Molecular engineering of Diketopyrrolopyrrole-based photosensitizer for solution processed small molecule bulk heterojunction solar cells

New symmetrical low band-gap small molecule materials, DPP-bis[ter-3HT-TPA] and DPP-bis[ter-3HT] as novel derivatives of Diketopyrrolopyrrole-thiophene with/without triphenylamine (TPA) end group have been synthesized and characterized. And the effects of TPA moiety were investigated. Compared to DPP-bis[ter-3HT], DPP-bis[ter-3HT-TPA] shows red-shifted absorption and significantly higher molar absorption coefficient. And the HOMO level of DPP-bis[ter-3HT-TPA] is elevated than DPP-bis[ter-3HT]. Moreover, DPP-bis[ter-3HT-TPA] exhibited one order higher hole mobility than DPP-bis[ter-3HT], suggesting that TPA contributes to a better hole mobility. The bulk-heterojunction photovoltaic devices with DPP-bis[ter-3HT-TPA] showed better efficiencies than DPP-bis[ter-3HT], showing the best power-conversion efficiency (PCE) of 1.5% (±0.12) under 100 mW/cm² with a short-circuit current (J_sc)=5.73 mA/cm², a fill factor (FF)=0.45, and an open-circuit voltage (V_oc)=0.59 mV.     

Novel symmetric squaraine chromophore containing triphenylamine for solution processed small molecule bulk heterojunction solar cells

New symmetrical low band-gap small molecule materials, SQ-bis[HP-HT2-TPA] and SQ-bis[HP-HT2-BT] incorporating as novel derivative of squaraine-pyrrole framework and π-extended thiophene with triphenyamine (TPA) and benzothiophene (BT) end group, have been synthesized and characterized. The effects of TPA moiety were investigated. Compared to SQ-bis[HP-HT2-BT], SQ-bis[HP-HT2-TPA] exhibited three times improved transporting property of hole carrier and four times enhanced absorptivity by more efficient intermolecular π−π interaction for high-efficiency bulk heterojunction (BHJ) device, suggesting that TPA contributes to a better hole mobility. The bulk-heterojunction photovoltaic devices fabricated with SQ-bis[HP-HT2-TPA]/C₇₁-PCBM BHJ film had an average power-conversion efficiency of 1.83%(±0.12) under 100 mW/cm², with a short-circuit current (J_sc) of 9.32 mA/cm², fill factor (FF) of 0.30, and open-circuit voltage (V_oc) of 0.65 V, which has ∼42% higher efficiency compared to SQ-bis[HP-HT2-BT]/C₇₁-PCBM BHJ films.     

Solution-processed bulk heterojunction organic solar cells with high polarity small molecule sensitizer

A new sensitizer molecule, HMBI (9,18-(di-2-hexyldecyl)-2,11-dimethoxy-9,18-dihydrobenzo[5,6]-s-indaceno[1,2-b]indeno[2,1-h]carbazol-6,15-dione), containing electron-donating carbazole and electron-accepting diketone units, has been synthesized for solution-processed bulk heterojunction organic solar cells. The HMBI material has good solubility in common organic solvents. Its HOMO and LUMO energy levels were found to be at 5.6 and 3.0 eV, respectively. It has absorption bands ranging from 300 to 500 nm. Dispersion of HMBI molecules in the P3HT/PCBM blend broadens the absorption bands over the spectral range of 350-500 nm. Uniform thin film devices doped with varying concentration of HMBI, incorporated within the P3HT/PCBM blend, were fabricated. The 3 wt% of HMBI doping produces an improvement in power-conversion efficiency (PCE) up to 11.5% compared with the reference P3HT/PCBM device. Efficient light harvesting caused by HMBI sensitizer molecules primarily yields increased carrier generation and short-circuit current. In addition, some morphological improvements in the P3HT/PCBM system may contribute to the generation of enhanced photocurrent.     

P3HT/PCBM bulk heterojunction solar cells: Relation between morphology and electro-optical characteristics

The performance of organic solar cells based on the blend of regioregular poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) is strongly influenced by blend composition and thermal annealing conditions. X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM) diffraction measurements show that in the considered blends, ordering of P3HT plays a key role in understanding the PV-performance. It is demonstrated that the natural tendency of regioregular P3HT to crystallize is disturbed by the addition of PCBM. Annealing however improves the crystallinity, explaining the observed spectral broadening and is also resulting in a higher mobility of the holes in P3HT.     

