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Chemically deposited In2S3–Ag2S layers to obtain AgInS2 thin films by thermal annealing

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(1)Applied Surface Science 263 (2012) 440–444. Contents lists available at SciVerse ScienceDirect. Applied Surface Science journal homepage: www.elsevier.com/locate/apsusc. Chemically deposited In2 S3 –Ag2 S layers to obtain AgInS2 thin films by thermal annealing ˜ a,∗ , M. Calixto-Rodriguez b , C. López-Mata c , M.L. Ramón b , I. Gómez a , A. Acosta a S. Lugo a , Y. Pena a. Universidad Autónoma de Nuevo León, UANL, Fac. de Ciencias Químicas, Av. Universidad S/N Ciudad Universitaria San Nicolás de Los Garza Nuevo León, C.P. 66451 Mexico Centro de Investigación en Energía-Universidad Nacional Autónoma de México, 62580, Temixco, Morelos, Mexico c Instituto Tecnológico de Chetumal, Av. Insurgentes No. 330, C.P. 77013, Col. David Gustavo Gtz., Chetumal, Quintana Roo, Mexico b. a r t i c l e. i n f o. Article history: Received 9 February 2012 Received in revised form 1 September 2012 Accepted 16 September 2012 Available online 24 September 2012. a b s t r a c t AgInS2 thin films were obtained by the annealing of chemical bath deposited In2 S3 –Ag2 S layers at 400 ◦ C in N2 for 1 h. According to the XRD and EDX results the chalcopyrite structure of AgInS2 has been obtained. These films have an optical band gap, Eg , of 1.86 eV and an electrical conductivity value of 1.2 × 10−3 ( cm)−1 . © 2012 Elsevier B.V. All rights reserved.. Keywords: Silver indium sulfide Thin films Chemical bath deposition. 1. Introduction The AgInS2 compound can be grown as tetragonal and orthorhombic phase [1]. In the tetragonal crystal structure it shows two direct band gaps, at 1.86 and 2.02 eV [1], while in the orthorhombic crystal structure it shows two band gaps at 1.96 and 2.04 eV [2]. AgInS2 belongs to the I-III-VI2 group. It is one of the least studied materials compared to the thorough investigated copper indium chalcogenides (CIS) used in photovoltaic device applications [2,3]. For example, making a comparison between CuInS2 and AgInS2 we have found out that CuInS2 has an optical band gap of 1.5 eV while AgInS2 has a wider band gap (1.86–2.04 eV); both materials have a high absorption coefficient; CuInS2 shows a p-type electrical conductivity, and although AgInS2 shows a n-type electrical conductivity [4], it can be doped with Sb [5] and Sn [6] atoms to change its conductivity to p-type. Several methods such as thermal evaporation [7], spray pyrolysis [8], co-evaporation [9], and chemical bath deposition (CBD) [10] have been used to obtain AgInS2 thin films, but CBD has proved to be the most attractive, easy to apply, less expensive and suitable for large area deposition. Moreover, in comparison with thermal evaporation and co-evaporation methods CBD does not require high vacuum systems.. ∗ Corresponding author. Tel.: +52 8183294000x6363/8183294010; fax: +52 8183765375. ˜ E-mail address: yolapm@gmail.com (Y. Pena). 0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apsusc.2012.09.077. In this work, the results of the structural, chemical composition, optical and electrical characterization of the polycrystalline silver indium sulfide thin films obtained through the annealing of chemically deposited In2 S3 –Ag2 S layers are presented. 2. Experimental details 2.1. Deposition of In2 S3 thin films In2 S3 thin films were deposited by chemical bath deposition method using a mixture of the following reagents in the order described here: 10 mL of In(NO3 )3 0.1 M, 2 mL of CH3 COOH 0.1 M, 16 mL of CH3 CSNH2 1 M, and water to complete a volume of 100 mL. The glass substrates (Corning, 25 mm × 75 mm) were placed vertically in the solution. The chemical deposition was carried out at 35 ◦ C for 22 h, since lower deposition temperature produces thinner films, and higher deposition temperature accelerates the precipitation of the solution resulting in films of low quality. 2.2. Deposition of Ag2 S thin films Chemically deposited silver sulfide thin films were obtained by following the procedure given in Ref. [11] using: 12.5 mL of 0.1 M solution of AgNO3 , 4.5 mL of 1 M solution of Na2 S2 O3 , 5 mL of 0.5 M solution of C3 H8 N2 S in the given sequence then adding deionized water while stirring the solution until completing a 100 mL volume. Indium sulfide thin films prepared previously were used as.

