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T. Ngo, S. Chavhan, I. Kosta, Ó. Miguel, H. Grande, R. Tena-Zaera (2014)
Electrodeposition of antimony selenide thin films and application in semiconductor sensitized solar cells.ACS applied materials & interfaces, 6 4
Mauricio Solís, M. Rincón, J. Calva, G. Alvarado (2013)
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A. Kulkarni, S. Arote, H. Pathan, R. Patil (2015)
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Yanxue Chen, Lin Wei, Guanghua Zhang, J. Jiao (2012)
Open structure ZnO/CdSe core/shell nanoneedle arrays for solar cellsNanoscale Research Letters, 7
J. Rhee, Chih‐Chun Chung, E. Diau (2013)
A perspective of mesoscopic solar cells based on metal chalcogenide quantum dots and organometal-halide perovskitesNpg Asia Materials, 5
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A photoelectrochemical cell based on chemically deposited Sb2Se3 thin film electrode and dependence of deposition on various parametersSolar Energy Materials, 6
Y. Choi, T. Mandal, Woon Yang, Yong Lee, S. Im, J. Noh, S. Seok (2014)
Sb(2)Se(3) -sensitized inorganic-organic heterojunction solar cells fabricated using a single-source precursor.Angewandte Chemie, 53 5
Chong Chen, Yinjuan Xie, G. Ali, S. Yoo, S. Cho (2011)
Improved conversion efficiency of Ag2S quantum dot-sensitized solar cells based on TiO2 nanotubes with a ZnO recombination barrier layerNanoscale Research Letters, 6
N. Platakis, H. Gatos (1972)
Threshold and memory switching in crystalline chalcogenide materialsPhysica Status Solidi (a), 13
A. Kulkarni, S. Arote, H. Pathan, R. Patil (2015)
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C. Patrick, F. Giustino (2011)
Structural and Electronic Properties of Semiconductor‐Sensitized Solar‐Cell InterfacesAdvanced Functional Materials, 21
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T Tuyen Ngo, S Chavhan, I Kosta, O Miguel, H Grande, R Tena-Zaera, ACS Appl (2014)
Electrodeposition of antimony selenide thin films and application in semiconductor sensitized solar cellsAppl. Mater. Interfaces, 6
Mater Renew Sustain Energy (2015) 4:15 DOI 10.1007/s40243-015-0058-5 ORIGINAL PAPER Sb Se sensitized heterojunction solar cells 2 3 2 1 1 2 • • • Anil N. Kulkarni Sandeep A. Arote Habib M. Pathan Rajendra S. Patil Received: 26 February 2015 / Accepted: 29 July 2015 / Published online: 15 August 2015 The Author(s) 2015. This article is published with open access at Springerlink.com Abstract The study deals with the sensitization of the Introduction porous SnO films deposited on fluorine-doped tin oxide with nanocrystalline Sb Se . The sensitization was Metal chalcogenides such as CdS [1], CdSe [2], Ag S[3], 2 3 2 achieved for three different sensitization times employing Sb S [4], Bi S [5] and Sb Se [6] have recently attracted 2 3 2 3 2 3 chemical solution deposition with antimony chloride and considerable attraction of researchers due to their potential 3? 2- sodium selenosulphate as precursors for Sb and Se , applications in electrical and optical devices. Among these respectively. The unsensitized and sensitized photoelec- materials, antimony selenide (Sb Se ) is a group V –VI 2 3 2 3 trodes were characterized using X-ray diffractometry, layered structured direct band gap semiconductor with scanning electron microscopy and diffused reflectance orthorhombic crystal structure [7]. Sb Se displays a nar- 2 3 spectroscopy. The solar cells fabricated using three dif- row band gap of 1.1–1.3 eV, [8–10] which approaches the ferent photoelectrodes were characterized for their photo- ideal Shockley–Queisser value, [11] and has the ability to voltaic performance using the photocurrent density versus extend light harvesting over the near-IR region up to photovoltage curves. The study revealed that sensitization approximately 1000 nm. Besides, the relative positions of time significantly influences the photovoltaic parameters the conduction