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Fabrication processes of Organometal Perovskite-based Solar Module 124x116mm (300 x 300 DPI)

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DOI: 10.1039/C3CP55313B

Physical Chemistry Chemical Physics

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DOI: 10.1039/C3CP55313B

solar

module

based

on

mesoscopic

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organometal halide perovskite: a route towards the upscaling process F. Matteoccia,1, S. Razzaa,1, F. Di Giacomoa, S. Casalucia, G. Mincuzzia, T.M. Browna, A. D’Epifaniob, S. Licocciab and A. Di Carloa,*

We fabricated the first solid state modules based on organometal halide perovskite CH3NH3PbI3-xClx using Spiro-OMeTAD and poly(3-hexylthiophene) as hole transport materials. Device up-scaling was performed using innovative procedures to realize large area cells and the integrated series-interconnections. The perovskite-based modules show a maximum conversion efficiency of 5.1% using both poly(3-hexylthiophene) and SpiroOMeTAD. A long term stability test was performed (in air, under AM1.5G,

1 Sun

illumination condition) using both materials showing different behaviour under continuous light stress. Whilst, the poly(3-hexylthiophene)-based module efficiency drops by about 80% respect to initial value after 170 hours, the Spiro-based module shows a promising long term stability maintaining more than 60% of its initial efficiency after 335 hours.

Dye Solar Cells (DSCs) are a suitable technology to realize large area devices by using low cost processes and materials1-4. These kinds of solar cells have already shown outstanding features including easy up-scaling, solution processing and applicability to flexible substrates5, 6. Alternative architectures called solid state DSCs (SDSCs) are investigated in order to resolve problems due to insufficient electrochemical stability of the liquid electrolyte under reverse bias conditions and

Physical Chemistry Chemical Physics Accepted Manuscript

Solid-state

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thermal stress7. The liquid electrolyte can be replaced with a hole transport material (HTM) for the

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few reports showing the up-scaling of this device. Recently, we have reported the first attempt to fabricate a SDSC module using an organic dye (called D35) as light harvester and poly(3hexylthiophene-2,5-diyl) (P3HT) polymer as HTM. A 2% PCE value was obtained for the seriesconnected

SDSC

module

with

an

active

area

13.44cm2

of

12

.

A new promising class of light harvesting materials, namely the hybrid organic halide based perovskites, have been recently employed to realize high efficiency photovoltaic solar cells 13. This kind of crystalline material shows good properties in terms of light harvesting (high absorption in a broad region of the visible spectrum) and of electron and hole mobilities

14-24

. A maximum power

conversion efficiency (PCE) of 15% was reported using CH3NH3PbI3-sensitized TiO2 together with the Spiro-OMeTAD as HTM for small area devices21. Alternative HTMs have been also studied to replace the Spiro-OMeTAD in order to reduce the fabrication cost for scaled-up devices

20,27

.

Perovskite solar cells made with polymeric HTMs such as poly-triarylamine (PTAA) and P3HT have shown a PCE of 12% and 6.7%, respectively 15. Recently, we have reported the use of a regioregular, doped, high molecular weight P3HT in combination with CH3NH3PbI3-xClx showing a PCE of 9.3% for small area devices (0.1cm2) 23. However, scaling up to module size is still an open issue for perovskite solar cell technology and reports on the feasibility of large area devices are still missing. In this paper, the first perovskite-based monolithic series-type module was realised showing very promising results in terms of the power conversion efficiency, the reproducibility of the fabrication process and long-term stability. To achieve these results, important innovative procedures were implemented in order to realize an efficient up-scaling process including: -a customised formulation of TiO2 paste to realize a uniform thin titania scaffold by Screen Printing technique; - a proper cleaning procedure of the CH3NH3PbI3-xClx on the interconnection area between single cells to realize a patterned perovskite deposition; -a c-TiO2 patterned deposition adapting and optimizing the one as already reported in our previous work12. Furthermore, two

Physical Chemistry Chemical Physics Accepted Manuscript

dye regeneration process8. Although, small area devices have been widely studied 8-11 there are very

Physical Chemistry Chemical Physics

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different HTMs were used, i.e. the Spiro-OMeTAD and the P3HT polymer both reaching a PCE

