Effect of annealing of poly(3-hexylthiophene)/fullerene bulk heterojunction composites on structural and optical properties

Composite films of P3HT/PCBM-(poly[3-2,5-diyl]/[6,6]-phenyl C₆₁ butyric acid methyl ester) are widely used as an active layer in plastic solar cells. We have studied the influence of thermal annealing on nano-structural and optical properties of thin spin-coated P3HT/PCBM-films. Their structural properties were studied by X-ray diffraction in grazing incidence geometry. It was found that the crystallinity of the investigated films is drastically increased upon annealing. Furthermore, the anisotropic dielectric function of such films was determined by spectroscopic ellipsometry. Significant changes were observed both in parallel and perpendicular components of the dielectric function after annealing. These changes were attributed to the formation of crystalline domains upon annealing.     

Composition depth profile analysis of bulk heterojunction layer by time-of-flight secondary ion mass spectrometry with gradient shaving preparation

Composition depth profile analysis of bulk heterojunction (BHJ) layer was performed by time-of-flight secondary ion mass spectrometry with gradient shaving preparation. The BHJ layer comprised of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61butyric acid methyl ester (PCBM) was formed on the substrate coated with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) followed by annealing. The P3HT component increased toward the top surface in the BHJ layer. In addition, C₈H₇SO₃⁻ was detected inside the BHJ layer, suggesting penetration of PSS. P3HT was uniformly distributed in the BHJ layer without PEDOT:PSS. The P3HT-rich distribution in the top surface may be attributed to PSS penetration.     

P3HT:PCBM, best seller in polymer photovoltaic research

In the field of polymer‐based photovoltaic cells, poly(3‐hexylthiophene) (P3HT) and 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl[6,6]C₆₁ (PCBM) are, to date, the most‐studied active materials around the world for the bulk‐heterojunction structure. Various power‐conversion efficiencies are reported up to approximately 5%. This Research News article is focused on a survey of the tremendous literature published between 2002 and 2010 that exhibits solar cells based on blends of P3HT and PCBM.     

Studying polymer/fullerene intermixing and miscibility in laterally patterned films with X-ray spectromicroscopy

Films of the fullerene derivatives [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(61) BM) and [6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71) BM) are patterned on silicon nitride membranes using photolithography to study, with X-ray spectromicroscopy, the lateral, solid-state diffusion of fullerene derivatives into conjugated polymer films. After patterning of the fullerene film, a film of conjugated polymer is laminated on top and the structure is annealed in order to study lateral intermixing and facilitate measurement of fullerene miscibility. Lateral intermixing of polymer and fullerene readily occurs for poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) and regiorandom poly(3-hexylthiophene) (RRa-P3HT). A 42 wt.% miscibility of PC(61) BM in PBTTT is measured, while miscibilities of 20 and 41 wt.% are measured for PC(61) BM and PC(71) BM, respectively, in RRa-P3HT, thereby demonstrating a significant difference in the miscibilities of these two fullerene derivatives. For regioregular poly(3-hexylthiophene) (RR-P3HT), incomplete lateral intermixing of fullerene and RR-P3HT is observed with PCBM crystallite formation competing with the lateral diffusion of PCBM molecules into the polymer film.     

Photo-stability study of a solution-processed small molecule solar cell system: correlation between molecular conformation and degradation

Solution-processed organic small molecule solar cells (SMSCs) have achieved efficiency over 11%. However, very few studies have focused on their stability under illumination and the origin of the degradation during the so-called burn-in period. Here, we studied the burn-in period of a solution-processed SMSC using benzodithiophene terthiophene rhodamine:[6,6]-phenyl C₇₁ butyric acid methyl ester (BTR:PC₇₁BM) with increasing solvent vapour annealing time applied to the active layer, controlling the crystallisation of the BTR phase. We find that the burn-in behaviour is strongly correlated to the crystallinity of BTR. To look at the possible degradation mechanisms, we studied the fresh and photo-aged blend films with grazing incidence X-ray diffraction, UV–vis absorbance, Raman spectroscopy and photoluminescence (PL) spectroscopy. Although the crystallinity of BTR affects the performance drop during the burn-in period, the degradation is found not to originate from the crystallinity changes of the BTR phase, but correlates with changes in molecular conformation – rotation of the thiophene side chains, as resolved by Raman spectroscopy which could be correlated to slight photobleaching and changes in PL spectra.     

