Low band gap polymers for photovoltaic device with photocurrent response wavelengths over 1000 nm

To pursue high power conversion efficiency (PCE) of polymer solar cells (PSCs), many new semiconducting polymers with low band gaps have been developed in the past several years. In this perspective paper, we focused on super low band gap photovoltaic polymers with photocurrent response extending over 1000 nm. This kind of micrometer-response polymers (μmR-polymer) could increase the short circuit current (J_SC) due to better match of absorption spectra of the polymers with the solar irradiation and show tremendous potential for application in tandem solar cells and transparent solar cells. The necessary conditions for the design of this kind of μmR-polymers are discussed. Furthermore, the remaining problems and challenges, and the key research direction in near future are discussed.     

Photostability of organic materials used in polymer solar cells

To make polymer solar cells (PSCs) a competitive market technology, integrated efforts are required toward the development of highly efficient light harvesting and charge transporting materials with good thermal and photochemical stability, and which can be processed from solution. Nowadays, a critical issue to be solved is enhancing the stability and durability of PSCs. Indeed, the photoactive material used in the active layer dictates the efficiency of the device on the one hand but, on the other hand, it is well known that organic materials are unstable when exposed to light irradiation, which provokes a degradation of their properties. Making long lifetime solar cells with polymers that are susceptible to degradation under light exposure could be an unrealistic challenge. Therefore, elucidating the mechanism of polymer photodegradation is a key point for developing strategies to decrease or prevent the loss of the functional properties of the material. In this paper, the basic concepts of polymer photo‐aging are explained first. Then the photodegradation mechanisms of conjugated polymers currently used in PSCs are reported. Finally, as barrier materials able to cut off moisture and oxygen ingress are essential for the stability of PSCs, methods for designing coatings for PSC encapsulation are presented, based on recent publications. © 2013 Society of Chemical Industry     

Thin film of a porphyrin‐end‐functionalized poly(cyclohexane)/fullerene‐end‐functionalized poly(4‐diphenylaminostyrene) blend: Control of microphase separation in a light‐harvesting system for polymer solar cells

Thin films of a tetraphenylporphyrin‐end‐functionalized polycyclohexane zinc complex (ZnTPP‐PCHE)/fullerene‐C₆₀ (C₆₀) end‐functionalized poly(4‐diphenylaminostyrene) (C₆₀‐PDAS) were prepared to investigate their potential as a light‐harvesting system for polymer solar cells (PSCs). The microphase separation in the ZnTPP‐PCHE/C₆₀‐PDAS blends had a significant effect on the optical properties; the absorption band of the microphase separation structure that overlaps the visible‐light region was considerably enhanced with an increase in the C₆₀ concentration in the polymer film, although both pristine ZnTPP‐PCHE and C₆₀‐PDAS thin films had only weak absorption bands in that region. Therefore, this polymer blend is considered to be suitable for use as a light‐harvesting system for PSCs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of a selenium and germanium containing random copolymer as an acceptor for all‐polymer solar cells

For the need of electron‐transporting and electron‐affinity materials, n‐type polymers (as acceptor) have gained a lot of attention recently. We have synthesized a selenium and germanium containing copolymer as the acceptor for all‐polymer solar cells (all‐PSCs). The copolymer has larger p‐orbital selenium and germanium atoms for more electron transition from pi to pi* to enlarge light harvest of polymer. To prepare the copolymer, a monomer containing d‐orbital atom, selenium, was first synthesized from low‐cost starting materials. A random copolymer was prepared from the monomer with a commercial germanium containing monomer via palladium catalyzed Stille coupling reaction. Taking the side‐chain effect into account, we incorporated dodecyloxy group to increase the solubility of the polymer and also increase the coplanarity by oxygen–sulfur (S–O) interaction. Despite the low short‐circuit current density (Jsc) value, the random copolymer with 3d‐orbital electrons has the potential to be the candidate for n‐type material. In comparison, we also fabricated P3HT/PffBT4T‐2OD all‐PSCs, acquiring PCE of about 0.5% without any additive. POLYM. ENG. SCI., 58:387–394, 2018. © 2017 Society of Plastics Engineers     

