Shorter alkyl chain in thieno[3,4-c]pyrrole-4,6-dione(TPD)-based large bandgap polymer donors – Yield efficient non-fullerene polymer solar cells

Typically,conjugated polymers are composed of conjugated backbones and alkyl side chains.In this contribution,a cost-effective strategy of tailoring the length of alkyl side chain is utilized to design highperforming thieno[3,4-c]pyrrole-4,6-dione(TPD)-based large bandgap polymer donors PBDT-BiTPD(Cχ)(χ=48,52,56),in which x represents the alkyl side chain length in term of the total carbon number.A combination of light absorption,device,and morphology examinations make clear that the shorter alkyl side chains yield(i) higher crystallinity and more predominant face-on crystallite orientation in their neat and BHJ blend films,(ii) higher charge mobilities(6.7×10^(-4) cm~2 V^(-1) s^(-1) for C48 vs.3.2×10^(-4) cm~2 V^(-1) s^(-1) for C56),and negligible charge recombination,consequently,(iii) significantly improved fill-factor(FF) and short current(J_(SC)),while almost the same open circuit voltage(V_(OC)) of ca.0.82 V in their corresponding BHJ devices.In parallel,as alkyl side chain lengths decrease from C56 to C48,power conversion efficiencies(PCEs) increased from 7.8% for C56 to 11.1% for C52,and further to14.1% for C48 in their BHJ solar cells made with a narrow bandgap non-fullerene acceptor Y6.This systematic study declares that shortening the side chain,if providing appropriate solubility in device solution processing solvents,is of essential significance for developing high-performing polymer donors and further improving device photovoltaic performance.

Recent advances and prospects of asymmetric non-fullerene small molecule acceptors for polymer solar cells

Recently,polymer solar cells developed very fast due to the application of non-fullerence acceptors.Substituting asymmetric small molecules for symmetric small molecule acceptors in the photoactive layer is a strategy to improve the performance of polymer solar cells.The asymmetric design of the molecule is very beneficial for exciton dissociation and charge transport and will also fine-tune the molecular energy level to adjust the open-circuit voltage(Voc)further.The influence on the absorption range and absorption intensity will cause the short-circuit current density(Jsc)to change,resulting in higher device performance.The effect on molecular aggregation and molecular stacking of asymmetric structures can directly change the microscopic morphology,phase separation size,and the active layer's crystallinity.Very recently,thanks to the ingenious design of active layer materials and the optimization of devices,asymmetric non-fullerene polymer solar cells(A-NF-PSCs)have achieved remarkable development.In this review,we have summarized the latest developments in asymmetric small molecule acceptors(A-NF-SMAs)with the acceptor-donor-acceptor(A-D-A)and/or acceptor-donor-acceptor-donor-acceptor(A-D-A-D-A)structures,and the advantages of asymmetric small molecules are explored from the aspects of charge transport,molecular energy level and active layer accumulation morphology.

Optimizing polymer aggregation and blend morphology for boosting the photovoltaic performance of polymer solar cells via a random terpolymerization strategy

Compared to regular conjugated polymers,the random conjugated terpolymers are usually not beneficial to achieve highly efficient non-fullerene(NF)-based polymer solar cells(PSCs)due to their disordered chemical structures.In this work,we report two random terpolymer donors(PBNB80 and PBNB50)by tuning the molar ratio of electron-accepting units of 1,3-di(thiophen-2-yl)naphtho[2,3-c]thiophene-4,9-dione(NTD)and 1,3-bis(4-chlorothiophen-2-yl)-4 H,8 H-benzo[1,2-c:4,5-c’]dithiophene-4,8-dione(ClBDD),at the same time,the parent polymers(PBNB100 and PBNB00)are also compared to study.These four polymer donors exhibit similar optical bandgaps and gradually deepen highest occupied molecular orbital levels.Importantly,aggregation and self-organization properties of the random terpolymer donors are optimized,which result in the better morphology and crystal coherence length after blending with NF acceptor of BO-4 Cl.Particularly,a PBNB80:BO-4 Cl blend forms an optimal nanoscale phase-separation morphology,thereby producing an outstanding power conversion efficiency of 16.0%,which is much higher than those(12.8%and 10.7%)of their parent binary polymer donor-based devices.This work demonstrates that rational using terpolymerization strategy to prepare random terpolymer is a very important method to achieve highly efficient NF-PSCs.