Effect of CsF interlayer on the performance of polymer bulk heterojunction solar cells

We fabricated polymer bulk heterojunction solar cells with blends of poly (2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) by using CsF as an interlayer. Under illumination, the device with Al/CsF cathode exhibited a higher energy conversion efficiency compared to the Al/LiF cathode. The performance improvement with the Al/CsF cathode comes from the lower series resistance, which is almost constant (~6 Ω cm²) for all the CsF layer thicknesses included in the present study. The mechanism responsible for this phenomenon is attributed to the dissociation of CsF upon Al deposition to liberate Cs with a low work function, which reduces the interface resistance of the active layer/cathode and enhances the interior electric field for more efficient charge transport in the device.     

Bulk heterojunction organic solar cells utilizing 1,4,8,11,15,18,22,25-octahexylphthalocyanine

Bulk heterojunction solar cells utilizing soluble phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH₂) have been investigated. The active layer was fabricated by spin-coating the mixed solution of C6PcH₂ and 1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM). The photovoltaic properties of the solar cell with bulk heterojunction of C6PcH₂ and PCBM demonstrated the strong dependence of active layer thickness, and the optimized active layer thickness was clarified to be 120 nm. By inserting MoO₃ hole transport buffer layer between the positive electrode and active layer, the FF and energy conversion efficiency were improved to be 0.50 and 3.2%, respectively. The tandem organic thin-film solar cell has also been studied by utilizing active layer materials of C6PcH₂ and poly(3-hexylthiophene) and the interlayer of LiF/Al/MoO₃ structure, and a high V_oc of 1.27 V has been achieved.     

Efficient organic tandem cell combining a solid state dye-sensitized and a vacuum deposited bulk heterojunction solar cell

In this letter, we report on an efficient organic tandem solar cell combining a solid state dye-sensitized with a ZnPc/C₆₀-based, vacuum deposited bulk heterojunction solar cell. Due to an effective serial connection of both subcells and to the complementary absorption of the dyes used, a power conversion efficiency of η_p=(6.0±0.1)% was achieved under simulated AM 1.5 illumination. The device parameters are , and FF=(54±1)%.     

Optimum design of ordered bulk heterojunction organic photovoltaics

Organic photovoltaics (OPVs) have recently received increasing attention as alternatives to inorganic solar cells because of their light weight, compatibility with flexible electronics, and low production cost. In this work, an ideal device structure for ordered bulk heterojunction (OBHJ) organic photovoltaics is proposed. Also suggested is a parameter related to the power conversion efficiency (PCE) of the devices. Such a parameter could serve as a rule of thumb for researchers. For cases in which it is difficult to reduce the pillar size and spacing, the proposed parameter dictates that an increase in the active layer thickness could be one way to increase the PCE of an OBHJ. To generate maximum PCE, (1) the pillar size and spacing must be two to three times less than the exciton diffusion length and (2) the thickness of the active layer has to be greater than half of the photon mean free path, which is the inverse of the absorption coefficient.     

Stacked organic solar cells based on pentacene and

In order to improve photon harvesting, two small molecule organic solar cells are placed in series on top of each other. These stacked cells need an efficient recombination center in between both cells. In this study we test vacuum deposited metal layers as recombination centers with pentacene and buckminsterfullerene (C₆₀) as donor and acceptor, respectively. S-shaped curves are visible in the I–V characteristics when using thin layers of aluminum, indicating a barrier for extraction inside the device. Thin metal layers of gold or silver result in an increased open-circuit voltage without the appearance of these S-shaped features.     

Effect of organic salt doping on the performance of single layer bulk heterojunction organic solar cell

The effect of organic salt, tetrabutylammonium hexafluorophosphate (TBAPF₆) doping on the performance of single layer bulk heterojunction organic solar cell with ITO/MEHPPV:PCBM/Al structure was investigated where indium tin oxide (ITO) was used as anode, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV) as donor, (6,6)-phenyl-C61 butyric acid methyl ester (PCBM) as acceptor and aluminium (Al) as cathode. In contrast to the undoped device, the electric field-treated device doped with TBAPF₆ exhibited better solar cell performance under illumination with a halogen projector lamp at 100 mW/cm². The short circuit current density and the open circuit voltage of the doped device increased from 0.54 μA/cm² to 6.41 μA/cm² and from 0.24 V to 0.50 V, respectively as compared to those of the undoped device. The significant improvement was attributed to the increase of built-in electric field caused by accumulation of ionic species at the active layer/electrode interfaces.     