Bis(thien-2-yl)-2,1,3-benzothiadiazole-diketopyrrolopyrrole-based acceptor–acceptor conjugated polymers: Design,synthesis, and the synergistic effect of the substituent on their solar cell properties

Three acceptor–acceptor conjugated copolymers ( TBT-DPP , FTBT-DPP , and HFTBT-DPP ) with different substituent groups have been synthesized with palladium-catalyzed Stille coupling condensation polymerization assisted with microwave. Polymer solar cells (PSCs) based on these copolymers as the electron donors and PC71BM as the acceptor have been fabricated. The synergistic effect of the substituent between two fluorine atoms and hexyl alkyl chains in bis(thien-2-yl)-2,1,3-benzothiadiazole fragment on their solar cell properties has been investigated. Both the fluorine atoms and the synergistic effect can improve the solubility of the polymers effectively while the excellent thermal stability properties are still retained. Two fluorine atoms (polymer FTBT-DPP ) increased the power conversion efficiency of the PSCs twice compared with TBT-DPP (without substituent). The synergistic effect (polymer HFTBT-DPP ) decreased that seriously to zero. Density function theory calculations showed that the conjugation level of the polymer backbone is one of key factors. It demonstrates that the synergistic effect of fluorine atoms and alkyl chains in the same fragment does not always work well in improving the PSCs performance.     

Synthesis of a terpolymer containing fluorene,side chain conjugated thiophene and benzothiadiazole and its applications in photovoltaic devices

A terpolymer (POTVTh‐8FO‐DBT) containing fluorene, side chain conjugated thiophene and 4,7‐dithieny‐2,1,3‐benzothiadiazole was synthesized by palladium‐catalyzed Suzuki coupling method. The polymer is soluble in common organic solvents. The thermal, absorption, and electrochemical properties of the polymer were examined. Photovoltaic properties of POTVTh‐8FO‐DBT were studied by fabricating the polymer solar cells (PSCs) based on POTVTh‐8FO‐DBT as donor and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) as acceptor. With the weight ratio of POTVTh‐8FO‐DBT : PC₆₁BM of 1 : 1 and the active layer thickness of 80 nm, the power conversion efficiency (PCE) of the device reached 0.47% with V_oc = 0.61 V, J_sc = 1.61 mA/cm², and filled factor (FF) = 0.49 under the illumination of AM 1.5, 100 mW/cm². The results indicated that this polymer was promising donor candidates in the application of PSCs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thiophene π‐bridge effect on photovoltaic performances of dithienosilole and bithiazole backboned polymers

In this article, two dithienosilole (DTS) and bithiazole (BTz) backboned donor–acceptor (D‐A) copolymers with (poly{5‐(5‐(4,4‐bis(2‐ethylhexyl)‐4H‐silolo[3,2‐b:4,5‐b']dithiophen‐2‐yl)thiophen‐2‐yl)‐4,4'‐dinonyl‐5'‐(thiophen‐2‐yl)‐2,2'‐bithiazole} (PDTS‐DTBTz)) and without (poly{5‐(4,4‐bis(2‐ethylhexyl)‐4H‐silolo[3,2‐b:4,5‐b']dithiophen‐2‐yl)‐4,4'‐dinonyl‐2,2'‐bithiazole} (PDTS‐BTz)) thiophene π‐bridge were synthesized to study the influence of thiophene π‐bridge on their photovoltaic performances. Both polymers show similar band gap, but polymer with thiophene π‐bridge (PDTS‐DTBTz) has a higher molecular weight, narrower polydispersity index (PDI), more planar geometry, higher crystallinity, higher hole mobility, and better miscibility with fullerene (polymer solar cells (PSCs) acceptor). Although PDTS‐BTz polymer based PSCs devices show higher open circuit voltage (V_oc), PDTS‐DTBTz polymer does show higher power conversion efficiency (PCE) with improved short circuit current density (J_sc) and fill factor (FF). The present results indicate that thiophene π‐bridge does contribute to the PSCs performances of dithienosilole and bithiazole backboned copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42798.     