CONTROLLING THE 3D NANOSCALE ORGANIZATION OF BULK HETEROJUNCTION POLYMER SOLAR CELLS

In this study,the three dimensional nanoscale organization in the photoactive layers of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM) is revealed by transmission electron tomography.After annealing treatment,either at elevated temperature or during slow solvent evaporation,nanoscale interpenetrating networks are formed with high crystalline order and favorable concentration gradients of both components through the thickness of the photoactive layer.Such a tailored morphology account...

Inverted polymer solar cells with employing of electrochemical-anodizing synthesized TiO_2 nanotubes

An inverted structure of polymer solar cells based on Poly（3-hexylthiophene）（P3HT）：[6-6] Phenyl-（6） butyric acid methyl ester （PCBM） with using thin films of TiO2 nanotubes and nanoparticles as an efficient cathode buffer layer is developed. A total of three cells employing TiO2 thin films with different thickness values are fabricated. Two cells use layers of TiO2 nanotubes prepared via self-organized electrochemical-anodizing leading to thickness values of 203 and 423.7 nm, while the other cell uses only a simple sol-gel synthesized TiO2 thin film of nanoparticles with a thickness of 100 nm as electron transport layer. Experimental results demonstrate that TiO2 nanotubes with these thickness values are inefficient as the power conversion efficiency of the cell using 100-nm TiO2 thin film is 1.55%, which is more than the best power conversion efficiency of other cells. This can be a result of the weakness of the electrochemical anodizing method to grow nanotubes with lower thickness values. In fact as the TiO2 nanotubes grow in length the series resistance （Rs） between the active polymer layer and electron transport layer increases, meanwhile the fill factor of cells falls dramatically which finally downgrades the power conversion efficiency of the cells as the fill factor falls.

Properties of Plasma Enhanced Chemical Vapor Deposition Barrier Coatings and Encapsulated Polymer Solar Cells

In this paper, we report silicon oxide coatings deposited by plasma enhanced chem- ical vapor deposition technology （PECVD） on 125 pm polyethyleneterephthalate （PET） surfaces for the purpose of the shelf lifetime extension of sealed polymer solar cells. After optimiza- tion of the processing parameters, we achieved a water vapor transmission rate （WVTR） of ca. 10-a g/m2/day with the oxygen transmission rate （OTR） less than 0.05 cc/m2/day, and succeeded in extending the shelf lifetime to about 400 h in structure of coatings related to the properties of encapsulated solar cells. And then the chemical encapsulated cell was investigated in detail

Modeling and implementation of tandem polymer solar cells using wide-bandgap front cells

Tandem device architectures offer a route to greatly increase the maximum possible power conversion efficiencies(PCEs)of polymer solar cells,however,the complexity of tandem cell device fabrication(such as selecting bandgaps of the front and back cells,current matching,thickness,and recombination layer optimization)often result in lower PCEs than are observed in single-junction devices.In this study,we analyze the influence of front cell and back cell bandgaps and use transfer matrix modeling to rationally design and optimize effective tandem solar cell structures before actual device fabrication.Our approach allows us to estimate tandem device parameters based on known absorption coefficients and open-circuit voltages of different active layer materials and design devices without wasting valuable time and materials.Using this approach,we have investigated a series of wide bandgap,high voltage photovoltaic polymers as front cells in tandem devices with PTB7-Th as a back cell.In this way,we have been able to demonstrate tandem devices with PCE of up to 12.8%with minimal consumption of valuable photoactive materials in tandem device optimization.This value represents one of the highest PCE values to date for fullerene-based tandem solar cells.

