Two effects of 1,8-diiodooctane on PTB7-Th:PC71BM polymer solar cells

To obtain higher device performance, the ideal bulk heterojunction (BHJ) morphology should feature both nanophase separation to increase charge generation and bi-continuous percolating networks to increase charge transport. In this paper, solvent additive, 1,8-diiodooctane (DIO), was used in PTB7-Th:PC₇₁BM blend to improve BHJ morphology. The effect of DIO on charge generation and charge transport were studied carefully. Experimental study indicated that the effect of DIO on charge generation and charge transport are conflicted. Positive effects of DIO, which were induced by nanophase separation for charge generation in BHJ, are proved by the results of internal quantum efficiency (IQE) and photocurrent density (J_ph), and negative effects of DIO on charge transport has been investigated according to the time-of-flight secondary ion mass spectrometer (TOF-SIMS).     

Air-processed high performance ternary blend solar cell based on PTB7-Th:PCDTBT:PC70BM

Ternary bulk heterojunctions (BHJs) are promising candidates that can improve the power conversion efficiencies (PCEs) of organic solar cells (OSCs). In this paper, a ternary OSC with two donors, including one wide bandgap polymer poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT), one low bandgap polymer Poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-co-3-fluorothieno[3,4-b]thiophene-2-carboxylate] (PTB7-Th), and one acceptor [6,6]-phenyl C70 butyric acid methyl ester (PC₇₀BM), is fabricated in atmospheric conditions. By incorporating a 20% content of PCDTBT, an optimized PCE of 7.86% for ternary OSC is characterized by a short-circuit current density (J_sc) of 15.21 mA cm⁻², a fill factor of 69.70% and an open-circuit voltage (V_oc) of 0.74 V. The V_oc values increased steadily from 0.73 to 0.86 V as the increase of PCDTBT fraction, which indicates that the V_oc of ternary OSC is not limited by the smallest one of the corresponding binary OSC. We show that the J_sc of the ternary OSC is better than those of the binary OSC in virtue of the complementary polymer absorption and cascade energy levels, as well as optimized morphology of the ternary system. Furthermore, the lifetime of the devices with PCDTBT is greatly enhanced. This work indicates that two donors (PTB7-Th/PCDTBT) ternary BHJs system provide a simple and effective method to improve the performance and also the stability of OSCs.     

Photo-physics of PTB7, PCBM and ICBA based ternary solar cells

Indene-C₆₀bisadduct (ICBA) is one of the rare acceptors which can supersede commonly used phenyl-C71-butyric acid methyl ester (PCBM70) in enhancing the performance of bulk heterojunction (BHJ) solar cells owing to its shallower lowest unoccupied molecular orbital (LUMO) level. However, ICBA tends to decrease the photocurrent for most of the low band-gap polymers synthesized to date. Here we examine the interaction of ICBA with the one of the popular low band-gap polymers poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl) carbonyl] thieno[3,4-b]thiophenediyl]] (PTB7), at femtosecond level, to explore key dynamics governing the operation of BHJ cells involving ICBA. The photo-physics of binary and ternary systems based on PTB7 coupled with PCBM70 and/or ICBA are studied by means of transient absorption spectroscopy (TAS) and electrochemical impedance spectroscopy (EIS) and supported by morphology analysis. Our study suggests that both inefficient charge-separation and poor charge transport of ICBA is responsible for relatively low photocurrent generation.     