Semiconducting Carbon Nanotube Aerogel Bulk Heterojunction Solar Cells

Using a novel two‐step fabrication scheme, we create highly semiconducting‐enriched single‐walled carbon nanotube (sSWNT) bulk heterojunctions (BHJs) by first creating highly porous interconnected sSWNT aerogels (sSWNT‐AEROs), followed by back‐filling the pores with [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM). We demonstrate sSWNT‐AERO structures with density as low as 2.5 mg cm^?3, porosity as high as 99.8%, and diameter of sSWNT fibers ≤10 nm. Upon spin coating with PC₇₁BM, the resulting sSWNT‐AERO‐PC₇₁BM nanocomposites exhibit highly quenched sSWNT photoluminescence, which is attributed to the large interfacial area between the sSWNT and PC₇₁BM phases, and an appropriate sSWNT fiber diameter that matches the inter‐sSWNT exciton migration length. Employing the sSWNT‐AERO‐PC₇₁BM BHJ structure, we report optimized solar cells with a power conversion efficiency of 1.7%, which is exceptional among polymer‐like solar cells in which sSWNTs are designed to replace either the polymer or fullerene component. A fairly balanced photocurrent is achieved with 36% peak external quantum efficiency (EQE) in the visible and 19% peak EQE in the near‐infrared where sSWNTs serve as electron donors and photoabsorbers. Our results prove the effectiveness of this new method in controlling the sSWNT morphology in BHJ structures, suggesting a promising route towards highly efficient sSWNT photoabsorbing solar cells.     

Efficient inverted bulk heterojunction photovoltaic devices using a transparent polymeric interfacial buffer layer with C60 pendant and UV curable groups

We demonstrate the synthesis of a transparent, polymeric n-type material (M1) consisting of C60 pendant and UV curable groups in side chains. This material (M1) is employed as a polymeric n-type interfacial buffer layer for an efficient inverted bulk heterojunction (BHJ) photovoltaic device based on regioregular poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester (P3HT:PC61BM) active layer. Under simulated solar illumination of AM 1.5G (100 mW/cm2), the highest efficient devices fabricated with a configuration of ITO/interfacial buffer layer (M1,10 nm)/P3HT:PC61BM (1:0.9 w:w) (120 nm)/PEDOT:PSS (30 nm)/Ag (100 nm) achieve an average power conversion efficiency PCE of 2.16%, with short-circuit current J(SC) = 6.70 mA/cm2, fill factor FF = 54.2%, and open-circuit voltage V(OC) = 0.60 V. This result is comparable to the inverted BHJ photovoltaic devices fabricated with Cs2CO3, one of widely used as a buffer layer. The synthesized M1 have thus proven to be promising polymeric interfacial buffer layer for high efficient BHJ photovoltaic devices.     

Efficiency enhancement in DIBSQ:PC<Subscript>71</Subscript>BM organic photovoltaic cells by using Liq-doped Bphen as a cathode buffer layer

We have improved the photovoltaic performance of 2,4-bis[4-(N,Ndiisobutylamino)- 2,6-dihydroxyphenyl] squaraine:[6,6]-phenyl C71-butyric acid methyl ester (DIBSQ:PC₇₁BM) organic photovoltaic (OPV) cells via incorporating Liq-doped Bphen (Bphen-Liq) as a cathode buffer layer (CBL). Based on the Bphen-Liq CBL, a DIBSQ:PC₇₁BM OPV cell possessed an optimal power conversion efficiency of 4.90%, which was 13% and 60% higher than those of the devices with neat Bphen as CBL and without CBL, respectively. The enhancement of the device performance could be attributed to the enhanced electron mobility and improved electrode/active layer contact and thus the improved photocurrent extraction by incorporating the Bphen-Liq CBL. Light-intensity dependent device performance analysis indicates that the incorporating of the Bphen-Liq CBL can remarkably improve the charge transport of the DIBSQ:PC₇₁BM OPV cell and thus decrease the recombination losses of the device, resulting in enhanced device performance. Our finding indicates that the doped Bphen-Liq CBL has great potential for high-performance solution-processed small-molecule OPVs.     

Exploiting optical properties of P3HT:PCBM films for organic solar cells with semitransparent anode

In this study, we demonstrate optical properties of multilayer system in an organic solar cell based on poly (3-hexylthiophene) (P3HT) and 6,6-phenyl C61-butyric acid methyl ester (PCBM) with semitransparent anode through thermal annealing effect. The optical absorption is enhanced via optimizing annealing treatment which further elevates near-field electric field amplitude. The electric field amplitude at the interface (active layer/semitransparent anode) is enhanced after thermal annealing corresponding to effective absorption near to semitransparent anode. Moreover, the thickness of the active layer is optimized via optical thin-film model for enhancing the organic solar cell efficiency.     