Recent advances in rylene diimide polymer acceptors for all-polymer solar cells

In recent years, a large library of n-type polymers have been developed and widely used as acceptor materi- als to replace fullerene derivatives in polymer solar cells （PSCs）, stimulating the rapid expansion of research on so-called all-polymer solar cells （aPSCs）. In particular, rylene diimide-based n-type polymer acceptors have attracted broad research interest due to their high electron mobility, suitable energy levels, and strong light-harvesting ability in the visible region. Among various polymer acceptors, rylene diimide-based poly- mers presented best performances when served as the acceptor materials in aPSCs. Typically, a record power conversion efficiency （PCE） of 7.7% was very recently achieved from an aPSC with a rylene diimide polymer derivative as the acceptor component. In this review, we highlight recent progress of n-type polymers orig- inated from two significant classes of rylene diimide units, namely naphthalene diimide （NDI） and perylene diimide （PDI）, as well as their derivatives for aPSC applications.

Performance and Stability of Polymer Solar Cells Based on the Blends of Poly(3-Hexylthiophene) and Indene-C_(60) Bis-Adduct

The performance and morphology stability of polymer bulk heterojunetion solar cells based on poly（3-hexylthiophene） （P3HT） as the donor and indene-C6o bisadduct （ICBA） or methanofullerene [6,6]-phenyl C61-butyric acid methyl ester （PCBM） as the aeceptor are compared. Effect of the different donor and aeeeptor weight ratios on photo- voltaic performance of the P3HT：ICBA device is studied. The optimal device achieved power conversion emeiency of 5.51~o with dso of l0.86mA/cm2, Voc of 0.83 V, and fill factor （FF） of 61.1 % under AM 1.5G （lOOmW/cm2） simulated solar illumination. However, the stability measurement shows that cells based on P3HT：ICBA are less stable than those of the device based on P3HT：PCBM. Atomic force microscope results reveal that the morphol- ogy of the P3HT：ICBA film changed considerably during the storage periods due to unstable interpenetrating D-A network. This observation can be explained by the fact that there is lack of intermolecular hydrogen bonds in the P3HT：ICBA system. However, in the P3HT：PCBM system the molecules in the blend film are firmly held together in the solid state by means of intermoleeular hydrogen bonds originating from C-H. ~. Os bonds （where Os comes from the singly-bonded 0 atom of PCBM）, forming a stable three-dimensional network. The measured PL decay lifetimes for P3HT：PCBM and P3HT：ICBA systems are 33.66 ns and 35.34 ns, respectively, indicating that the P3HT：ICBA system has a less efficient exciton separation eftleiency than that of P3HT：PCBM, which may result in the interracial photogenerated charges accumulated on the D： A interface. Such progressive phase segregation between P3HT and ICBA eventually leads to the degradation in performance and deteriorates the stability of the device. We also present an approach to enhance the stability of P3HT：ICBA systems by adding PCBM as the second acceptor. Our results show that by carefully tuning the contents of PCBM as the second acceptor, more stable polymer solar cells can be obtained.

Effects of annealing rate and morphology of sol–gel derived ZnO on the performance of inverted polymer solar cells

The effects of annealing rate and morphology of sol–gel derived zinc oxide （ZnO） thin films on the performance of inverted polymer solar cells （IPSCs） are investigated. ZnO films with different morphologies are prepared at different annealing rates and used as the electron transport layers in IPSCs. The undulating morphologies of ZnO films fabricated at annealing rates of 10 ℃/min and 3 ℃/min each possess a rougher surface than that of the ZnO film fabricated at a fast annealing rate of 50 ℃/min. The ZnO films are characterized by atomic force microscopy （AFM）, optical transmittance measurements, and simulation. The results indicate that the ZnO film formed at 3 ℃/min possesses a good-quality contact area with the active layer. Combined with a moderate light-scattering, the resulting device shows a 16% improvement in power conversion efficiency compared with that of the rapidly annealed ZnO film device.