Effect of incorporation of CdS NPs on performance of PTB7: PCBM organic solar cells

It has been well known that incorporation of nano-heterostructures of various metals, semiconductors and dielectric materials in the active layer of organic solar cells (OSCs) helps in improving power conversion efficiency (PCE). In the present study, we demonstrated microwave synthesis of CdS nanoparticles (NPs) for their application in one of most efficient OSCs consisting of poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl] [3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]thiophenediyl]] (PTB7): [6,6]-phenyl C₇₁-butyric acid methyl ester (PCBM) photoactive blend. This is crucial to fully explore the promising features of low cost and scalability in organic-inorganic hybrid solar cells. Synthesized CdS NPs are slightly elongated and highly crystalline with their absorption lies in the visible region as confirmed by High resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), UV–Vis absorption spectroscopy studies. Our experimental results for the devices in an inverted geometry having a structure ITO/ZnO/PTB7: CdS: PCBM/MoO₃/Ag has shown increase in Jsc and PCE by nearly 10%. However, it was observed that this increase is only when NPs were added in the low concentration in active layer. UV–Vis absorption spectroscopy, Photoluminescence (PL) and atomic force microscopy (AFM) studies were carried out in order understand the device performance.     

Linear and propeller-like fluoro-isoindigo based donor–acceptor small molecules for organic solar cells

Two donor–acceptor type fluoro-isoindigo based small molecule semiconductors are synthesized and their optical, electrochemical, thermal, and charge transport properties are investigated. The two molecular chromophores differ by their architecture, linear (M1) vs propeller-like (M2). Both molecules present a broad absorption in the visible range and a low optical HOMO–LUMO gap (∼1.6 eV). AFM images of solution-processed thin films show that the trigonal molecule M2 forms highly oriented fibrils after a few seconds of solvent vapor annealing. The materials are evaluated as electron donor components in bulk heterojunction organic solar cells using PC₆₁BM as the electron acceptor. The devices based on the propeller-like molecule M2 exhibit a high open-circuit voltage (around 1.0 V) and a power conversion efficiency of 2.23%.     

High-performance hole transport layer based on WS2 doped PEDOT:PSS for organic solar cells

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Solution-processed small molecules based on indacenodithiophene for high performance thin-film transistors and organic solar cells

Solution-processed indacenodithiophene (IDT)-based small molecules with 1,3-indanedione (ID) as terminal acceptor units and 3,3′-hexyl-terthiophene (IDT-3Th-ID(I)) or 4,4′-hexyl-terthiophene (IDT-3Th-ID(II)) as π-bridges, have been designed and synthesized for the application in organic field-effect transistors (OFETs) and organic solar cells (OSCs). These molecules exhibited excellent solubility in common organic solvents, good film-forming ability, reasonable thermal stability, and low HOMO energy levels. For the OFETs devices, high hole motilities of 0.52 cm² V⁻¹ s⁻¹ for IDT-3Th-ID(I) and 0.61 cm² V⁻¹ s⁻¹ for IDT-3Th-ID(II) were achieved, with corresponding high I_ON/I_OFF of ca. 10⁷ and ∼10⁹ respectively. The OSCs based on IDT-3Th-ID(I)/PC₇₀BM (2:1, w/w) and IDT-3Th-ID(II)/PC₇₀BM (2:1, w/w) without using any treatment of solvent additive or thermal annealing, showed power conversion efficiencies (PCEs) of 3.07% for IDT-3Th-ID(I) and 2.83% for IDT-3Th-ID(II), under the illumination of AM 1.5G, 100 mW/cm². The results demonstrate that the small molecules constructed with the highly π-conjugated IDT as donor unit, 3Th as π-bridges and ID as acceptor units, could be promising organic semiconductors for high-performance OFETs and OSCs applications.     

Improved mobility and lifetime of carrier for highly efficient ternary polymer solar cells based on TIPS-pentacene in PTB7: PC71BM

Highly efficient ternary polymer solar cells (T-PSCs) realized by the improved mobility and lifetime of carrier in PTB7: PC₇₁BM: TIPS-pentacene blends were fabricated. By adjusting the weight ratios of third component TIPS-pentacene in the binary PTB7: PC₇₁BM blends, we found that the short circuit current and fill factor (FF) were simultaneously enhanced, resulting in a maximum power conversion efficiency (PCE) of 8.09% with 21.3% improvement. The improved photovoltaic performance of T-PSC was mainly due to the enhanced light absorption, energy level cascading, optimized blend morphology, and increased hole mobility. It was also found that the incorporation of TIPS-pentacene increased the average hole lifetime, ensuring efficient hole transport and collection with suppressed bimolecular recombination, contributing to the photocurrent. Additionally, the low thickness dependent row-off of FF indicates TIPS-pentacene is a promising third component for the realization of thick film T-PSC. The improved PCEs were obtained as well for other ternary donor: acceptor: TIPS-pentacene systems, demonstrating that the incorporation of TIPS-pentacene is a wide practicable methodology for the development of highly efficient T-PSCs.     