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reproducibility of the fabrication process. The picture of a perovskite-based module is reported in Fig. 1a. Five single cells (active area of 3.36 cm2) are connected by using a monolithic scheme for series-interconnection with an overall active area of 16.8cm2 and an aperture area of 25cm2, as shown in fig 1.b. The layout of the module allows the measurement of each cell individually. In fact, the gold cathode (i.e. the back contact) can be easily accessed when the module was not encapsulated. By masking all the cells except for the one under test and taking the current between the photo-anode and gold cathode of each cell, it was possible to extract the I-V characteristics of each large area cell forming the module. Whereas, the stability of un-encapsulated devices was sufficient to carry out single measurements, long term degradation studies were carried out after encapsulating the module. SEM Micrographs reported in Fig.2a-b show the cross-section of the monolithic structure with different magnifications. The images confirm the expected thicknesses of the constituent layers: 110 nm of compact TiO2, 700 nm of TiO2 scaffold and 150nm of P3HT layer. As already shown by M.M. Lee et al13, the CH3NH3PbI3-xClx in fig.2 produces a rough discontinuous capping layer over the TiO2 scaffold. Moreover, strong adhesion of the compact TiO2 layer (highlighted in fig.2b with green colour) over the FTO surface was obtained as reported in our previous work11. Figures 2c-d show the difference between the morphology of the titania scaffold before (Fig 2c) and after (Fig 2d) the CH3NH3PbI3-xClx perovskite deposition. The presence of a continuous network of large CH3NH3PbI3-xClx perovskite aggregates with size of up to one hundred nanometers can be identified with crystals interpenetrating into the titania scaffold (which in turn is composed of distinguishable nanoparticles with a size of around 20 nm). The main photovoltaic parameters of the large area cells with the doped P3HT HTM are reported in Table1. The results show average values of: Voc = 913mV ± 40 mV, JSC = 10.6mA/cm2 ± 1.6

Physical Chemistry Chemical Physics Accepted Manuscript

equal to 5.1%. The P3HT was utilized as cost-effective alternative material also to test the

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mA/cm2, FF = 51.2% ± 6.7% and finally a PCE = 5.0% ± 1.1% . Averages are calculated on the

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the VOC is very similar for each cell, whilst a ±15% relative variation in FF and JSC was measured between the constituent cells. This effect is probably due to the non-uniformity of HTM capping layers using the spin coating deposition. This aspect was confirmed by SEM characterization (Fig 2a). In fact, photovoltaic parameters such as FF and JSC can be affected from the recombination processes occurring at the CH3NH3PbI3-xClx/P3HT interface due to different thicknesses and quality of the P3HT capping layers deposited over the rough perovskite/TiO2 layer 20,23. This issue causes slight JSC mismatches between the constituent cells of the module limiting the module current to the lower one, as expected for the series-type configuration. Furthermore, a single perovskite-based solar cell using the Spiro-OMeTAD as HTM was fabricated. The best large area cell using the Spiro-OMeTAD shows VOC = 896mV,

JSC = 10.1mA/cm2,

FF = 65.1% and PCE = 5.9%.

Recombination in P3HT is faster compared to Spiro-based samples24 as can be observed from a smaller shunt resistance and fill factor of the P3HT cell with respect to the Spiro-OMeTAD one (FF=51.2% and 210 Ω FF=65.1% %, 1090 Ω respectively). Fig.3 presents the I-V characteristics of the perovskite-based solar modules together with the I-V of the best cells using both HTMs. Comparing the I-V measurements of the best solar cell and module for both HTMs, we can affirm that the module layout was correctly designed since the ISC for the best cells is only slightly higher compared to the current of the modules with both HTMs devices (+3% for Spiro-based and +11% for P3HT based, respectively). This proves that, notwithstanding the difficulty of obtaining a uniform deposition of the HTM on the large underlying patterned and rough surfaces using the spin coating technique, the fabricated modules have sufficient uniformity between the cells yielding a module ISC which is very close to the one of the best single cell. Tab.2 reports the main photovoltaic parameters for P3HT and Spiro-OMeTAD. The module with the P3HT HTM shows VOC= 4.5V, ISC = -36.8 mA, FF = 52.6 % and PCE = 5.1 % on active area. The IV characteristics of the P3HT-based module measured under different illumination conditions