Unraveling the Role of Substrates on Interface Energetics and Morphology of PCDTBT:PC70BM Bulk Heterojunction

In the pursuit of developing highly efficient polymer solar cells, it is indispensable to experimentally determine the molecular electronic and geometrical structures of distributed donor/acceptor bulk heterojunctions for understanding the processes inside the cell. In this article, substrate effect on interface energetics and film morphology of the poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)]:[6,6]‐phenyl‐C₇₀ butyric acid methyl ester (PCDTBT:PC₇₀BM) blends with various blending ratios on various conductive substrates is clarified based on the characterization of photoelectron spectroscopy and atomic force microscope, where the PCDTBT:PC₇₀BM blend film serves as an important model system due to efficient charge generation and transport with low recombination. The energetics of the PCDTBT:PC₇₀BM blend film is demonstrated to be highly dependent on the substrate work function, showing the transition from vacuum level alignment to Fermi level pinning with the variation of PC₇₀BM ratio in the blend film. The resulting morphology is in good agreement with the observed formation of a PCDTBT‐rich layer at the top of the PCDTBT:PC₇₀BM blend film irrespective of the variation of the PC₇₀BM blending ratio and annealing temperature. The results show the possibility of tuning the interfacial electronic structures by utilizing the substrate effects and potential applications on performance enhancement in polymer solar cells.     

Improvement of photovoltaic properties by addition of a perylene compound in P3HT:PCBM BHJ system

The synthesized n-type perylene derivative, N,N'-bis-(4-bromophenyl)-1,6,7,12-tetrakis(4-n-butoxy-phenoxy)-3,4,9,10-perylene tetracarboxdiimide (PIBr), was applied as an additive to polymer solar cells (PSCs) with P3HT [poly(3-hexylthiophene)]:PCBM [[6,6]-phenyl C61-butyric acid methyl ester] blend films. Without post thermal annealing, a considerable improvement of about 98% in power conversion efficiency was achieved by the addition of 1 wt% PIBr into a P3HT:PCBM layer, when compared with that of reference cell without the additive. The results, in combination with relevant data from UV-Vis. absorption, photoluminescence, X-ray measurements and carrier mobility studies, revealed that the addition of the perylene compound within active layer contributed to more effective charge transfer and enhanced electron mobility.     

Effect of thermal annealing on the efficiency of heterojunction photovoltaic cells fabricated using poly(3-hexylthiophene) and methanofullerene, [6,6]-phenyl C61-butyric acid methyl ester

The effects of thermal annealing on the efficiency of heterojunction photovoltaic (PV) cells that were fabricated using poly(3-hexylthiophene) (P3HT) and methanofullerene, [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were investigated. The absorption spectra showed that the absorption intensity of the P3HT:PCBM layer that was annealed for 5 min had the highest value among the several samples with different annealing temperatures. The atomic force microscopy image showed that the P3HT:PCBM layer that was annealed for 5 min had the best surface morphology. The X-ray photoelectron spectroscopy demonstrated that the P3HT:PCBM layer that was annealed at 140 degrees C for 10 min enhanced the PCBM aggregation on the surface Al layer that was covered by the P3HT:PCBM layer. The efficiencies of the PV cells that were annealed at 3, 5, and 10 min were approximately 2.7, 4.2, and 3.5%, respectively. Based on the experiment results, the variations in the efficiency of the PV cells due their thermal treatment were described.     

Morphology evolution via self-organization and lateral and vertical diffusion in polymer:fullerene solar cell blends

Control of blend morphology at the microscopic scale is critical for optimizing the power conversion efficiency of plastic solar cells based on blends of conjugated polymer with fullerene derivatives. In the case of bulk heterojunctions of regioregular poly(3-hexylthiophene) (P3HT) and a soluble fullerene derivative ([6,6]-phenyl C61-butyric acid methyl ester, PCBM), both blend morphology and photovoltaic device performance are influenced by various treatments, including choice of solvent, rate of drying, thermal annealing and vapour annealing. Although the protocols differ significantly, the maximum power conversion efficiency values reported for the various techniques are comparable (4-5%). In this paper, we demonstrate that these techniques all lead to a common arrangement of the components, which consists of a vertically and laterally phase-separated blend of crystalline P3HT and PCBM. We propose a morphology evolution that consists of an initial crystallization of P3HT chains, followed by diffusion of PCBM molecules to nucleation sites, at which aggregates of PCBM then grow.     

Inverted polymer solar cells with an ultrathin lithium fluoride buffer layer

An ultrathin lithium fluoride (LiF) buffer layer was applied to inverted polymer solar cells with P3HT [poly(3-hexylthiophene)]:PCBM [[6,6]-phenyl C61-butyric acid methyl ester] blend films. By inserting the LiF layer between the transparent electrode and the P3HT:PCBM blend film, all parameters, including the short-circuit current, the open-circuit voltage and the fill factor, were enhanced compared to those of a reference cell without the LiF layer. The power conversion efficiency of the device with the LiF layer was thereby improved by more than 300% relative to the reference cell.     

