Performance of Bulk Heterojunction Solar Cells Fabricated Using Spray-Deposited Poly [ [ 9-( 1-octylnonyl )-9 H-carbazole-2 , 7-diyl ]-2 , 5-thiophenediyl-2 , 1 , 3-benzothiadiazole-4 , 7-diyl-2 , 5-thiophenediyl ] / [ 6 , 6 ]-Phenyl C 71 Butyric AcidMethyl Ester Blend Active Layers

e Poly[[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothia diazole-4,7-diyl-2,5-thiophenediyl]/[6,6]phenyl C71 butyric acid methyl ester blend active layers were prepared by spray deposition method with different preparative conditions. e active layers were prepared with and without TiOxx layer in order to study the property changes. e absorption and surface morphology of the active layers were analyzed using UV-visible spectral and atomic force microscopic studies. e photovoltaic cells were fabricated using the spray-coated active layers with and without TiOxx layer.e results were compared with the cells fabricated using the conventional spin-coated active layers.


Introduction
Organic solar cells (OSCs) are the best alternate for inorganic solar cells because of their low cost roll-to-roll production, and large area processability on �exible substrates.erefore, organic solar cell (OSC) devices are of increasing interest as new materials for future light-activated energy sources.During the last two decades, the research activities and reports on OSC-based devices have been increased [1][2][3].In the recent years, a number of photoactive polymers, fullerene, and the bulk heterojunction concept has been put forth to increase the efficiency of OSC devices.Among them, conjugated low band gap polymers-based active layers yielded high PCE of 5-7% [4][5][6][7].Especially, poly (2,7-carbazole) derivatives are potential materials for solar cell applications [8][9][10][11].ere are several reports on the fabrication of organic photovoltaic cells using low-cost solution processes such as spin-coating, inkjet printing, screen printing, and spray coating [12][13][14].Spin coating is the most widely used method to prepare active layers and also most efficient devices still adopt this process.However, the spin-coating process cannot be used in large area devices.Spray deposition is widely used for painting in commercial production and is one of the cheapest processes for coating of polymer solutions.Spray-coating method has becomes important in the fabrication of large area polymer: fullerene based bulk heterojunction solar cells [15,16].Different approaches have been adopted to achieve high power conversion efficiency from spray deposited active layers by various research groups [17][18][19][20].In the present work, we report the bulk heterojunction solar cell devices fabricated using the spray-deposited active layers of polymer blend materials of poly[N-9 ′′ -hepta-decanyl-2,7-carbazole-alt-5,5-(4 ′ ,7 ′ -di-2-thienyl-2 ′ ,1 ′ ,3 ′ -benzothiadiazole)] (PCDTBT) and [6,6]phenyl-C71-butyric acid methyl ester (PC 71 BM).e effect  of various deposition parameters such as spraying time, substrate temperature, and substrate-nozzle distance has been investigated TiO  layer redistributes the light intensity within the bulk heterojunction by changing the optical interference between the incident light and the light re�ected from the metal electrode and thus enhances the power conversion efficiency of the solar cells [21].erefore, in the present study, we have introduced TiO  layer in between the active layer and metal electrode in order to improve the power conversion efficiency of the photovoltaic device.the schematic of the fabricated photovoltaic cell structure (ITO/PEDOT : PSS/PCDTBT : PC 71 BM/TiO  /Al).
To fabricate the bulk heterojunction solar cells indiumtin-oxide-(ITO-) coated glass substrates were cleaned with detergent, water, acetone, and ethanol and then treated with UV/ozone for 10 min.en the PEDOT : PSS layer was coated on the top of ITO electrode by spin coating at a rotation speed of 5000 rpm for 30 s followed by drying at 100 ∘ C for 10 min in air.An active layer of PCDTBT : PC 71 BM was deposited by spray coating on the top of the coated PEDOT : PSS layer.For active layers-coating, the precursor solution was prepared in 1 : 4 ratio of PCDTBT : PC 71 BM using chloroform as solvent.e blend PCDTBT : PC 71 BM solution was sprayed on the PEDOT : PSS layer.By introducing the nitrogen gas with the pressure of 7.85 × 10 4 Pa into the spray apparatus the solution was sprayed on the PEDOT : PSS layer.e blend �lms were prepared for 15 and 20 s and with the substrate-nozzle distance of 15 cm.e active layers with thickness from ∼100 to 110 nm were obtained.e active layers were prepared at room temperature as well as 60 ∘ C to study the effect of substrate temperature.In order to increase the photocurrent, an optical spacer (TiO  layer) between the photoactive layer and the top electrode has been introduced.e maximum light intensity is redistributed to be within the active charge separating bulk heterojunction layer while using the optical spacer.erefore, titanium suboxide (titanium isopropoxide in ethanol) layer was deposited on the active layer by spin coating at a rotation speed of 5000 rpm for 30 s followed by drying at 60 ∘ C for 10 min in air.Finally, Al electrode was evaporated on the active layer through a shadow mask at 10 −6 Torr.e absorption spectra of the spray-coated blend layers were recorded using a Shimadzu UV2450 UV-vis.spectrometer.e surface morphology of the blend layers was examined by atomic force microscopy using a Seiko Instrument SPA400-SPI4000.All AFM images were taken in dynamic force mode at optimal force.Silicon cantilevers (Tip radius: ∼10 nm; SI-DF20; Seiko Instruments Inc.), with spring constant of 14 N/m and resonance frequency of 136 kHz, was used to record AFM images.For comparison, the solar cells were fabricated using conventional spin-coated active layers.For that, the precursor solution was prepared in 1 : 4 ratio of PCDTBT : PC 71 BM using the solvent of 5 mL chloroform.e active layers with ∼100 nm thickness were achieved with a spin speed of 1000 rpm by conventional spin coating method.e current-voltage characteristics of the fabricated