Physical Chemistry Chemical Physics Accepted Manuscript

five large-area cells forming the module. The best cell shows a PCE equal to 6.3%. Interestingly,

Physical Chemistry Chemical Physics

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are reported in Fig.4. The module under 0.3 Sun shows a higher PCE (6.7%) than the same device

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reduction of the influence of the series resistance, confirmed by a similar increase of FF (∆FF/FF = +32.8%) when the device is illuminated under low light intensity. A successive batch, composed by four modules, was fabricated in order to evaluate the reproducibility of the fabrication process utilizing doped P3HT as HTM. The results are summarized in Tab.3. In particular, the average photovoltaic parameters, calculated on four samples, are VOC = 4.3V ± 0.4V, ISC = 25.5mA ± 5.6 mA, FF = 57.0% ± 7.9% and PCE = 3.7% ± 0.6%. These results assess the good reproducibility of the fabrication process. As previously reported, the relatively large standard deviation for the short-circuit current and fill factor can be ascribed to a non uniformity in the large-area deposition of the P3HT capping layer due to the high surface roughness of the underlying perovskite layer, as reported in previous work 23. This problem could be solved by obtaining a smoother deposition of the perovskite layer by varying the deposition technique as recently demonstrated

28

. Afterwards, in order to evaluate the whole up-

scaling process, we plot the PCE values for different device sizes obtained maintaining the same experimental conditions for each device size. The results show that the PCE drops by about 30% migrating from the 0.1cm2 cell to the about 40 times larger one (3.36cm2) for both HTMs. This drop could be due to different factors including the resistivity of the FTO electrode and the non-uniform perovskite deposition on the large area substrates using the spin coating technique. By scaling from large-area cell to the module, the PCE drops by about 14% for Spiro-based devices and 19% for P3HT-based devices. As previously reported, these slight decreases are due to the mismatch on ISC between the constituent cells forming the series-connected module. These results represent a significant starting point for future development of the perovskite-based modules.

Physical Chemistry Chemical Physics Accepted Manuscript

measured under 1 Sun, (∆PCE/PCE = +30.0%). This behaviour could be mainly ascribed to a

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Subsequently, a light soaking ageing test of 335h was performed to evaluate the long-term stability

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40°C illuminated by Class A Light Soaker in air) as reported in Fig.5a-b. To evaluate lifetime, the sealing procedure was performed in a glove box environment as described in the experimental section to reduce the impact of moisture on the perovskite material. In parallel, the optical longterm stability of the perovskite was also tested by monitoring the absorbance spectra during the stability test for sealed and un-sealed FTO/TiO2/CH3NH3PbI3-xClx samples (as already reported from M.M. Lee at al.13). Interestingly, very little variation in the absorbance spectra was measured when the samples were sealed ( ≤ 4% at 500nm). These results and procedures are reported in Supplementary Information. As shown in figure 6a, a P3HT-based solar module shows insufficient long-term stability. In fact, the PCE drops drastically after about 170 hours (∆PCE/PCE = -80% with respect to the initial value) due to a huge decrease of VOC (∆VOC/VOC = -60%) and ISC (∆ISC/ISC = -65%). This issue is due to the photo-chemical degradation of the P3HT polymer when exposed to light soaking test at 1 Sun (called “Burn in” Effect), as reported in literature29-31. The long-term stability of Spiro-OMeTAD-based module is reported in Fig.6b. The results show an significant decrease of conversion efficiency after about 72 hours due to a drop of the module’s Voc. As recently reported by Leijtens et al.33, this effect could be also ascribed to a partial dedoping of the Spiro-OMeTAD that induces a change in its oxidation state in the first part of the light soaking test carried out at VOC condition32-33. From 72h to 330h, the PCE value remains stable. This characterization represent the first attempt to evaluate the long-term stability of large area device under standard illumination conditions using a class A Light Soaker at 1 Sun at 40°C in air. These promising results open up a path for future further systematic studies on the effect of different sealing materials and procedures on lifetime.