Molecular design of photovoltaic materials for polymer solar cells: toward suitable electronic energy levels and broad absorption

Bulk heterojunction (BHJ) polymer solar cells (PSCs) sandwich a blend layer of conjugated polymer donor and fullerene derivative acceptor between a transparent ITO positive electrode and a low work function metal negative electrode. In comparison with traditional inorganic semiconductor solar cells, PSCs offer a simpler device structure, easier fabrication, lower cost, and lighter weight, and these structures can be fabricated into flexible devices. But currently the power conversion efficiency (PCE) of the PSCs is not sufficient for future commercialization. The polymer donors and fullerene derivative acceptors are the key photovoltaic materials that will need to be optimized for high-performance PSCs. In this Account, I discuss the basic requirements and scientific issues in the molecular design of high efficiency photovoltaic molecules. I also summarize recent progress in electronic energy level engineering and absorption spectral broadening of the donor and acceptor photovoltaic materials by my research group and others. For high-efficiency conjugated polymer donors, key requirements are a narrower energy bandgap (E(g)) and broad absorption, relatively lower-lying HOMO (the highest occupied molecular orbital) level, and higher hole mobility. There are three strategies to meet these requirements: D-A copolymerization for narrower E(g) and lower-lying HOMO, substitution with electron-withdrawing groups for lower-lying HOMO, and two-dimensional conjugation for broad absorption and higher hole mobility. Moreover, better main chain planarity and less side chain steric hindrance could strengthen π-π stacking and increase hole mobility. Furthermore, the molecular weight of the polymers also influences their photovoltaic performance. To produce high efficiency photovoltaic polymers, researchers should attempt to increase molecular weight while maintaining solubility. High-efficiency D-A copolymers have been obtained by using benzodithiophene (BDT), dithienosilole (DTS), or indacenodithiophene (IDT) donor unit and benzothiadiazole (BT), thienopyrrole-dione (TPD), or thiazolothiazole (TTz) acceptor units. The BDT unit with two thienyl conjugated side chains is a highly promising unit in constructing high-efficiency copolymer donor materials. The electron-withdrawing groups of ester, ketone, fluorine, or sulfonyl can effectively tune the HOMO energy levels downward. To improve the performance of fullerene derivative acceptors, researchers will need to strengthen absorption in the visible spectrum, upshift the LUMO (the lowest unoccupied molecular orbital) energy level, and increase the electron mobility. [6,6]-Phenyl-C(71)-butyric acid methyl ester (PC(70)BM) is superior to [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) because C(70) absorbs visible light more efficiently. Indene-C(60) bisadduct (ICBA) and Indene-C(70) bisadduct (IC(70)BA) show 0.17 and 0.19 eV higher LUMO energy levels, respectively, than PCBM, due to the electron-rich character of indene and the effect of bisadduct. ICBA and IC(70)BA are excellent acceptors for the P3HT-based PSCs.     

Semitransparent inverted polymer solar cells employing a sol-gel-derived TiO2 electron-selective layer on FTO and MoO3/Ag/MoO3 transparent electrode

We report a new semitransparent inverted polymer solar cell (PSC) with a structure of glass/FTO/nc-TiO₂/P3HT:PCBM/MoO₃/Ag/MoO₃. Because high-temperature annealing which decreased the conductivity of indium tin oxide (ITO) must be handled in the process of preparation of nanocrystalline titanium oxide (nc-TiO₂), we replace glass/ITO with a glass/fluorine-doped tin oxide (FTO) substrate to improve the device performance. The experimental results show that the replacing FTO substrate enhances light transmittance between 400 and 600 nm and does not change sheet resistance after annealing treatment. The dependence of device performances on resistivity, light transmittance, and thickness of the MoO₃/Ag/MoO₃ film was investigated. High power conversion efficiency (PCE) was achieved for FTO substrate inverted PSCs, which showed about 75% increase compared to our previously reported ITO substrate device at different thicknesses of the MoO₃/Ag/MoO₃ transparent electrode films illuminated from the FTO side (bottom side) and about 150% increase illuminated from the MoO₃/Ag/MoO₃ side (top side).     