(2) S. Lugo et al. / Applied Surface Science 263 (2012) 440–444. substrates. The substrates were placed vertically in the solution at 35 ◦ C for 1, 2 or 3 h. For this study we chose a deposition time of 1 h. 2.3. Thermal annealing The thin films of In2 S3 –Ag2 S were thermally annealed in a tubular furnace (Thermolyne 21100). We have made some annealing experiments of the In2 S3 /Ag2 S layers at 350 ◦ C for 60 min and at 400 ◦ C for 60 and 90 min in N2 atmosphere. For this study we chose an annealing temperature and time of 400 ◦ C and 60 min in order for it to react and convert the In2 S3 –Ag2 S films into AgInS2 . 2.4. Characterization. 441. A second route can be proposed for the deposition of thin films of In(O;OH)S, thioacetamide was used as source of S2− through the hydrolysis in an acidic environment; and acetic acid (AcOH) was used as complexing agent; the entire reaction can be written as follows [13]: [In(Ac)4−x ] + CH3 SCNH2 → [In(O; OH)S]film + (4 − x)HAc + NCNH2 + H2 O. (3). The chemical reactions for the deposition of Ag2 S films taking place in the chemical bath could be considered as below. Silver ions, Ag+ , in the bath combine with S2 O3 2− to initially form an insoluble Ag2 S2 O3 , which in excess of S2 O3 2− , form soluble complexes: [Ag2 (S2 O3 )3 ]4− → 2Ag+ + 3(S2 O3 )2−. X-ray diffraction (XRD) patterns were recorded on a Rigaku ˚ D-Max 2000 diffractometer using Cu K␣ radiation ( = 1.5406 A). The chemical composition of the annealed films was determined by energy dispersive X-ray spectroscopy (EDX) using an Inca Oxford Instruments system attached to the scanning electron microscope. The surface morphology was studied by scanning electron microscopy (SEM) JEOL model JSM 5800LV at 1 kV and 25,000×. Field emission atomic force microscopy (FE-AFM) analysis was done using a JEOL JSM-6701 F equipment, the thickness of the film was measured by AFM and SEM. The optical transmittance at normal incidence, T(), and specular reflectance spectra, R(), of the films were measured with a spectrophotometer Shimadzu model UV-1800 in the UV–vis-NIR region (190–1100 nm wavelength range). Hall measurements were recorded to obtain the value and type of the electrical conductivity. The temperature dependent conductivity measurements were performed using equipment named Janis CCS 400/202 N with a temperature range of 300–10 K, and in order to do this it was necessary to apply a pair of coplanar carbon paint electrodes. 3. Results and discussion 3.1. Structural characterization and chemical compositional analysis The AgInS2 films were obtained by the deposition in sequence of layers of Ag2 S, deposited at 35 ◦ C for 1 h, over an In2 S3 film previously deposited at 35 ◦ C for 22 h. When we performed the annealing of the structure In2 S3 /Ag2 S using a Ag2 S layer deposited for 2 or 3 h, the XRD results showed that the film has a mixture of phases: AgInS2 (tetragonal and orthorhombic) and Ag2 S (acanthite). When we made the annealing experiments of the In2 S3 /Ag2 S layers at 400 ◦ C for 60 and 90 min we found from the XRD results that there is no difference between the annealing time considered