In-situ investigation of interfacial effects on charge accumulation and extraction in organic solar cells based on transient photocurrent studies

In organic solar cells, the interfacial and bulk photovoltaic processes are typically coupled based on charge transport and accumulation. In this article, we demonstrated that the in situ transient photocurrent measurements can be a powerful approach to separately investigate the interfacial effects on interfacial and bulk photovoltaic process. Based on this method, the effects of interfacial dipoles on charge extraction, accumulation, and recombination are solely studied by comparing Ca and Al devices with standard architecture of ITO/PEDOT/P3HT:PCBM/cathode. We observe that stronger interfacial dipoles can significantly decrease the charge extraction time and consequently increase the charge extraction efficiency. More importantly, stronger interfacial dipoles can also decrease the charge accumulation within the bulk photovoltaic layer. Furthermore, our experimental results indicate that the bulk-accumulated charges can act as recombination centers under device-operating condition, resulting in the recombination loss in photogenerated carriers. Clearly, our studies of transient photocurrents elucidated the charge extraction, accumulation, and recombination in OSCs.     

Revealing the effect of donor/acceptor intermolecular arrangement on organic solar cells performance based on two-dimensional conjugated small molecule as electron donor

A series of solution processed organic solar cells (OSCs) were fabricated with a two-dimensional conjugated small molecule SMPV1 as electron donor and fullerene derivatives PC₇₁BM or ICBA as electron acceptor. The champion power conversion efficiency (PCE) of OSCs arrives to 7.05% for the cells with PC₇₁BM as electron acceptor. A relatively large open circuit voltage (V_OC) of 1.15 V is obtained from cells using ICBA as electron acceptor with an acceptable PCE of 2.54%. The fill factor (FF) of OSCs is 72% or 61% for the cells with PC₇₁BM or ICBA as electron acceptor, which is relatively high value for small molecule OSCs. The relatively low performance of OSCs with ICBA as electron acceptor indicates that ICBA cannot play positive role in photoelectric conversion processes, which is very similar to the phenomenon observed from the OSCs with high efficient narrow band gap polymers other than P3HT as electron donor, the underlying reason is still in debate. The SMPV1 has strong self-assemble ability to form an ordered two dimensional lamellar structure, which provides an effective platform to investigate the effect of electron acceptor chemical structure on the performance of OSCs. Experimental results exhibit that ICBA molecules may prefer to vertical cross-intercalation among side chains of SMPV1, PC₇₁BM molecules may have better miscibility with SMPV1 in the active layer. The different donor/acceptor (D/A) intermolecular arrangement strongly influences photon harvesting, exciton dissociation and charge carrier transport, which may provide a new sight on performance improvement of OSCs by adjusting D/A intermolecular arrangements.     

High open-circuit voltage of the solution-processed organic solar cells based on benzothiadiazole–triphenylamine small molecules incorporating π-linkage