Effects of acetone-soaking treatment on the performance of polymer solar cells based on P3HT/PCBM bulk heterojunction

The improvement of the acetone-soaking treatment to the performance of polymer solar cells based on the P3HT/PCBM bulk heterojunction is reported. Undergoing acetone-soaking, the PCBM does not distribute uniformly in the vertical direction, a PCBM enrichment layer forms on the top of the active layer, which is beneficial to the collec- tion of the carriers and blocking the inverting diffusion carriers. X-ray photoelectron spectroscopy （XPS） analysis reveals that the PCBM weight ratio on the top of the active layer increases by 20% after the acetone-soaking treatment. Due to the nonuniform distribution of PCBM, the short-circuit current density, the open-circuit voltage, and the fill factor are enhanced significantly. Finally, the power conversion efficiency of the acetone-soaking device increases by 31% compared with the control device.

Influence of small-molecule material on performance of polymer solar cells based on MEH-PPV:PCBM blend

In this work, the influence of a small-molecule material, tris（8-hydroxyquinoline） aluminum （Alq3）, on bulk heterojunction （BHJ） polymer solar cells （PSCs） is investigated in devices based on the blend of poly（2-methoxy-5-（2- ethylhexyloxy）-1,4-phenylenevinylene） （MEH-PPV） and [6,6]-phenyl-C61-butyric acid methyl ester （PCBM）. By doping Alq3 into MEH-PPV：PCBM solution, the number of MEH-PPV excitons can be effectively increased due to the energy transfer from Alq3 to MEH-PPV, which probably induces the increase of photocurrent generated by excitons dissociation. However, the low carrier mobility of Alq3 is detrimental to the efficient charge transport, thereby blocking the charge collection by the respective electrodes. The balance between photon absorption and charge transport in the active layer plays a key role in the performance of PSCs. For the case of 5 wt.% Alq3 doping, the device performance is deteriorated rather than improved as compared with that of the undoped device. On the other hand, we adopt Alq3 as a buffer layer instead of commonly used LiF. All the photovoltaic parameters are improved, yielding an 80% increase in power conversion efficiency （PCE） at the optimum thickness （1 nm） as compared with that of the device without any buffer layer. Even for the 5 wt.% Alq3 doped device, the PCE has a slight enhancement compared with that of the standard device after modification with 1 nm （or 2 nm） thermally evaporated Alq3. The performance deterioration of Alq3-doped devices can be explained by the low solubility of Alq3, which probably deteriorates the bicontinuous D-A network morphology; while the performance improvement of the devices with Alq3 as a buffer layer is attributed to the increased light harvesting, as well as blocking the hole leakage from MEH-PPV to the aluminum （Al） electrode due to the lower highest occupied molecular orbital （HOMO） level of Alq3 compared with that of MEH-PPV.

Polymer Solar Cells Using a PEDOT:PSS/Cu Nanowires/PEDOT:PSS Multilayer as the Anode Interlayer

We compare the electrical, optical, and surface properties of the PEDOT：PSS/Cu nanowires （Cu NWs）/PEDOT： PSS （PCP） multilayer for organic solar cells. It is demonstrated that the electrical and optical properties of the PEDOT could be improved by the insertion of a Cu NW layer due to its very low resistivity and surface morphology. The organic bulk heterojunction solar cell fabricated on the multil^yer exhibits a higher power conversion ef^ciency than devices based on the PEDOT：PSS or PEDOT：PSS/Cu NWs layer. Moreover, the PCP multilayer can improve cell-performances such as a fill factor and the internal resistance in the device due to horizontally well-aligned Cu NWs. The results suggest that the PCP multilayer is a promising low-cost and low-temperature processing buffer layer candidate for low-cost organic photovoltaics.