at 60 and 90 min. When we performed the annealing of the In2 S3 /Ag2 S layers at 350 ◦ C, we found out a mixture of phases (In2 S3 and AgInS2 ), not just the one which corresponds to the AgInS2 . In addition, the XRD results showed that AgInS2 film has not crystallized completely at 350 ◦ C. So, this was the reason, we decided to perform the annealing of the structure In2 S3 /Ag2 S at 400 ◦ C for 1 h. The chemical reactions for the formation of AgInS2 are described below: The presence of the air in the solution environment favoured the production of oxide at a lower deposition temperature (35 ◦ C). There are two possibilities proposed to explain the formation of In2 O3 from the thioacetamide–In(III) solution. On one hand, the precipitation of the hydroxide [12]:. Ag2 S2 O3 + H2 O ⇔ Ag2 S + SO4. 2−. + 2H. (4) +. (5). The overall reaction of the ternary system films containing the AgInS2 phase is given by: [In(O; OH)S]film + Ag2 Sfilm 400 ◦ C → 2Ag+ + 2In3+ + 2S2−. (6). 2Ag+ + 2In3+ + 2S2− → 2AgInS2 film or In2 S3 film + Ag2 Sfilm → 2Ag+ + 2In3+ + 2S2−. (7). 2Ag+ + 2In3+ + 2S2− 400 ◦ C → 2AgInS2 film From the XRD pattern of the sample it was found that the ternary system contains the AgInS2 phase (see Fig. 1), which is in agreement with literature [14]. The XRD pattern shown in Fig. 1 corresponds to both structures of AgInS2 : the tetragonal (chalcopyrite) structure of AgInS2 T(JCPDS 25-1330) with reflections in (1 1 2), (2 0 0), (2 2 0), (2 0 4), and (3 1 2); and the orthorhombic structure of AgInS2 O(JCPDS 25-1328) with reflections in (2 0 0), (0 0 2), (1 2 1), (0 4 0), (3 2 0), and (0 4 2). Additionally, Fig. 1 shows two peaks (2 2 2) and (6 2 2) which correspond to indium oxide (In2 O3 ). From the chemical compositional analysis we found the following results Ag = 22.21 at%, In = 29.52 at%, and S = 48.27 at%. The error margin in EDX data is 5%. These results showed that the composition of the film is close to the stoichiometric composition of AgInS2 . 3.2. SEM and AFM measurements Fig. 2(a) shows a typical SEM image of the morphology of the In2 S3 –Ag2 S samples, measured after the films reacted thermally in N2 at 400 ◦ C for 1 h. In this picture we can see that there are clusters of quasi-spherical shape of varying sizes. Fig. 2(c) shows a cross sectional SEM image of the same In2 S3 –Ag2 S sample. In this picture we can see that the film thickness is in the order of 200 nm. Fig. 2(b) shows a typical AFM image of the surface topography in 3D of the In2 S3 –Ag2 S samples. This film shows that after the thermal annealing small grains had coalesced, resulting in bigger grains on the film surface. The average film thickness was 270 nm for the resulting AgInS2 film. 3.3. Optical and electrical characterization. In3+ + 3H2 O → In(OH)3 + 3H+. (1). Optical transmission, T(), and reflection spectra, R(), were recorded in the range of 300–1100 nm. Fig. 3 shows T() and R() responses for AgInS2 film. The absorption coefficient (˛) was calculated using T() and R() data and the well known expression, for direct optical transitions [15,16], given by. 2In(OH)3 → In2 O3 + 3H2 O. (2). ˛h = A(h − Eg ). r. (1).