Two novel small molecular photovoltaic (PV) materials, BDPTBT and BDATBT were designed and synthesized, consisting of 5,6-bis-(octyloxy)benzo[c][1,2,5]thiadiazole (DOBT) as electron-withdrawing core (A), and triphenylamine (TPA) as electron-donating side group (D). Moreover, the benzene and ethynylbenzene as π-linkage were introduced to form donor–π-acceptor–π-donor (D–π-A–π-D) typed molecular structures, respectively. To fully investigate the linkage effect of a series of small molecules, two reference compounds BDCTBT and BDETBT were also studied systematically, consisting of 2-phenylacrylonitrile and styrene as π-linkage, respectively. As a result, the π-linkage units, benzene, styrene, ethynylbenzene and 2-phenylacrylonitrile played an important role in modifying molecular structure and improving PV performance. Bulk heterojunction (BHJ) solar cells based on BDPTBT/PC₆₁BM and BDATBT/PC₆₁BM yielded the power conversion efficiencies (PCEs) of 2.99% and 2.03%, respectively. Notably, BDATBT based device showed a high open-circuit voltage (Voc) of 1.03 V. Compared to the results we have reported previously, the reference devices based on BDCTBT/PC₆₁BM and BDETBT/PC₆₁BM with the optimized weight ratio showed dramatically enhanced PCEs of 4.84% and 3.40%, respectively, and BDCTBT based device showed a high Voc of 1.08 V. To our knowledge, the Voc of 1.08 V is the highest voltage reported to date for devices prepared from solution-processed small-molecule-donor materials, and the PCE of 4.84% is the highest efficiency reported so far for D–A–D-typed benzothiadiazole (BT)–TPA based solution-processed small molecules PV devices.     

High efficient ITO free inverted organic solar cells based on ultrathin Ca modified AZO cathode and their light soaking issue

Aluminum doped zinc oxide (AZO) was used to be the cathode instead of indium-tin-oxide (ITO) in the poly (3-hexylthiophene-2,5-diyl):[6,6]-phenyl C₆₁ butyric acid methyl ester (P3HT:PCBM) based bulk heterojunction inverted organic solar cells (IOSCs). For the AZO only IOSC, the device shows a poor power conversion efficiency (PCE) of 1.34% and a light soaking issue related to the energy barrier at the AZO/P3HT:PCBM interface. When a 5 nm Ca modifying layer is inserted between AZO and P3HT:PCBM, the obtained AZO/Ca (5 nm) IOSC shows an increased PCE from 1.74% to 2.69% after 15 min illumination. It is thought that the increased photoconductivity of AZO/Ca (5 nm) film upon illumination and the enhanced electron transport across the AZO/Ca interface may be responsible for the light soaking issue. When an ultrathin Ca modifying layer of 1 nm is employed, a further improved PCE of 3.17% is obtained, and remarkably, no light soaking issue is observed in this case. However, this unexpected issue appears after the un-encapsulated AZO/Ca (1 nm) IOSC has been stored in air for several days, which may be due to the energy loss in the electron transport across the interface between partly oxidized Ca and AZO layers induced by the oxidization of Ca. Furthermore, the AZO/Ca (1 nm) IOSC has a comparable PCE to the referenced ITO/Ca (1 nm) IOSC and presents a better air-stability. It is thus concluded that the AZO cathode is a promising alternative of ITO to fabricate the high efficient and long-lifetime IOSCs.     

Effect of bulk and planar heterojunctions based charge generation layers on the performance of tandem organic light-emitting diodes

Tandem organic light-emitting diodes (OLEDs) were fabricated using organic planar and bulk heterojunctions based charge generation layers (CGLs), which were composed of cobalt phthalocyanine (CoPc) and fullerene (C₆₀). The electroluminescent (EL) characteristics of these two kinds of devices were systematically studied. The results showed that, compared to the corresponding devices with planar heterojunction (PHJ) based CGL, the tandem OLEDs with bulk heterojunction (BHJ) based CGL exhibited a dramatic improvement of performance. By investigating the electrical characteristics of CGLs, it was found that more hetero-interfaces introduced in the BHJ blend were beneficial for generating more interfacial dipoles and charge carriers, and the optimized charge transport pathways were favorable to promote both electron and hole mobilities. As a result, the improved charge carrier balance led to the efficiency enhancement of device performance. The results demonstrated the advantageous effect of BHJ blend film for the rational design of CGLs on the realization of high OLEDs performance.     