Non-Halogenated Solvent-Processed High-Efficiency Polymer Solar Cells:the Role of Diphenyl Ether in Morphology,Light-Trapping,Transport Properties

There is an urgent need to use green non-halogenated solvents to prepare polymer solar cells(PSCs) for industrialization.It is time-consuming but necessary to find a suitable non-halogenated solvent/additive combination for a given donor:acceptor materials system.In this research,we report a non-halogenated binary solvent system toluene/diphenyl ether(DPE) for the PBDTT-DTffBT:PC_(71)BM and PM6:Y6 blending systems that exhibit comparable power conversion efficiency(PCE) to that of devices prepared with halogenated solvents.The nano scale morphology indicates that blending film processed solely with toluene has poor phase segregation and a rough surface,which hinders charge separation and interfacial contact.Besides,the total absorption spectra revealed significant light-trapping losses in the toluene-processed solar cells,resulting in low photocurrent generation.DPE incorporation addresses these issues and significantly improves the short-circuit current density and fill factor.Moreover,non-halogen solvent-processed devices exhibit high hole mobility and low transporting impedance properties.The present study enriches the families of eco-friendly,high-efficiency PSCs fabricated using nonhalogenated solvents.

Effect of dual annealing upon photovoltaic properties of polymer solar cells based on poly(3-hexylthiophene)

A dual annealing method comprised of toluene vapor treatment and post thermal annealing was employed to fabricate polymer solar cells （PSCs） based on poly（3-hexylthiophene） （P3HT） and [ 6,6 J-phenyl-C61-butyric acid methyl ester （PCBM） film. It is found that the P3HT crystallinity and chain ordering can be dramatically enhanced by this annealing process as compared with the films treated merely with solvent vapor annealing, which is verified by a higher X-ray diffraction intensity peak and clearly visible fibrillar crystalline domains of P3HT. The result suggests that a favorable e- quilibrium condition was established by dual annealing in the morphology reorganization. Due to the morphological improvement of active layer, the dually annealed PSCs show better overall perform- ances, with a mean power conversion efficiency of 4. 06% and an increase in each electrical parame- ter, than any solely annealed ones.

Effect of Crystallinity of Fullerene Derivatives on Doping Density in the Organic Bulk Heterojunction Layer in Polymer Solar Cells

Polymer solar cells （PSCs） based on poly（3-hexylthiophene） （P3HT） and [6,6]-phenyl-C61-butyric acid methyl ester （PCBM） are fabricated by using 1,8-diiodooctane （DIO） as a solvent additive to control the doping density of the PSCs. It is shown that the processing of DIO does not change the doping density of the P3HT phase, while it causes a dramatic reduction of the doping density of the PCBM phase, which decreases the doping density of the whole blend layer from 3.7 × 10^16 cm-3 to 1.2 ×10^16 cm-3. The reduction of the doping density in the PCBM phase originates from the increasing crystallinity of PCBM with DIO addition, and it leads to a decreasing doping density in the blend film and improves the short circuit current of the PSCs.

Improved performance of polymer solar cells by using inorganic, organic, and doped cathode buffer layers

The interface between the active layer and the electrode is one of the most critical factors that could affect the device performance of polymer solar cells. In this work, based on the typical poly（3-hexylthiophene）：[6,6]-phenyl C61-butyric acid methyl ester （P3HT：PCBM） polymer solar cell, we studied the effect of the cathode buffer layer （CBL） between the top metal electrode and the active layer on the device performance. Several inorganic and organic materials commonly used as the electron injection layer in an organic light-emitting diode （OLED） were employed as the CBL in the P3HT：PCBM polymer solar cells. Our results demonstrate that the inorganic and organic materials like Cs2CO3, bathophenanthroline （Bphen）, and 8-hydroxyquinolatolithium （Liq） can be used as CBL to efficiently improve the device performance of the P3HT：PCBM polymer solar cells. The P3HT：PCBM devices employed various CBLs possess power conversion efficiencies （PCEs） of 3.0%-3.3%, which are ca. 50% improved compared to that of the device without CBL. Furthermore, by using the doped organic materials Bphen：Cs2CO3 and Bphen：Liq as the CBL, the PCE of the P3HT：PCBM device will be further improved to 3.5%, which is ca. 70% higher than that of the device without a CBL and ca. 10% increased compared with that of the devices with a neat inorganic or organic CBL.