Efficient hybrid bulk heterojunction solar cells based on phenylenevinylene copolymer, perylene bisimide and TiO2

A soluble alternating phenylenevinylene copolymer P containing a side anthracene, which was attached to the thiophene ring via a vinylene bridge, was synthesized by Heck coupling. The copolymer had relatively low glass transition temperature (61 °C) and decomposed above 400 °C. The absorption maximum of P was located at 387–402 nm with an optical band gap of 2.32 eV. The emission spectra of P indicated that an intramolecular energy transfer from the side anthracene to the main chain took place via the vinylene bridge. In addition, a new symmetrical compound A based on perylene–anthracene was synthesized and used as electron acceptor in the device. Photovoltaic devices were fabricated using a blend of copolymer P as donor and compound A as acceptor, as photoactive layer film sandwiched between indium tin oxide-coated glass and Al electrodes. This device showed a power conversion efficiency of 0.72%. However, when TiO₂ nanoparticles were incorporated on the pristine P:A blend, the power conversion efficiency of the device was enhanced up to 1.32%, which is attributed to the enhanced photoinduced excitons due to the increase of the interfacial area and improved charge carrier mobility. The power conversion efficiency of the P:A:TiO₂ based photovoltaic device was further improved up to 2.64%, when the hybrid composite was treated with a mixture of Li salt and 4-tert-butylpyridine, which is attributed to the reduction in the recombination of charge carriers.     

Total charge amount as indicator for the degradation of small molecule organic solar cells

We show that the number of extracted charge carriers is a suitable measure to compare lifetime measurements on organic solar cells at different intensities. In detail, we used pin-structures with active layers containing a bulk heterojunction of Zincphthalocyanine (ZnPc) and C₆₀. Extended lifetime measurements under constant monochromatic or white illumination at defined temperatures of 50 °C or 90 °C are done. On the one hand, we show that the number of extracted charge carriers is important to determine the degree of degradation. On the other hand, our results show that the energy of irradiated photons is significant for accelerated measurements. This is an major advantage for the realisation of accelerated lifetime measurements. Additionally, we find that not single charge carriers, but excitons cause the degradation of the observed solar cells.     

Photocarrier generation in organic thin-film solar cells with an organic heterojunction

Photocurrent–voltage characteristics for organic solar cells with a heterojunction formed between copper phthalocyanine and a perylene derivative (or C₆₀) were studied. The photocurrent was observed under both reverse and forward biases. From the analysis of the photocurrent action spectra, the origin of the reverse photocurrent was attributed to the excitons formed in both the organic layers, whereas that of the forward photocurrent was attributed to the excitons formed in the perylene derivative (or C₆₀) layer. The photocurrent density under reverse bias increased at higher temperatures, suggesting that the charge recombination possibility was lowered at higher temperatures. On the basis of the time responses of the photocurrents observed after pulsed photoirradiation, the charge separation and transport processes are discussed.     

Progress in organic tandem solar cells

有机太阳能电池是20世纪90年代发展起来的新型太阳能电池,它是以有机半导体作为实现光电转换的活性材料.与无机太阳能电池相比,它具有成本低,厚度薄,质量轻,制造工艺简单,易于做成大面积柔性器件等优点,具有广阔的发展和应用前景.有机叠层太阳能电池由于相对于单结电池具有更高的能量转换效率,越来越吸引研究者的注意.本综述将会从有机叠层太阳能电池的结构,中间层设计,窄带隙活性层材料及高效率有机叠层太阳能电池研究进展等方面阐述有机叠层太阳能电池的研究现状和未来的发展趋势.     

Tetrabutyl-tetraphenyl-diindenoperylene derivatives as alternative green donor in bulk heterojunction organic solar cells

We present the material 2,3,10,11-tetrabutyl-1,4,9,12-tetraphenyl-diindeno[1,2,3-cd:1′,2′,3′-lm] perylene (Bu4-Ph4-DIP) as alternative green donor for bulk heterojunction small molecule organic solar cells (SMOSC). It is shown that Bu4-Ph4-DIP exhibits suitable absorption characteristics to be a potential material to fill the absorption gap between the commonly used standard absorbers ZnPc and C₆₀.Devices with bulk heterojunctions of Bu4-Ph4-DIP:C₆₀ display very high open circuit voltages of 0.99 V, high fill factors of up to 57%, and experiments yield promising efficiencies of η>2%. Such green-blue absorbing SMOSC are characterized by current voltage and external quantum efficiency measurements, and material properties are studied. It is shown that the devices are responsive to substrate heating, and that different donor-acceptor mixing ratios can increase device performance. Possible influences of mixing ratio and heating on device morphology and electrical properties are discussed.     