band edges of nanostructured Sb Se and 2 3 namely, short circuit current density (J ), open circuit SnO display favourable energetics for electron transfer at sc 2 voltage (V ) and fill factor (FF) and hence the photovoltaic their interface [12]. In addition, theoretical calculations oc efficiency (g). performed by Giustino et al. [9, 10] demonstrated the improved performance of Sb Se -based devices compared 2 3 to Sb S based cells, and suggested Sb Se as a promising 2 3 2 3 Keywords Sb Se Photosensitization SnO 2 3 2 candidate for achieving 20 % PCE. In spite of these Heterojunction Solar cell advantages, Sb Se -based solar cells have rarely been 2 3 experimentally demonstrated. Of these one is photoelec- trical solar cell fabricated using a Sb Se photoanode 2 3 prepared by chemical bath deposition (CBD) reported by Bhattacharya et al. [13]. Second one is based on elec- trodeposited Sb Se thin films in TiO /Sb Se /CuSCN 2 3 2 2 3 planer heterojunction solar cells reported by Zaera et al. [14]. However, only one report is available on photovoltaic performance of Sb Se as a sensitizer spin coated on TiO 2 3 2 & Anil N. Kulkarni photoanode in semiconductor sensitized solar cell appli- kulkarni.may29@gmail.com cations [6]. Conversely, the reports available on Bi S and 2 3 Sb S sensitized SnO photoanode-based solar cells are 2 3 2 Advanced Physics Laboratory, Department of Physics, Savitribai Phule University, Pune 411007, India limited [4, 5], which showed very low power conversion efficiency (PCE) as compared to other nanocrystalline Department of Physics, PSGVPM’s ASC College, Shahada, semiconductor sensitized solar cells. Till date, TiO has India. 123 15 Page 2 of 6 Mater Renew Sustain Energy (2015) 4:15 widely been used as photoanode material in most of the and double distilled water, respectively, in two different 3? SSSCs [1–5]. However, the promising optical and electrical beakers, wherein SbCl acts as a precursor of Sb and 2- properties of SnO , such as higher electronic mobility and Na SeSO that of Se . TEA (20 %; 5 ml), a complexing 2 2 3 large band gap (3.8 eV), draw the attention of researchers agent, was then added to the bath containing antimony towards it as an alternative photoanode for SSSC. Fur- source. The solution containing selenium source was then 3? thermore, SnO has a 0.4 V more positive band edge as slowly added to the bath containing Sb and TEA. The compared to TiO ; hence, effective charge injection into deposition process of Sb Se was considered to be based on 2 2 3 3? 2- E of SnO from excited sensitizer is expected compared slow release of Sb and Se ions in the solution, which was CB 2 3? to TiO [12]. In spite of merits of these semiconductor achieved using TEA. TEA controls the Sb ion concen- 3? materials for its solar cell application, reasons for the low tration and allows for obtaining soluble species of Sb in the conversion efficiencies of cells based on stibinite family bath. The pH of the combined bath was adjusted to be around members still elude better understanding. Studies on dif- 8–10, by adding few drops of 1 M NaOH solution. The ferent factors responsible for the photoconversion in these previously prepared SnO photoelectrodes were introduced 3? 2- cells need to be carried out and optimized for obtaining the vertically into this bath containing both Sb and Se ,at theoretically projected efficiencies of these nanostructured room temperature for the deposition of Sb Se over the 2 3 excitonic solar cells. Therefore, to investigate the effect of porous nanocrystalline SnO . After carrying out sensitiza- various parameters such as photoanode properties, counter tion for different time durations of about 30, 60 and 120 min, electrode, electrolyte and sensitization time of photoanode, the photoelectrodes were withdrawn from the bath and the which decide performance of cells based on Sb Se still corresponding photoanodes were named as P-30, P-60 and 