(3) 442. S. Lugo et al. / Applied Surface Science 263 (2012) 440–444. Fig. 1. X-ray diffraction pattern for AgInS2 film (after annealing the In2 S3 –Ag2 S sample in N2 at 400 ◦ C for 1 h). “T” corresponds to the tetragonal (chalcopyrite) structure and “O” to the orthorhombic structure of the AgInS2 .. where A is a constant, and Eg is the optical band gap. In this equation r = 1/2 for direct allowed optical transitions and 3/2 for the direct forbidden ones. The band-gap value can be obtained from the best linear approximation in the (˛h)1/r vs. h plot and its extrapolation to (˛h)1/r = 0. Fig. 4 shows the (˛h)2 vs. h plot for AgInS2 film. The band gap value obtained was Eg = 1.86 eV, this value agrees with what was reported for chalcopyrite AgInS2 (Eg = 1.87 eV) [17]. The value of the electrical conductivity for AgInS2 thin film was 1.2 × 10−3 ( cm)−1 . Hall measurements indicated that the AgInS2 film has n-type electrical conductivity.. The temperature dependent conductivity measurements were carried out (see Fig. 5). The conductivity is given by Ref. [18]:.  = 1 exp.  −E  a. KT. where  1 is the pre-exponential factor proportional to the grain size; Ea is the activation energy, K the Boltzmann constant, and T the temperature in Kelvin. From this equation and the data given. Fig. 2. (a) SEM, (b) AFM, and (c) cross sectional SEM images for AgInS2 film (after annealing the In2 S3 –Ag2 S samples in N2 at 400 ◦ C for 1 h)..

(4) S. Lugo et al. / Applied Surface Science 263 (2012) 440–444. 443. Fig. 5. Temperature dependent conductivity plot for AgInS2 film (after annealing the In2 S3 –Ag2 S sample in N2 at 400 ◦ C for 1 h).. Fig. 5 we can see that semiconducting behavior of the sample is demonstrated. The activation energy (Ea ) was determined for a temperature range of 290–283 K and 166–220 K being 0.17 eV and 5 meV, respectively. 4. Conclusions Fig. 3. T() and R() spectra for AgInS2 films (after annealing the In2 S3 –Ag2 S samples in N2 at 400 ◦ C for 1 h).. in Fig. 5 we can calculate the activation energy in a given range of temperature. The above equation becomes to: ln  = ln 1 −. Ea KT. Calculating the slop in the plot we can determine the activation energy of the film for different ranges of temperature. From. We have reported the results of the structural, morphological, optical, and electrical characterizations of AgInS2 thin films obtained by annealing the chemically deposited In2 S3 –Ag2 S layers. According to the XRD and EDX results, heating In2 S3 –Ag2 S layers at 400 ◦ C in N2 for 1 h, the chalcopyrite structure of AgInS2 can be obtained. This film has an optical band gap, Eg , of 1.86 eV and an electrical conductivity value of 1.2 × 10−3 ( cm)−1 . The obtained AgInS2 films are suitable for solar cell applications (as a possible buffer layer). Acknowledgements This work was supported by PAICYT-UANL 2010 (México) grant ˜ Technical assistance of Hugo Salas (Laboratorio de of Dra. Y. Pena. Caracterización Microestructural de Materiales Avanzados-UANL) with FE-SEM measurements, and José Campos (CIE-UNAM) with temperature dependent conductivity measurements, which are strongly appreciated. References. Fig. 4. Plot of (˛h)2 vs. h for AgInS2 film (after annealing the In2 S3 –Ag2 S sample in N2 at 400 ◦ C for 1 h).. [1] J.L. Shay, B. Tell, L.M. Schiavone, H.M. Kasper, F. Thiel, Physical Review B 9 (1974) 1719–1723. [2] J.L. Shay, J.H. Wernick, Ternary Chalcopyrite Semiconductors: Growth, Electronic Properties, and Applications, Pergamon Press, USA, 1975. [3] R.W. Birkmire, Proc. 26th IEEE PVSC, Anaheim, CA, 1997, p. 295. [4] K. Okamoto, K. Kinoshita, Solid-State Electronics 19 (1976) 31–35. [5] K. Yoshino, H. Komaki, T. Kakeno, Y. Akaki, T. Ikari, Journal of Physics and Chemistry of Solids 64 (2003) 1839–1842. [6] M.L. Albor-Aguilera, D. Ramírez-Rosales, M.A. González-Trujillo, Thin Solid Films 517 (2009) 2535–2537. [7] Y. Akaki, S. Kurihara, M. Shirahama, K. Tsurugida, T. Kakeno, K. Yoshino, Journal of Materials Science: Materials in Electronics 16 (7) (2005) 393–396. ˜ D. Martínez-Escobar, [8] M. Calixto-Rodriguez, H. Martínez, M.E. Calixto, Y. Pena, A. Tiburcio-Silver, A. Sanchez-Juarez, Materials Science and Engineering B 174 (2010) 253–256. [9] C.A. Arredondo, J. Clavijo, G. Gordillo, Journal of Physics: Conference Series 167 (2009) 012050. [10] L. Li-Hau, W. Ching-Chen, L. Chia-Hung, L. Tai-Chou, Chemistry of Materials 20 (2008) 4475–4483. ˜ [11] A. Núnez, M.T.S. Nair, P.K. Nair, Semiconductor Science and Technology 20 (6) (2005) 576–585..

(5) 444. S. Lugo et al. / Applied Surface Science 263 (2012) 440–444. [12] B. Asenjo, A.M. Chaparro, M.T. Gutiérrez, J. Herrero, C. Maffiotte, Electrochimica Acta 49 (2004) 737–744. ˜ [13] W. Vallejo, C. Quinones, G. Gordillo, Journal of Physics and Chemistry of Solids 72 (2012) 573–578. [14] Ch. Kong-Wei, H. Chao-Ming, P. Guan-Ting, Ch. Wen-Sheng, L. Tai-Chou, C.K.Y. Thomas, Journal of Photochemistry and Photobiology A: Chemistry 190 (2007) 77–87.. [15] T.S. Moss, Optical Properties of Semiconductors, Butterworths, London, UK, 1959. [16] K.L. Chopra, S.R. Das, Thin Film Solar Cells, Plenum Press, New York, 1983. [17] M. Ortega-López, A. Morales-Acevedo, O. Solorza-Feria, Thin Solid Films 385 (2001) 120–125. [18] R. Caballero, C. Guillén, Thin Solid Films 431-432 (2003) 200–204..

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Tribunal Central de Trabajo Seguridad Social Jurisprudencia del TCT en materia de seguridad social correspondiente a los meses de julio, agosto y septiembre de 1979
el causante en la fecha de su fallecimiento, acaecido el día 19 de julio de 1969, no se encontraba en situación de alta ni asimilada al alta, al haber cesado en la prestación de sus
Tribunal Supremo, Salas I y V
En el primer motivo del recurso al amparo del número 1.° del artículo 1692 de la Ley de Enjuiciamiento Civil, se denuncia la infracción por interpretación errónea del artículo 1.°, 1,
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c Servicios médicos de empresa Si se trata de la organización del servicio por una sola empresa, habrá de aplicarse el criterio del artículo 5.° agrupamiento de centros de la misma
Tribunal Supremo, Sala VI Cuestiones de Seguridad Social
[dado] que el artículo 28.2 del Decreto regulador del Régimen Especial de la Seguridad Social del Servicio Doméstico, de 25 de septiembre de 1969, dispone que las prestaciones derivadas
Tribunal Supremo, Sala VI Cuestiones de trabajo
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Resoluciones administrativas Ministerio de Trabajo: Contrato de trabajo Convenios colectivos Cierre patronal Clasificación profesional Jornada de trabajo y horas extraordinarias Turnos de trabajo Horario de trabajo Descanso dominical y semanal Va
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Crónica internacional
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