Physical Chemistry Chemical Physics Accepted Manuscript

of the perovskite-based module using both HTMs under AM1.5 illumination conditions ( 1 Sun at

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Conclusions

process of hybrid organic halide perovskite-based devices reaching a PCE of 5.1% on the large area series-interconnected monolithic modules. Thus, to accomplish the purpose of achieving an efficient perovskite module, important innovative procedures were studied and optimized. Here we mention the key ones: the patterned deposition procedure of the TiO2 underlayer, the optimization of the monolithic interconnection between constituent cells, the uniform deposition of the thin titania scaffold by screen-printing and finally the large area CH3NH3PbI3-xClx deposition by spin coating. These fabrication processes were here used for the first time to define a reproducible fabrication procedure applicable to large area. A promising long-term stability was reached using the SpiroOMeTAD as HTM under AM 1.5 illumination at 1 Sun maintaining more than 60% of its initial PCE after 335 hours. To achieve better performance in terms of PCE and long-term stability, future developments will concentrate on the study of efficient sealants, the optimisation of the perovskite deposition and the cleaning procedure of the interconnection area between neighbouring cells. .

Experimental Section FTO/glass substrates (Pilkington, 8 Ω/□, 57mm × 57mm) were etched with a raster scanning laser (Nd:YVO4 pulsed at 30 kHz average output power P = 10 W) to form the desired electrode patterns consisting of five FTO strips (10mm x 57mm) each separated by 1mm wide etched areas. FTO patterned substrates were cleaned with detergent, de-ionized water and ethanol in an ultrasonic bath. By using the Spray Pyrolysis Deposition (SPD) technique as reported 11, a compact c-TiO2 (120nm) film was deposited onto the FTO surface (heated at 450°C) after screen-printing of a metallic mask in order to obtain a patterned c-TiO2 deposition. Then, the metallic mask was removed by

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In conclusion, this work was devoted to the definition of an efficient and reproducible up-scaling

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immerging the substrate in an acid solution of TiCl4 and de-ionized water for 5 minutes at later

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ethilcellulose, isopropanol and ethanol) was screen-printed onto the c-TiO2 and successively sintered at 480°C for 30 min. The final thickness of the nc-TiO2 film was measured via a profilometer (Dektak Veeco 150) to be 700 nm. A perovskite solution (composed of methylammonium iodide CH3NH3I and lead chloride PbCl2 in N,N-dimethylformamide, molar ratio 3:1) was spin-coated (2000rpm for 40s) over the nc-TiO2 film in air and successively heated at 120°C for 45 minutes obtaining the final crystalline structure. Afterwards, a doped P3HT solution (Merck, 15mg/ml, MW 94100 with LiN(CF3SO2)2N and 4-tertbutylpyridine in chlorobenzene additivies at concentrations according to previous work

21

) was in

turn spin coated (30 s waiting time after the deposition onto the substrate, 600 rpm for 12 s and finally at 1500 rpm for 40 s) over the crystalline perovskite layer (capping layer thickness 150nm). Both perovskite and P3HT layers were successively cleaned from the interconnection area between cells by using a mixture of N,N-dimethylformamide and chlorobenzene (1:10 v/v). Subsequently, samples were introduced into a high vacuum chamber (10-6 mbar) to evaporate an Au layer used as back electrode (thickness 150 nm) and to interconnect cells in series configuration. The deposition mask for Au was fabricated by cutting (via a CO2 Universal Laser System) a polyethylene terephthalate (PET) sheet. The module was tested in air atmosphere without encapsulation under a Class B Sun Simulator (Solar Constant 1200 KHS) at AM 1.5, 1000W/m2 calibrated with a Skye SKS 1110 sensor. Sun Simulator is Class B in the visible and near-infrared range (Class B between 700–800 nm and class A in the rest of the 400–1100 nm range) and has a spatial uniformity < 5% (3.5% in the 15x15 cm region of measurement). The single constituent cell was measured with a slit slightly bigger with the respect to the active area (3.92cm2). The thicknesses and morphologies of the constituent layers were evaluated from Cross-sectional Scanning Electron Microscopy micrographs (FE-SEM Leo Supra 35). The Class A Light Soaker (Solaronix, model. SOLARTEST

Physical Chemistry Chemical Physics Accepted Manuscript

stage. A nanocristalline (nc) mesoporous TiO2 layer (18NR-T paste, Dyesol, diluited with terpineol,

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65- STF65) was used to test the long-term stability at standard illumination conditions (AM1.5,

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a chiller. To test the long term stability of the perovskite-based module some changes have been performed on the layout to allow an encapsulation of the devices. The module layout was slightly modified in order to permit the sealing procedure. Four single cells (active area of 2.88 cm2) are connected by using a monolithic scheme for series-interconnection with an overall active area of 11.52 cm2 keeping the same cells width, interconnection distance and thus the same aperture ratio of the unsealed device. The interconnection area between cells and the width of the cell were left unchanged. Thus, the device was sealed with a thermoplastic sealant deposited over the whole scaffold area at 90°C and with a secondary sealing on the edge of the protective glass using an cyanoacrylate glue.