Chlorinated polymer solar cells simultaneously enhanced by fullerene and non-fullerene ternary strategies

To achieve efficient polymer solar cells(PSCs)with full utilization of the whole spectrum,the multicomponent devices are of great importance to be deeply explored,especially for their capability of one-step fabrication.However,the research about one same binary system simultaneously derivated various multi-component PSC is still very limited.Herein,we achieved the whole constructions from one binary host to different ternary systems and even the quaternary one.The ternary strategies with fullerene acceptor,PC_(71)BM,and non-fullerene acceptor,BT_(6)IC-BO-4Cl,as the third component,both boosted the device efficiencies of PBT4Cl-Bz:IT-4F binary system from about 9% to comparatively beyond 11%.Despite the comparable improvement of performance,there existed other similarities and differences in two ternary strategies.In detail,the isotropic carrier transport of PC_(71)BM which largely elevated the fill factor(FF)in the corresponding devices,while the strong absorption of BT_(6)IC-BO-4Cl enhanced the short current density(J_(SC))most.More interestingly,quaternary devices based on PBT4Cl-Bz:IT-4F:PC71 BM:BT_(6)IC-BO-4Cl could combine both advantages of fullerene and non-fullerene ternary strategies,further pumped the J_(SC) from 16.44 to the highest level of 19.66 mA cm^(-2) among all devices,eventually resulted in an optimized efficiency of 11.69%.It reveals that both fullerene and non-fullerene ternary strategies have their unique feature to elevate the device performance either by efficient isotropic carrier transport or better coverage of whole sunlight spectrum and easy tunable energy levels from organic materials.The key is how to integrate the two pathways in one system and provide a more competitive solution facing high-quality PSCs.

Improving the performance of polymer solar cells by adjusting the crystallinity and nanoscale phase separation

In this paper, we report a high-perfornmnce P3HT/PCBM bulk-heterojunction solar cell with a power conversion efficiency of 4.85% fabricated by adjusting the polymer crystallinity and nanoscale phase separation using an ultrasonic irradiation mixing approach for the polymer. The grazing incidence X-ray diffraction, UV/Vis spectroscopic, and atomic force microscopic measurement results for the P3HT/PCBM blend films reveal that the P3HT/PCBM film fabricated by ultrasonic irradiation mixing of the P3HT and PCBM solutions for 10 min has a higher degree of crystallinity, a higher absorption efficiency, and better phase separation, which together account for the higher charge transport properties and photovoltaic cell performance.

Design and Synthesis of Acceptor-Donor-Acceptor Type Non-Fullerene Acceptors Using Oxindole-Based Bridge for Polymer Solar Cells Applications

Two acceptor-donor-acceptor(A-D-A)type non-fullerene acceptors(namely WH1 and WH7)containing the oxindole-based bridge are designed and synthesized for polymer solar cells(PSCs)applications.The bridge unit is introduced through a precursor(6-bromo-1-octylindoline-2,3-dione)that contains both bromine and carbonyl and provides the feasibility of the Pd-catalyzed cross-coupling reaction and the Knoevenagel condensation,respectively.This facile synthetic approach exhibits the potential to gain high performance non-fullerene acceptors through extendingπ-conjugated backbone with strong light-absorbing building blocks.The synthesis and properties of WH1 and WH7 are demonstrated with different endcap units,then PSCs are fabricated using PBDB-T:WH1 and PBDB-T:WH7 as the active layers,and attain an average power conversion efficiency(PCE)of 2.58%and 6.24%,respectively.Further device physics studies afford the deep insight of structure variation influence on the device performance.This work provides a facile non-fullerene acceptor design strategy and shows how structure variations impact the PSC performance.