2 3 need further studies and optimization. P-120, respectively. The sensitized photoelectrodes were In this work, porous SnO photoelectrodes have been observed to be coated with increased darkening of brownish prepared by doctor blade method. Sensitization of SnO tinge of the photoanodes from P-30 to P-120. This may be photoelectrode with nanocrystalline Sb Se has been due to the enhanced level of deposition of nanocrystalline 2 3 achieved using chemical bath deposition by varying the Sb Se onto the bare photoanodes of SnO with increase in 2 3 2 sensitization time from 30 to 120 min. To the best of our sensitization time. knowledge, first time we are exploring the SnO /Sb Se 2 2 3 combination in semiconductor sensitized solar cells and of Solar cell assembly the many influencing factors, the effect of sensitization time is given emphasis in the present study. Preparation of electrolyte and counter electrode (a) Electrolyte: The aqueous solution of polysulphide Experimental electrolyte was prepared using the 0.5 M Na S, 0.1 M sulfur powder and 0.2 M KCl. Materials (b) Counter electrode: To prepare the counter electrode, the FTO glass was washed with acetone, water, and All chemicals [antimony chloride (SbCl ) (Merck), sodium ethanol. After removing contaminants, carbon-coated sulphite (SRL), selenium metal powder (Thomas baker), counter electrode was prepared on the conductive side triethanolamine (TEA) (SRL)] were of the highest purity of the FTO substrate using mild flame. available and they were used without further purification. For cell assembly, the carbon-coated FTO was used as a Preparation of SnO photoanode counter electrode. The Sb Se sensitized SnO photoelec- 2 3 2 trode and counter electrode were clamped together into a To make SnO paste, 0.5 gm of SnO powder was mixed with sandwich type configuration with a droplet of polysulphide 2 2 ethanol, acetic acid, ethylene glycol and a-terpineol in mortar electrolyte injected between them. The fabricated solar and pestle for 40 min, then SnO film was prepared on fluo- cells using photoelectrodes P-30, P-60 and P-120 were rine-doped tin oxide (FTO) glass by doctor blade method. named C-30, C-60 and C-120, respectively, and charac- terized to study their photovoltaic performance. After drying, all samples were annealed at 450 C for 1 h. The analysis of structural, morphological properties and elemental composition of unsensitized SnO photoanode Chemical bath deposition of Sb Se on porous SnO 2 3 2 2 photoanode and Sb Se sensitized photoanode of SnO was carried out 2 3 2 using X-ray diffractometry (XRD) (model: XRD, Rigaku In the present synthesis, solutions of SbCl (0.01 M; 10 ml) ‘‘D/B -2400’’, Cu K = 0.154 nm), scanning electron max a and Na SeSO (0.01 M; 10 ml) were prepared in acetone microscopy (SEM) (model: JEOL-JSM 6360-A) and 2 3 123 Mater Renew Sustain Energy (2015) 4:15 Page 3 of 6 15 energy-dispersive X-ray spectroscopy (EDAX), respec- However, for all sensitized photoelectrodes, the absorbance tively. A UV–Vis spectrophotometer (model: JASCO is enhanced in the visible region. It may be noted that the V-670) was used to record optical absorption spectra of intensity of the absorption spectra increases in the visible unsensitized and sensitized photoelectrodes in diffused region from 400 to 600 nm with the increasing sensitiza- reflectance mode in the range 200–800 nm at room tem- tion time from P-30 to P-120. This fact suggests that perature. The cell performance was measured by a semi- amount of loading of a sensitizer increases with increase of conductor characterization unit [Keithley 2420 (source loading time resulting in enhanced absorption of visible -2 meter)] under illumination of 30 mW cm . light from P-30 to P-120. Also, there is an apparent red shift in the absorption feature from P-30 to P-120, which is probably a consequence of increase in particle size of Results and discussions sensitizer with increase of