and Rede Mineira de Química (RQ-MG) supported by Fapemig (project CEX-RED-00010-4). We are also thankful for use of facilities for the TEM measurements at the Laboratório Multiusuário de Microscopia de Alta Resolução (LabMic), of the Universidade Federal de Goiás and the Raman Spectroscopy at the Physics Institute of the Universidade Federal de Uberlândia.

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Dhandayuthapani,

T.;

Girish,

M.;

Sivakumar,

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Sanjeeviraja,

C.;

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