Acknowledgements

The authors thank Arch. Maria Luigia Fiorentino for discussions and rendering. Thanks are due to Ms. Catia D'Ottavi and Mr. Alessandro Palma for their valuable technical support. We acknowledge “Polo Solare Organico” Regione Lazio and the “DSSCX” MIUR-PRIN2010 for funds.

Notes and references

1

Both authors contributed equally to this work.

a

C.H.O.S.E. (Centre for Hybrid and Organic Solar Energy), Department of Electronic Engineering,

University of Rome “Tor Vergata”,via del Politecnico 1, Rome, 00133 Italy.

Physical Chemistry Chemical Physics Accepted Manuscript

1000W/m2) in air using a UV filter (150µm thick PEN Foil). The temperature was fixed at 40°C by

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b

Department of Chemical Science and Technologies, University of Rome "Tor Vergata", Via della

*

Corresponding Author: Prof. Aldo Di Carlo

Email: [email protected] Tel: +39 06 72597456 Affiliation: C.H.O.S.E. (Centre for Hybrid and Organic Solar Energy), Department of Electronic Engineering, University of Rome “Tor Vergata”,via del Politecnico 1, Rome, 00133 Italy

[1] B. O’Regan, M. Graetzel, Nature, 1991, 353, 24. [2] F. Giordano, A. Guidobaldi, E. Petrolati, L. Vesce, R. Riccitelli, A. Reale, T.M. Brown, A. Di Carlo, Progress in Photovoltaics: Research and Applications, 2012, DOI: 10.1002/pip.2228. [3] S. Dai, K. Wang, J. Weng, Y. Sui, Y. Huang, S. Xiao, S. Chen, L. Hu, F. Kong, X. Pan, C. Shi, L. Guo, Solar Energy Material and Solar Cells, 2005, 85, 447. [4] H. Arakawa, T. Yamaguchi, T. Sutou, Y. Koishi, N. Tobe, D. Matsumoto, T. Nagai, Current Applied Physics, 2010, 10, S157. [5] V. Zardetto, T.M. Brown, A. Reale, A. Di Carlo, Journal of Polymer Science Part B: Polymer Physics, 2011, 49, 638. [6] M. Pagliaro, R. Ciriminna, G. Palmisano, ChemSusChem, 2008, 1, 880. [7] S. Mastroianni, A. Lanuti, S. Penna, A. Reale, T.M. Brown, A. Di Carlo, F. Decker, Chemphyschem : a European journal of chemical physics and physical chemistry, 2012, 13, 2925. [8] U. Bach, D. Lupo, P. Comte, J. Moser, F. Weissörtel, J. Salbeck, H. Spreitzer, M. Grätzel, Nature, 1998, 395, 583. [9] H.J. Snaith, A. Petrozza, S. Ito, H. Miura, M. Grätzel, Advanced Functional Materials, 2009, 19, 1810.

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Ricerca Scientifica 00133, Rome, Italy.

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[10] R. Zhu, C.-Y. Jiang, B. Liu, S. Ramakrishna, Advanced Materials, 2009, 21, 994.

Published on 07 January 2014. Downloaded by Lomonosov Moscow State University on 08/01/2014 17:57:45.