High performance airbrush spray coated organic solar cells via tuning the surface tension and saturated vapor pressure of different ternary solvent systems

In this work, thieno [3,4-b] thiophene/benzodithiophene (PTB7): [6,6]-phenyl C71-butyric acid methyl ester (PC₇₁BM) based organic solar cell (OSC) with a new record of power conversion efficiency (PCE) of ∼7.62% has been realized using airbrush spray (AS) coating method in air ambient which can be well compatible with large-scale fabrication. By investigating the physical mechanism of AS coated blend films, a series of ternary solvent systems (TSS) are used to simultaneous optimize the surface tension and the saturated vapor pressure of solution. Therefore, different TSS further controls the morphology of PTB7:PC₇₁BM blend films precisely and systematically. It is elucidated that the chlorobenzene (CB)/o-Xylene (o-Xy)/1, 8-diiodoctane (DIO) TSS with a ratio of 37:60:3 vol.% could lead to a homogeneous surface morphology with a decreased aggregation domain size of active layer. In addition, the high fill factor, increased PC₇₁BM absorption and internal quantum efficiency indicate the formation of bicontinuous interpenetrating and fully percolated networks with nanostructured phase separation in BHJ blend films. Ultimately, the AS coated OSCs based on the TSS of CB/o-Xy/DIO gains a 34% enhancement in PCE, compared with the conventional CB/DIO solvent based OSCs.     

High efficiency perovskite solar cells using a PCBM/ZnO double electron transport layer and a short air-aging step

Solution processed CH₃NH₃PbI_xCl_3–x based planar heterojunction perovskite solar cells with power conversion efficiency (PCE) above 14% are reported. The devices benefit from a phenyl-C₆₁-butyric acid methyl ester (PCBM)/ZnO double electron transport layer (ETL) as well as a short air-aging step. The role of the additional ZnO ETL is studied by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and secondary ions mass spectroscopy (SIMS). Apart from improving the energy level alignment, the ZnO layer blocks the reactions between the metal electrode and perovskite components, increasing the air stability of the device. A crucial step in our processing is a short air-aging step for the device, which significantly increases the device performance by reducing the recombination process. Since the ZnO nanoparticle layer requires no thermal annealing, the maximum temperature to fabricate the device can be kept below 100 °C, making this structure compatible with roll-to-roll processing on plastic films.     

Effect of drying temperature on structural and electrical properties of PANI:PVDF composite thin films and their application as buffer layer for organic solar cells

Spin coated polyaniline:polyvinylidene-fluoride (PANI: PVDF) composites films were prepared by the optimized mass ratios of 5:95. The effect of drying temperature on the structure, morphology and electrical conductivity of PANI: PVDF films were studied, and their use as buffer layer for organic solar cells performance was explored. The PANI: PVDF film which dried at 90 °C exhibit higher β-phase content in PVDF (F_β=94%). Furthermore, solar cells conversion efficiency (η=3.06%) is better when using ITO/PVDF:PANI (dried at 90 °C) as photo-anode than that containing only ITO (η=0.96%) and ITO/PEDOT:PSS (η=1.78%).     

High photo-current in solution processed organic solar cells based on a porphyrin core A-π-D-π-A as electron donor material

Two new conjugated acceptor-donor-acceptor (A-π-D-π-A) molecules with a porphyrin core linked by ethynylene bridges to two thiophene (1a) or thienylenevinylenethiophene (1b) units and both capped by N-ethylrhodanine have been synthesized. These compounds were used as the main electron donor moieties for bulk heterojunction small molecule organic solar cells (BHJ-SMOSC). The optimized devices, with PC71BM as the main electron acceptor molecule, show remarkable short circuit currents, up to 13.2 mA/cm², an open circuit voltage of around 0.85 V, and power conversion efficiencies up to 4.3% under 100 W/cm². The External Quantum Efficiency (EQE), Atomic Force Microscopy (AFM), hole mobility, Photo-Induced Charge Extraction (PICE) and Photo-Induced Transient Photo-Voltage (PIT-PV) were analyzed in devices based on 1a and 1b in order to account for differences in the final performance of the two molecules. The PIT-PV decays showed slower recombination kinetics for devices fabricated with 1b. Moreover, the EQE was greater for 1b and this is ascribed to the better nanomorphology, which allows better charge collection before carrier recombination takes place.     