deposition time and may be attributed to the aggregation of sensitizer on the surface of Structural analysis of bare SnO and SnO /Sb Se bare photoelectrode. This observation is in accordance with 2 2 2 3 photoanodes the other metal chalcogenides including Sb Se deposited 2 3 with SILAR technique [9, 16]. Figure 1 shows diffraction pattern for unsensitized SnO photoelectrode with defined peaks at 2h = 26.63, 34.07, Morphological and elemental analysis of SnO / 38.20, 52.18 and 55.19 corresponding to the diffraction Sb Se photoanodes 2 3 from planes which confirm its tetragonal phase (JCPDS file no: 41-1445). Figure 1 also shows the diffraction patterns To further analyse the effect of sensitization time on the related to P-10, P-20 and P-30, respectively. P-30, P-60 and SnO photoelectrode, morphology of both bare and sensi- P-120 show diffraction signatures corresponding to both, tized photoelectrode was studied. Figure 3 shows the Sb Se and SnO . In P-30, P-60 and P-120, Sb Se scanning electron micrographs of Sb Se sensitized SnO 2 3 2 2 3 2 3 2 nanocrystals appeared in the orthorhombic phase (JCPDS photoelectrode with different sensitization times. It is file no: 72-1184). clearly seen from Fig. 3 that the pores in SnO photo- electrode are filled up with nanocrystalline Sb Se . The 2 3 Optical properties of bare SnO and SnO /Sb Se pore-filling apparently increased with increase of deposi- 2 2 2 3 photoanodes tion time from P-30 to P-120. In addition to this, there is no observable alteration in the surface quality and structure of The absorption spectra of the unsensitized SnO , P-30, the SnO photoelectrodes with the increase in sensitization 2 2 P-60 and P-120 are shown in Fig. 2. It is seen from the time. figure that the absorption for unsensitized SnO is limited Supplementary elemental analysis by energy-dispersive to the ultraviolet region of electromagnetic spectrum. X-ray spectroscopy (EDAX) for unsensitized and sensi- tized photoelectrode was carried out and shown in Fig. 4. EDAX spectrum for unsensitized film reveals the presence of only Sn and O, while that of all sensitized films show the presence of Sb and S in addition to Sn and O. The quan- titative analysis obtained by EDAX shows an overall increment in the amount of Sb and Se from P-30 to P-120, with increasing deposition time. It is also observed that Sb/ Se ratio leads to the average stoichiometric value of 2/3 for sensitization time of 120 m (Table 1). Therefore, the XRD results along with EDAX spectrum analysis demonstrate sensitization of SnO qualitatively using CBD. Photovoltaic performance analysis The photovoltaic performance of solar cells C-30, C-60 and C-120 was investigated by conducting photocurrent density (J) versus voltage (V) measurements. Figure 5 shows photocurrent density (J) versus photovoltage (V) charac- Fig. 1 XRD spectra of bare SnO and SnO /Sb Se photoanodes 2 2 2 3 teristics curves of the fabricated solar cells namely, C-30 sensitized with different deposition times; P-30: 30 min, P-60: 60 min and C-60. The photovoltaic parameters like short circuit and P-120: 120 min 123 15 Page 4 of 6 Mater Renew Sustain Energy (2015) 4:15 Fig. 2 Optical absorption spectra of bare SnO and SnO /Sb Se photoanodes sensitized with different deposition times; P-30: 30 min, P-60: 2 2 2 3 60 min and P-120: 120 min Fig. 3 Elemental (% atomic) analysis of bare SnO and SnO /Sb Se photoanodes sensitized for 30 min 2 2 2 3 Table 1 Elemental (% atomic) analysis of bare SnO and SnO 2 2 photoanodes sensitized with Sb Se 2 3 Photoanode Sensitization time (min) Sn O Sb Se Bare SnO – 39.97 60.03 – – P-30 30 24.32 73.64 1.08 0.96 P-60 60 21.84 65.63 5.43 7.10 P-120 120 21.05 62.89 6.02 10.04 It is observed from the Table 2 that, with increase in sensitization time, the value of J increases, while V sc oc shows decrease in its value from C-30 to C-60. However, in spite of better optical absorbance of P-120 vis-a`-vis others, cell