Brown, A. Reale, A. Di Carlo, Organic Electronics, 2013, 14, 1882. [12] F. Matteocci, S. Casaluci, S. Razza, A. Guidobaldi, T. Brown, A. Reale, A.D. Carlo, Journal of Power Sources, 2014, 246, 361. . [13] M.M. Lee, J. Teuscher, T. Miyasaka, T.N. Murakami, H.J. Snaith, Science, 2012, 338, 643. [14] A.Kojima, K.Teshima, Y. Shirai, T. Miyasaka, Journal ofthe American Chemical Society, 2009, 131, 6050. [15] J.H.Im, C.R. Lee, J.W. Lee, S.W. Park, N.G. Park, Nanoscale, 2011, 3, 4088. [16] H.S. Kim, I. Mora-Sero, V. Gonzalez-Pedro, F. Fabregat-Santiago, E.J. Juarez-Perez, N.G. Park, J. Bisquert, Nature Communications, 2013, 4, 2242. [17] H.S. Kim, C.R. Lee, J.H.Im, K.B. Lee, T. Moehl, A. Marchioro, S.J. Moon, R. HumphryBaker, J.H.Yum, J.E. Moser, M. Graetzel, N.G. Park, Scientific Reports, 2012, 2, 591. [18] H.S. Kim, J.W. Lee, N. Yantara, P.P. Boix, S.A. Kulkarni, S. Mhaisalkar, M. Graetzel, N.G. Park, Nano Letters, 2013, 13, 2412. [19] J.M. Ball, M.M. Lee, A. Hey, H.J. Snaith, Energy and Environmental Science, 2013, 6, 1739. [20] J.H. Heo, S.H. Im, J.H. Noh, T.N. Mandal, C.S. Lim, J.A. Chang, Y.H. Lee, H.J. Kim, A. Sarkar, M.K. Nazeeruddin, M. Grätzel, S.I. Seok, Nature Photonics, 2013, 7, 486. [21] J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M.K. Nazeeruddin, M. Grätzel, Nature, 2013, 499, 316. [22] N.G. Park, The Journal of Physical Chemistry Letters, 2013, 4, 2423. [23] F. Di Giacomo, S. Razza, F. Matteocci, A. D'Epifanio, S. Licoccia, A. Reale, T. Brown, A. Di Carlo, Journal of Power Sources, DOI: 10.1016/j.jpowsour.2013.11.053. [24] D. Bi, L. Yang, G. Boschloo, A. Hagfeldt, E.M.J. Johansson, Journal of Physical Chemistry Letters, 2013, 4, 1532.

Physical Chemistry Chemical Physics Accepted Manuscript

[11] F. Matteocci, G. Mincuzzi, F. Giordano, A. Capasso, E. Artuso, C. Barolo, G. Viscardi, T.M.

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[25] J. Kruger, R. Plass, L. Cevey, M. Piccirelli, M. Gratzel, U. Bach, Applied Physics Letters,

Published on 07 January 2014. Downloaded by Lomonosov Moscow State University on 08/01/2014 17:57:45.

[26] P. Docampo, A. Hey, S.Guldin, R. Gunning, U. Steiner, H. Snaith, Advanced Functional Materials, 2012, 22, 5010. [27] B. Cai, Y. Xing, Z. Yang, W.H. Zhang, J. Qiu, Energy and Environmental Science, 2013, 6, 1480. [28] M. Liu, M.B. Johnson, H. Snaith, Nature, 2013, 501, 395. [29] M. Manceau, A. Rivaton, J.L. Gardette, S. Guillerez, N. Lemaitre, Polymer Degradation and Stability, 2009, 94, 898. [30] M.V. Madsen, T. Tromholt, K. Norrman, F.C. Krebs, Advanced Energy Material, 2012, 3, 424. [31] C.H. Peters, I.T. Sachs-Quintana, W.R. Mateker, T. Heumueller, J.Rivnay, R. Noriega, Z.M. Beiley, E.T. Hoke, A. Salleo, M. McGehee, Advanced Material, 2012, 24, 663. [32] U.B. Cappel, T. Daeneke, U. Bach, Nano Letter, 2012, 12, 4925. [33] T. Leijtens, G.E. Eperon, S. Pathak, A. Abate, M.M. Lee, H.J. Snaith, Nature Communications, 2013, 4, 2885.

Best Device

Voc [mV]

Isc [mA]

909

12.2

FF

(%)

56.4

PCE (%)

6.3

Physical Chemistry Chemical Physics Accepted Manuscript

2001, 79, 2085.

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10.6 ± 1.6

51.2 ± 6.7

5.0 ± 1.1

Tab.1. Main photovoltaic parameters measured on large area single cell using P3HT as HTM are reported. The device structure is FTO/c-TiO2/nc-TiO2/CH3NH3PbI3-xClx/P3HT/Au. Averages are calculated on the five large area cells (active area of 3.36cm2) forming the module.