钙钛矿太阳能电池中D-A-D型空穴传输材料的研究进展

钙钛矿太阳能电池(Perovskite Solar Cells, PSCs)作为一种新型太阳能电池,由于其短时间内快速提升的光电转换效率而获得了全世界范围内的广泛关注。空穴传输材料(Hole Transporting Materials, HTM)是钙钛矿太阳能电池的重要组成部分,因此,设计开发经济、高效、稳定的HTM对PSCs的发展具有重要意义。本文综述了2009年以来线型给体-受体-给体(Donor-Acceptor-Donor, D-A-D)结构有机小分子空穴传输材料在PSCs中的应用,详细介绍了各空穴传输材料分子结构对PSCs的光电转换效率和器件稳定性等性能的影响。在此基础上,对未来线型D-A-D型空穴传输材料的发展进行了展望。     

One-Step Mask-Based Diffraction Lithography for the Fabrication of 3D Suspended Structures

We propose a novel one-step exposure method for fabricating three-dimensional (3D) suspended structures, utilizing the diffraction of mask patterns with small line width. An optical model of the exposure process is built, and the 3D light intensity distribution in the photoresist is calculated based on Fresnel-Kirchhoff diffraction formulation. Several 3D suspended photoresist structures have been achieved, such as beams, meshes, word patterns, and multilayer structures. After the pyrolysis of SU-8 structures, suspended and free-standing 3D carbon structures are further obtained, which show great potential in the application of transparent electrode, semitransparent solar cells, and energy storage devices.     

Dioctylfluorene‐thiophene based conjugated copolymers for bulk heterojunction solar cells and enhanced power conversion efficiency via methanol treatment

Sensible design and synthesis of conjugating polymers is important to the development of polymer solar cells (PSCs). In this work, we synthesized and characterized two dioctylfluorene‐thiophene based conjugated copolymers, PFTDPP and PFTpBT, having different acceptor groups on the backbone. The photovoltaic properties of the copolymers blended with 6,6‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) as an electron acceptor were obtained. The PSC based on a conventional device configuration ITO/PEDOT:PSS/ Polymer:PC₆₁BM/LiF/Al showed power conversion efficiencies (PCEs) of 2.42% and 3.02% for PFTDPP and PFTpBT, respectively. Methanol treatment was introduced to further optimize device performance, and the solvent treatment gave a dramatic increase in PCE. The best PCEs could reach 4.25% and 4.20% after methanol treatment under AM 1.5G illumination with an intensity of 100 mW cm^?2 from a solar simulator. © 2015 Society of Chemical Industry     

Sulfides as a new class of stable cost-effective materials compared to organic/inorganic hole transport materials for perovskite solar cells

Perovskite solar cells (PSCs) have received a remarkable attention compared to the other types of solar cells due to their high carrier mobility, low recombination rate, and rapid increase in terms of efficiency in short time. However, two essential parameters being stability and cost are still challenging with these kinds of solar cells. Hole transport materials (HTMs) play an important role in PSCs as they can be effective in the charge transportation, determining the device stability and having a large share of cell costs, and overall resulting in the enhancement of open-circuit voltage (V_oc), short-circuit current (J_sc), and fill factor (FF). In addition to the organic HTMs which are widely used in PSCs, various inorganic HTMs mainly divided into the oxide and sulfide subgroups, have been developed in order to improve both stability and cost of PSCs. Herein, we provide an overview of the diverse types of HTMs, from organic to inorganic, especially oxide and sulfide inorganic HTMs and investigate the physical properties, synthesis, and their applications in various PSCs for both mesoporous and planar structure in the hope of encouraging further research and the optimization of these materials.     