fabricated using it does not show considerable Fig. 4 SEM images of SnO /Sb Se photoanodes sensitized with 2 2 3 photovoltaic performance. This may be due to the over different deposition times; P-30: 30 min, P-60: 60 min and P-120: aggregation of sensitizer over the surface of the 120 min photoanode. current density (J ), open circuit voltage (V ), fill factor With increase of sensitization time, the optical absorp- sc oc (FF) and photovoltaic efficiency (g) are obtained from the tion spectra as given in Fig. 2 clearly show an enhanced J–V curves and listed in Table 2. amount of loading of the sensitizer into the 123 Mater Renew Sustain Energy (2015) 4:15 Page 5 of 6 15 Fig. 5 J-V characteristics of cells C-30 and C-60 fabricated with SnO /Sb Se photoanodes sensitized with deposition times of 30 and 2 2 3 60 min, respectively Fig. 7 Cartoon showing recombination of excited electron at SnO / Sb Se -electrolyte interface due to aggregation 2 3 Table 2 Photovoltaic parameters of Sb Se sensitized SnO pho- 2 3 2 photoelectrodes. This is evident from the improved optical toanode-based solar cell prepared with different sensitization time absorption in the visible region. Such an enhanced Solar Sensitization V J FF g oc sc absorption of light in the visible region leads to generation cell time (min) (V) (mA/cm ) (%) (%) of increased number density of excitons at the electrode– C-30 30 0.272 0.715 49 0.31 electrolyte interface. The excitons so generated get disso- C-60 60 0.182 0.795 41 0.19 ciated at the SnO /Sb Se interface due to the favourable 2 2 3 interfacial band energetics (see Fig. 6) leading to effective electron injection from excited Sb Se to the conduction 2 3 band of SnO [15], which further results in improved photocurrent (J) from C-30 to C-60 and hence J in from sc C-30 to C-60. But, such an aggregation of sensitizer may cause to delay the transfer of excited electrons from sensitizer to the conduction band of SnO , giving rise to the recombination of excited electron at electrode–electrolyte interface. This probable reason depicted in schematic form in Fig. 7 apparently explains the reduction of V , for C-60. oc However, as discussed earlier in optical analysis, optical absorption enhances with increase in deposition time, which may be attributed to the further aggregation of sensitizer in P-120. In spite of enhanced absorption in P-120, the increased number density of sensitizer mole- cules in it, may have offered the increased grain boundary resistance in C-120 vis-a-vis former, probably affected the photocurrent (J) and photovoltage (V).This probable reason depicted in schematic form in Fig. 7, which apparently rationalizes the poor values of photovoltage and pho- tocurrent in C-120 and hence not incorporated in the Table 2. The same was confirmed by the Solis and Co- Workers [16]. Relatively better photovoltaic efficiency of C-30 vis-a- vis other cells may be obviously attributed to its improved photovoltaic parameters. Fig. 6 Schematic showing band energetics of SnO /Sb Se interface 2 2 3 123 15 Page 6 of 6 Mater Renew Sustain Energy (2015) 4:15 2. Chen, Y.X., Wei, L., Zhang, G.H., Jiao, J.: Open structure ZnO/ The performance observed in present study in terms of CdSe core/shell nanoneedle arrays for solar cells. Nanoscale Res. photoconversion efficiency (g) about 0.31 % is relatively Lett. 7, 516–521 (2012) greater than that of as-prepared spin-coated TiO pho- 3. Chen, C., Xie, Y., Ali, G., Yoo, S.H., Cho, S.O.: Improved toanode with Sb Se -based solar cell showing efficiency of conversion efficiency of Ag S quantum dot-sensitized solar cells 2 3 based on TiO nanotubes with a ZnO recombination barrier layer. about 0.22 % reported by Seok et al. [6]. It can be seen 2 Nanoscale Res. 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Materials for Renewable and Sustainable Energy – Springer Journals
Published: Aug 15, 2015
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