New amorphous small molecules—Synthesis, characterization and their application in bulk heterojunction solar cells

We successfully synthesized a series of novel solution processible small molecules (2TAPM, 4TAPM and 2BTAPM) consisting of electron-accepting unit (2-pyran-4-ylidenemalononitrile) (PM) and electron-donating unit (Triphenylamine and different thiophene units). Differential scanning calorimetry (DSC) measurement indicates that these small molecules are amorphous. UV-vis absorption spectra show that the combination of PM with moieties having gradually increased electron-donating ability results in an enhanced intramolecular charge transfer (ICT) transition, leading to an extension of the absorption spectral range and a reduction of the band gap of the molecules. Both cyclic voltammetry measurement and theoretical calculations show that the highest occupied molecular orbital (HOMO) energy levels of the molecules could be fine-tuned by changing the electron-donating ability of the electron-donating moieties. The bulk heterojunction (BHJ) photovoltaic devices with a structure of ITO/PEDOT:PSS/small molecules:PC₇₁BM/LiF/Al were fabricated by using the small molecules as donors and (6,6)-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) as acceptor. Power conversion efficiencies of 1.76% and 2.47% were achieved for the photovoltaic devices based on 2TAPM:PC₇₁BM and 4TAPM:PC₇₁BM under simulated air mass 1.5 global irradiation (100 mW/cm²), respectively.     

Improved power conversion efficiency of bulk heterojunction poly(3-hexylthiophene):PCBM photovoltaic devices using small molecule additive

We report that the power conversion efficiency (PCE) of the bulk heterojunction organic photovoltaic device based on poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) blend was improved by incorporating a small molecule SM having absorption band in the longer wavelength region. SM is a small molecule containing thienothiadiazole central unit with terminal cyanovinylene 4-nitrophenyl at both sides, which were connected to the central unit via a thiophene ring. The combination of SM with P3HT and PCBM allows not only a broad band absorption up to longer wavelength, but also tuning the inter-energy level leading to a higher short circuit current (J_sc) and open circuit voltage (V_oc). The device based on the as cast P3HT:PCBM:SM exhibits a PCE of 3.69%, which is higher than the device based on P3HT:PCBM and SM:PCBM blends. The overall PCE of the device based on thermally annealed blend is further improved up to 4.1%. The improvement of the PCE has been attributed to a better charge transport in the device, due to the increased crystallinity of the blend through thermal annealing.     

Determination of photo-active region in organic thin film solar cells with an organic heterojunction

The photo-active region in the solar cells consisting of Cu-phthalocyanine (CuPc) and perylene-derivative (PV) layers was determined by using exciton blocking layers (EBLs) inserted in these layers. The photocurrent density was low when the EBL was placed near the CuPc/PV interface. With the increase of the distance between the EBL and the CuPc/PV interface, the photocurrent increased. However, when the distance reached a certain value, it leveled off owing to the limited diffusion length of excitons. From the analysis of the relationship between the position of EBL and the photocurrent density, the photo-active regions in the CuPc and PV layers were estimated to be 8 and 12 nm thick from the interface, respectively.     

Vacuum-free processed transparent inverted organic solar cells with spray-coated PEDOT:PSS anode

Spray coating is a high throughput coating technique that is scalable and adaptable for organic photovoltaic manufacturing. To ensure uniform coating of the organic layers, the wettability, surface tension and boiling points of the solvents have to be optimized. Here, we used microscopic videos to understand the dynamics of the spray coating process. By optimizing the wettability and drying time of the PEDOT:PSS suspension on a hydrophobic surface, we attained a spray coated transparent anode without compromising on device performance. We further applied this vacuum-free process to a near infrared absorber to achieve a transparent organic solar cell with close to 60% transparency.     

Solution processable quinacridone based materials as acceptor for organic heterojunction solar cells

Two series of novel quinacridone (QA) based materials that combined a strong absorption over a broad range in visible region with good electrical characteristics, which were used as the new electron-accepting materials for organic solar cells, are explored. Unique cyclic compounds 1-6 are synthesized by incorporating electron withdrawing groups (CN, COOH) at carbonyl position of alkyl substituted quinacridones, which lead to the compounds possessing the characteristics of solution-processed and being suitable for photovoltaic applications. Heterojunction solar cells with simple device configuration using these soluble materials as acceptor and effective donor poly (3-hexyl thiophene) (P3HT) were fabricated. The maximum power conversion efficiency (PCE) achieved in the solar cell based on compound 5 is 0.42% under simulated AM 1.5 solar irradiation with J_sc=1.80 mA cm⁻², V_oc=0.50 V and FF=47%. Although the aimed devices just exhibit moderate PCE, our results clearly suggest that the new-type electron-accepting materials different from fullerene have great potential as acceptor in heterojunction solar cell due to many advantages of the QA derivatives such as relatively inexpensive, good electrochemical stability and could be readily modified.