Transparent Conducting Electrodes from Conducting Polymer Nanofibers and Their Application as Thin‐Film Heaters

Transparent conducting electrodes attract attention in relation to solar cells, touch panels, displays, e‐readers, and transparent heaters. In many cases, rarefied metal nets with optical transmittance of ≈90% and with minimal sheet resistance are sought after. Here, a mesh of conducting polymer nanofibers is developed as a transparent conducting electrode. A sheet resistance of 8.4 kΩ sq⁻¹ with 84% optical transmittance is achieved with polyethylene oxide/poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEO/PEDOT:PSS) blended polymer nanofibers. This study also demonstrates that such nanofiber being deposited on a glass substrate can be used as a transparent film heater in relevant applications such as window heating or displays at harsh environments. Such a transparent heater is rated at 0.41 W in.⁻² for 120 V. It is also capable of heating a substrate up to ≈70 °C in 4 min at 60 V from room temperature without any degeneration of nanofiber network, rendering itself as a practically useful transparent heater. The performance of the PEO/PEDOT:PSS nanofiber‐coated transparent glass heater is comparable to that of the relatively expensive indium tin oxide thin‐film heaters.     

Semitransparent poly(styrene‐r‐maleic anhydride)/alumina nanocomposites for optical applications

This article presents the development and characterization of transparent poly(styrene‐r‐maleic anhydride) (SMA)/alumina nanocomposites for potential use in optical applications. Chemically treated spherical alumina nanoparticles were dispersed in an SMA matrix polymer via the solution and melt‐compounding methods to produce 2 wt % nanocomposites. Field emission scanning electron microscopy was used to examine the nanoparticle dispersion. When the solution method was used, nanoparticle reagglomeration occurred, despite the fairly good polymer wetting. However, through the coating of the alumina nanoparticles with a thin layer (ca. 20 nm) of low‐molecular‐weight SMA, reagglomeration was absent in the melt‐compounded samples, and this resulted in excellent nanoparticle dispersion. The resultant nanocomposites were semitransparent to visible light at a 2‐mm thickness with improved UV‐barrier properties. Their impact strengths, tensile strengths, and strains at break were slightly reduced compared with those of their neat resin counterpart, whereas a small enhancement in their moduli was achieved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Functionalized polythiophene for corrosion inhibition and photovoltaic application

Conjugated polymers are encouraging substitute for creating clean and renewable energy for photoinduced charge generation and transport media in polymer solar cells (PSCs). Successful synthesis of a new solution processable n-type polythiophene based π-conjugated polymer (P3HT-CN) is done where polythiophene units are substituted by cyano groups through post functionalization approach of synthesized P3HT which is cheap, stable, easily prepared, and inert against ambient conditions and is expected to be a competitive candidate for the acceptor material in non fullerene acceptors (NFAs) PSCs against fullerene derivative and used as the highly efficient active layer in the bulk heterojunction (BHJ) which increase the donor-acceptor interfacial area through controlling the phase separation indicating device structure ITO/PEDOT:PSS/P3HT:P3HT-CN/Al. Photovoltaic measurement of this PSCs device based on P3HT:P3HT-CN demonstrate the PCE of 0.008% with an increased short circuit current density (J_sc) of 0.11 mA cm⁻². The thermal, optical, and electrochemical properties are examined in detail showing high thermal stability, absorbance in the visible part of the solar spectrum, higher charge carrier mobility, and also mixed type corrosion inhibitive behavior with 90 and 78% inhibitor efficiency for P3HT and P3HT-CN, respectively, built this class of material as smart which can be used for many other applications.     