Correlation between ultrafast transient photomodulation spectroscopy and organic photovoltaic solar cell efficiency based on RR-P3HT/PCBM blends

Ultrafast transient spectroscopy was applied to various films of regio-regular polythiophene (RR-P3HT, donor-D) and C₆₀ derivative (PCBM, acceptor-A) blends, in conjunction with organic photovoltaic (OPV) solar cell fabrication and evaluation based on the same blends, for investigating the existence of a correlation between the device efficiency and the transient photophysics characteristics. For our transient spectroscopy measurements we used the ps pump–probe transient photomodulation (PM) technique having a unique probe spectral range in the mid-IR (0.25–1.05 eV). We found that the transient PM spectra contain photoinduced absorption bands of excitons in the donor polymer, charge transfer excitons (CTE) at the D–A interfaces, and free polarons. We compared the relative density of photogenerated CTE in D–A blends having various D–A weight ratio with the photocurrent density of fabricated solar cells based on the same blends. We found that the dissociation of CTE into free charges correlates well with the optoelectronic measurements of the corresponding solar cell. The more efficient CTE dissociation occurs in films having the optimum D–A weight ratio (which is 1.2:1 for the P3HT/PCBM system) that shows the highest OPV power conversion efficiency; this is due to the lowest CTE binding energy for this blend that results from the most suitable D- and A- grain sizes. We also show that the exciton lifetime is the shortest for the optimum blend, and this helps boosting the device efficiency by reducing energy loss.     

3-Dimensional non-fullerene acceptors based on triptycene and perylene diimide for organic solar cells

Two molecules based on triptycene and perylene diimide (PDI) were designed and synthesized as non-fullerene acceptors for organic solar cells (OSCs). The bay-substituted and the imide-substituted molecules, named as TPBA and TPI, respectively, have rigid three-dimensional backbones, which improved the morphological compatibility with the donor polymers. TPBA and TPI exhibit suitable energy levels as acceptors and efficient absorption in the range of 450–600 nm. Their blended films with PTB7-Th displayed power conversion efficiencies of 2.80% and 3.64%, respectively.     

D-A-D-A-D push pull organic small molecules based on 5,10-dihydroindolo[3,2-b]indole (DINI) central core donor for solution processed bulk heterojunction solar cells

Two D-A-D-A-D small molecules based on same 5,10-dihydroindolo [3,2-b]indole central donor core and different benzothiadiazole (BT) and fluorine substituted BT (FBT) acceptor units, denoted as p-DINI-(BTTh₃)₂ (1) and p-DINI-(FBTTTh₃)₂ (2), respectively were synthesized and their optical and electrochemical properties were investigated. These molecules were applied as donor along with PC₇₁BM as electron acceptor for the fabrication of solution processed bulk heterojunction organic solar cells. The solar cells prepared from the optimized active blended layer (1:2) cast from dichlorobenzene (DCB) showed overall power conversion efficiency (PCE) of 2.02% and 2.70% for 1 and 2, respectively as donor. The higher PCE of 2 as compared to 1 is attributed to the higher hole mobility and broader IPCE spectra. In order to improve the PCE we have employed a two step treatment of active layer i.e. solvent vapor annealing after thermal annealing (SVA-TA) and the PCE has been enhanced up to 4.14% and 5.27% for optimized 1:PC₇₁BM and 2:PC₇₁BM active layers, respectively. The improvement in the PCE has been resulted from the improvement in the balanced charge transport and better crystallinity of the donor in the blended active layer.