FTO/c-TiO2/n-TiO2/P3HT/Au

FTO/c-TiO2/n-TiO2/Spiro/Au

Voc [V] Isc [mA] FF (%) PCE (%) Voc [V] Isc [mA] FF (%) PCE (%) Best Cell 0.91

-41.1

56.4

6.28

0.89

-33.9

65.1

5.339

Module

-36.8

52.6

5.10

4.31

-32.9

60.3

5.081

4.45

Tab.2. Main photovoltaic parameters obtained for best large area cell and series-type module using P3HT and Spiro-OMeTAD as HTM.

Best Module

VMAX

IMAX

PMAX

VOC

ISC

FF

PCE

[V]

[mA]

[mW]

[V]

[mA]

(%)

(%)

3.0

-24.2

73.0

4.0

-33.2

55.03

4.3

Physical Chemistry Chemical Physics Accepted Manuscript

913 ± 40

Average

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3.3 ± 0.3

-19.2 ± 4.0

62.0 ± 10.6

4.3 ± 0.4 -25.5 ± 5.6

56.96 ± 7.90

3.7 ± 0.6

Tab.3. Average photovoltaic parameters obtained for series-type module using P3HT as HTM.

Figure 1. a) Image of the monolithic perovskite-based module. b) the monolithic interconnection scheme of the perovskite-based module. In particular, the length of active area is equal to 48 mm, the width of the each cell is 7 mm, the width of the etched FTO area is equal to 1 mm and the width of the contact area between the cells (where no c-TiO2 layer was deposited) is equal to 2.5mm.

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Average

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Figure 2. Cross-sectional FE-SEM images of a perovskite based solar module without the gold electrode. a) Cross-sectional FE-SEM image of the perovskite based solar module with lower magnification. b) Cross-sectional FE-SEM image of the perovskite based solar module with higher

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magnification. Each layer is coloured (FTO substrate, blue; compact TiO2 underlayer, green;

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Cross-sectional FE-SEM image of a sintered mesoporous TiO2 made with diluted screenprinted paste (18-NRT, Dyesol. d) Cross-sectional FE-SEM image of a sintered mesoporous TiO2 made with diluted screenprinted paste (18-NRT, Dyesol) covered with CH3NH3PbI3-xClx perovskite layer obtained by spin coating and annealing. The morphology is clearly different from the uncovered TiO2 of image c), with emerging perovskite crystal.

Physical Chemistry Chemical Physics Accepted Manuscript

peroskite/TiO2, yellow; P3HT polymer, red) and labeled to underline the device’s architecture. c)

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Figure 3. a) IV characteristic of series-connected large area P3HT-based device and best cell are reported. b) IV characteristic of series-connected large area Spiro-OMeTAD-based device and best cell. IV characteristics are measured under standard illumination conditions AM1.5G (1000W·cm-2) under Class B Sun Simulator (Solar Constant 1200 KHS).

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Figure 4. IV characteristic of the perovskite-based module using P3HT as HTM under different

Figure 5. Evolution of the PCE obtained during the up-scaling process using both HTM: SpiroOMeTAD (cyan colour) and P3HT (green colour) scaling the size of the active area (the small area cell (0.1cm2), the large area cells (3.36cm2) and the series-interconnected module (16.8cm2)). The up-scaling process was carried out maintaining the same perovskite deposition procedure.

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illumination conditions.

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Figure 6. Evolution of normalized photovoltaic parameters (PCE, red squares; VOC, cyan circles; ISC, blue triangles; FF, green stars) using different HTMs under AM1.5G illumination condition with a Class A Light Soaker (Solaronix, SOLARTEST 65- STF65) at 1000W/m2 and 40°C in air. The encapsulated modules are maintained at VOC condition during the light soaking test. a) Longterm stability of P3HT-based module after 170 hours. b) Long-term stability of Spiro-based module after 335 hours.

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DOI: 10.1039/C3CP55313B

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Solid-state solar modules based on mesoscopic organometal halide perovskite: a route towards the up-scaling process.

We fabricated the first solid state modules based on organometal halide perovskite CH3NH3PbI3-xClx using Spiro-OMeTAD and poly(3-hexylthiophene) as ho...
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