Carbazoles on same main chain for polymer solar cells

Planar conjugated 2,7‐linked carbazole blocks: Q1(2,7‐dibromo‐9‐octyl‐9H‐carbazole); Q2(7,7′‐dibromo‐9,9′‐dioctyl‐9H,9′H‐2,2′‐bicarbazole); Q3 (7‐bromo‐7′‐(7‐bromo‐9‐octyl‐9H‐carbazol‐2‐yl)‐9,9′‐dioctyl‐9H,9′H‐2,2′‐bicarbazole) were coupled with same acceptor (4,7‐di[2,5‐thiophene]‐5,6‐dioctyloxy‐2,1,3‐Benzothiadiazole) to prepare polymers HXS‐1, 2, 3 (Scheme 1 ). Bulk‐heterojunction polymer solar cells (BHJ PSCs) with these polymers were made. Power conversion efficiency of HXS‐1 was proved to be over 5.4%. It declined dramatically to 0.43% and 0.23% for HXS‐2 and 3 respectively. Their absorption and X‐ray diffraction pattern show the torsion angle in main chain increased when more carbazole units were added. More carbazoles will make polycondensation reaction more difficult to get high molecular weight polymers. The torsion angle was calculated using a semiempirical molecular orbital method. All the results pointed out that the coplanarity in the conjugated backbone was destroyed. Electron delocalization was disturbed because p‐orbital overlapping only occurs effectively in the parallel orbit so charge cannot move a longer distance. This study offers a useful and important insight to designing polymers for high performance PSCs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Carbon/polymer composite counter‐electrode application in dye‐sensitized solar cells

Carbon black was embedded in mixtures of poly(ethylene oxide) and poly(vinylidene fluoride–hexafluoropropylene) to make a carbon/polymer composite slurry, which was deposited onto a transparent conducting glass substrate by a doctor‐blade coating for application in dye‐sensitized solar cells (DSSCs) as a counter‐electrode (CE) material. The experiments indicated that the photovoltaic parameters of the DSSCs were strongly dependent on the carbon concentration in the slurry. The device with a carbon CE whose mass ratio was 1 : 1 (mass ratio = carbon black mass to polymer mass) exhibited an overall energy conversion efficiency of 4.62%; this was comparable to that of a device with platinum as a CE (5.32%) under the same test conditions. The better electrocatalytic activity of CE‐1.0 (where 1.0 indicates the mass ratio of carbon black to polymer) for the reduction of triiodide resulted a higher performance of the DSSC with such a CE. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The optimum titanium precursor of fabricating TiO<Subscript>2</Subscript> compact layer for perovskite solar cells

Perovskite solar cells (PSCs) have attracted tremendous attentions due to its high performance and rapid efficiency promotion. Compact layer plays a crucial role in transferring electrons and blocking charge recombination between the perovskite layer and fluorine-doped tin oxide (FTO) in PSCs. In this study, compact TiO₂ layers were synthesized by spin-coating method with three different titanium precursors, titanium diisopropoxide bis (acetylacetonate) (c-TTDB), titanium isopropoxide (c-TTIP), and tetrabutyl titanate (c-TBOT), respectively. Compared with the PSCs based on the widely used c-TTDB and c-TTIP, the device based on c-TBOT has significantly enhanced performance, including open-circuit voltage, short-circuit current density, fill factor, and hysteresis. The significant enhancement is ascribed to its excellent morphology, high conductivity and optical properties, fast charge transfer, and large recombination resistance. Thus, a power conversion efficiency (PCE) of 17.03% has been achieved for the solar cells based on c-TBOT.     

Using water‐soluble nickel acetate as hole collection layer for stable polymer solar cells

We report polymer solar cells (PSCs) based on poly(3‐hexylthiophene (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) using water‐soluble nickel acetate (Ni(CH₃COO)₂, NiAc) instead of acidic poly(3,4‐ethylenedioxythiophene) : poly(styrenesulfonate) (PEDOT : PSS) as hole collection layer (HCL) between the indium tin oxide (ITO) electrode and photoactive layer. The NiAc layer can effectively decrease R_s and increase R_p and shows effective hole collection property. Under the illumination of AM1.5G, 100 mW/cm², the short‐circuit current density (J_sc) of the NiAc based device (ITO/NiAc/P3HT : PCBM/Ca/Al) reach 11.36 mA/cm², which is increased by 11% in comparison with that (10.19 mA/cm²) of PEDOT : PSS based device (ITO/PEDOT : PSS/P3HT : PCBM/Ca/Al). The power conversion efficiency of the NiAc based devices reach 3.76%, which is comparable to that (3.77%) of the device with PEDOT : PSS HCL under the same experimental conditions. Moreover, NiAc based PSCs show superior long‐term stability than PEDOT : PSS based PSCs. Our work gives a new option for HCL selection in designing more stable PSCs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013