Results and Discussion
3.1.Absorption Spectral Studies.e absorption spectra of spray-coated active layers of PCDTBT : PC 71 BM from 1 : 4 ratio with and without TiO  layer and spin-coated active layers with TiO  layer are shown in Figure 3. e spincoated active layers show better absorption than the spraycoated active layers.e active layers with TiO  layer possess relatively better optical absorption.is is because the optical spacer is a nonabsorbing layer that redistributes the maximum light intensity to be within the charge-separating bulk heterojunction layer.In that, the active layer prepared using 15 cm substrate-nozzle distance and the spray time of 20 s shows better absorption than the active layer prepared from the spray time of 15 s.It is observed from the results that the blend molecules are more aggregated on the substrate when increasing the coating time to 20 s and hence the �lms formed were less uniform.e active layers with uniform thickness were observed when the substrate to nozzle distance was 15 cm and the spray time of 15 s.From this analysis, we have observed that the active layers prepared with TiO  for 15 s with substrate-nozzle distance of 15 cm show �at morphologies and speci�cally the active layer prepared at 60 ∘ C shows well �attened morphology (Figure 4(c)).e photovoltaic cells were fabricated using the sprayand spin-deposited PCDTBT : PC 71 BM active layers with and without TiO  layer.

Current-Voltage
Characteristics.e spray-and spincoated PCDTBT : PC 71 BM active layers with and without TiO  layer were used to fabricate the photovoltaic cells.e fabricated photovoltaic cells were characterized by J-V studies under illumination of AM 1.5 G (100 mW/cm 2 ). Figure 5 shows the current-voltage characteristics of photovoltaic cells fabricated using spray-deposited PCDTBT : PC 71 BM active layers.e effective area of devices is 5 mm 2 .From this analysis, it is observed that the devices fabricated using active layers with TiO  layer prepared for 15 s with substrate-nozzle distance of 15 cm at the substrate temperature of 60 ∘ C exhibit the power conversion efficiency of 4.01%.Table 1 gives the comparison data of root mean square value, peak to valley value, and power conversion efficiency of solar cells prepared using spray-and spin-coated active layers at different conditions.It is observed that the short circuit current and PCE of solar cells fabricated using spray-coated active layer are higher than those of photovoltaic cells fabricated using the conventional spin coated active layers.e devices fabricated using the spray-coated active layers with TiO  show higher open circuit voltage, short-circuit current, �ll factor, and power conversion efficiency.

Conclusions
Organic photovoltaic cell devices were fabricated using spinand spray-deposited PCDTBT : PC 71 BM active layers with and without TiO  layer.e effect of spray time and substrate temperature was investigated.Atomic force microscopic analysis shows that the active layers prepared in 1 : 4 ratio with the substrate-nozzle distance 15 cm and for 15 s possess well-�attened and smooth morphology.e cells fabricated using the PCDTBT : PC 71 BM active layers prepared at 60 ∘ C with TiO  layer show the power conversion efficiency (PCE) of 4.01%.e PCE of solar cells fabricated using the active layers coated by spray coating is relatively larger than that of the spin coated active layer.From this analysis, we observed that the device fabricated with TiO  layer shows better power conversion efficiency than that of the device without TiO  layer.

F 1 :F 2 :
Molecular structure of (a) PCDTBT and (b) PC 71 BM.(a) Schematic of spray deposition and (b) structure of BHJ device.

Figures 1 (
Figures 1(a) and 1(b) show the molecular structures of PCDTBT and PC 71 BM, respectively.Figure 2(a) shows the schematic of the spray deposition unit consisting of spray gun, spray nozzle, and substrate holder used to deposit the active layers.In the present work, the parameters such as spraying time, substrate temperature, and substratenozzle distance were varied to coat the active layers of PCDTBT:PC 71 BM by spray method.Figure 2(b) shows

Figure 2 (F 3 :F 4 :
Figures 1(a) and 1(b) show the molecular structures of PCDTBT and PC 71 BM, respectively.Figure 2(a) shows the schematic of the spray deposition unit consisting of spray gun, spray nozzle, and substrate holder used to deposit the active layers.In the present work, the parameters such as spraying time, substrate temperature, and substratenozzle distance were varied to coat the active layers of PCDTBT:PC 71 BM by spray method.Figure 2(b) shows

Figures 4 (
a)-4(d) show the AFM images of PCDTBT : PC 71 BM active layers prepared in 1 : 4 ratio at different preparative conditions.e images were recorded on a �lm area of 2000 × 2000 nm.Figures4(a) and 4(b) show the surface morphology of the active layer without TiO  layer prepared at room temperature and at 60 ∘ C with a spray-nozzle distance of 15 cm and spray T 1: Root means square, peak-valley value of active layers, and power conversion efficiency of photovoltaic devices fabricated using the active layers with and without TiO  layer.s, respectively.Blended �lms without TiO  layer and prepared at room temperature show more roughness than the surface of the active layer prepared at 60 ∘ C. e surface of the active layer with TiO  layer prepared at 60 ∘ C with the spray-nozzle distance of 15 cm for 15 s shows smooth and better morphology (Figure4(c)).e surface of the active layers prepared using spin coating (Figure4(d)) also shows smooth morphology when compared to spray-deposited active layer prepared at room temperature.