Control of Shell Morphology in p–n Heterostructured Water‐Processable Semiconductor Colloids: Toward Extremely Efficient Charge Separation

This article describes p–n heterostructured water‐borne semiconductor naonoparticles (NPs) with unique surface structures via control of shell morphology. The shell particles, comprising PC60–[6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) composite, having n‐type semiconductor characteristics, notably influence the charge carrier behavior in the core–shell NPs. A one‐ or two‐phase methodology based on a PC60 surfactant‐water phase and PC₆₁BM n‐type semiconductor‐organic phase provides highly specific control over the shell structure of the NPs, which promote their superior charge separation ability when combined with poly‐3‐hexyl‐thiophene (P3HT). Moreover, the resulting water‐borne NP exhibits shell morphology‐dependent carrier quenching and stability, which is characterized via luminescence studies paired with structural analysis. Corresponding to the results, outstanding performances of photovoltaic cells with over 5% efficiency are achieved. The results suggest that the surrounding shell environments, such as the shell structure, and its electronic charge density, are crucial in determining the overall activity of the core–shell p–n heterostructured NPs. Thus, this work provides a new protocol in the current fields of water‐based organic semiconductor colloids.     

Large [6,6]-phenyl C61 butyric acid methyl (PCBM) hexagonal crystals grown by solvent-vapor annealing

We propose that solvent-vapor annealing is an efficient method for fabricating large [6,6]-phenyl C₆₁ butyric acid methyl (PCBM) single crystals. The morphology and size of PCBM crystals are influenced by different substrates and annealing solvents. Hexagonal PCBM crystals >150 μm in size were obtained when crystallization was performed on bare SiO₂ substrate under the saturated vapor of chloroform for annealing. The proposed method was also applied to a bi-component system, which led to the spontaneous formation of PCBM and dioctylbenzothienobenzothiophene single crystals.     

Comparative study: the effect of annealing conditions on the properties of P3HT:PCBM blends

This paper presents a detailed study on the role of various annealing treatments on organic poly(3-hexylthiophene) and [6]-phenyl-C₆₁-butyric acid methyl ester blends under different experimental conditions. A combination of analytical tools is used to study the alteration of the phase separation, structure and photovoltaic properties of the P3HT:PCBM blend during the annealing process. Results showed that the thermal annealing yields PCBM “needle-like” crystals and that prolonged heat treatment leads to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM crystals. The substrate annealing method demonstrated an optimal morphology by eradicating and suppressing the formation of fullerene clusters across the film, resulting in longer P3HT fibrils with smaller diameter. Improved optical constants, PL quenching and a decrease in the P3HT optical bad-gap were demonstrated for the substrate annealed films due to the limited diffusion of the PCBM molecules. An effective strategy for determining an optimized morphology through substrate annealing treatment is therefore revealed for improved device efficiency.     

The role of solvent and morphology on miscibility of methanofullerene and poly(3-hexylthiophene)

A bicontinuous, percolating bulk heterojunction morphology is integral to organic polymer solar cells. Understanding the factors affecting the miscibility of photovoltaic polymers with a fullerene electron acceptor molecule is a key to controlling the morphology. Starting from discreet pure phases - a poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) bilayer film - the evolution of the P3HT-PCBM interface was studied with particular attention to the role of residual solvent in P3HT on PCBM interdiffusion. This investigation shows that in the bilayer geometry PCBM can rapidly diffuse into amorphous P3HT, but phase separation is maintained if the P3HT layer is cast from a very volatile solvent or if it is annealed prior to casting the PCBM overlayer to complete the bilayer geometry.     

Air‐Processed,Stable Organic Solar Cells with High Power Conversion Efficiency of 7.41%

High efficiency, excellent stability, and air processability are all important factors to consider in endeavoring to push forward the real‐world application of organic solar cells. Herein, an air‐processed inverted photovoltaic device built upon a low‐bandgap, air‐stable, phenanthridinone‐based ter‐polymer (C₁₅₀H₂₁₈N₆O₆S₄)_n (PDPPPTD) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) without involving any additive engineering processes yields a high efficiency of 6.34%. The PDPPPTD/PC₆₁BM devices also exhibit superior thermal stability and photo‐stability as well as long‐term stability in ambient atmosphere without any device encapsulation, which show less performance decay as compared to most of the reported organic solar cells. In view of their great potential, solvent additive engineering via adding p‐anisaldehyde (AA) is attempted, leading to a further improved efficiency of 7.41%, one of the highest efficiencies for all air‐processed and stable organic photovoltaic devices. Moreover, the device stability under different ambient conditions is also further improved with the AA additive engineering. Various characterizations are conducted to probe the structural, morphology, and chemical information in order to correlate the structure with photovoltaic performance. This work paves a way for developing a new generation of air‐processable organic solar cells for possible commercial application.