Enhancement of vertical phase separation in sequentially deposited organic photovoltaics through the independent processing of additives

Herein,the impact of the independent control of processing additives on vertical phase separation in sequentially deposited (SD) organic photovoltaics (OPVs) and its subsequent effects on charge carrier kinetics at the electron donor-acceptor interface are investigated.The film morphology exhibits notable variations,significantly depending on the layer to which 1,8-diiodooctane (DIO) was applied.Grazing incidence wide-angle X-ray scattering analysis reveals distinctly separated donor/acceptor phases and vertical crystallinity details in SD films.Time-of-flight secondary ion mass spectrometry analysis is employed to obtain component distributions in diverse vertical phase structures of SD films depending on additive control.In addition,nanosecond transient absorption spectroscopy shows that DIO control significantly affects the dynamics of separated charges in SD films.In SD OPVs,DIO appears to act through distinct mechanisms with minimal restriction,depending on the applied layer.This study emphasizes the significance of morphological optimization in improving device performance and underscores the importance of independent additive control in the advancement of OPV technology.

Non-Fullerene-Based Inverted Organic Photovoltaic Device with Long-Term Stability

In this work,we developed the PM6:Y6-based inverted structure organic photovoltaic(i-OPV)with improved power conversion efficiency(PCE)and long-term stability by resolving the origins of the performance deterioration.The deep defects between the metal oxide-based electron transport layer and bulk-heterojunction photoactive layer interface were responsible for suboptimal PCE and facilitated degradation of devices.While the density of deep traps is increased during the storage of i-OPV,the penetrative oxygen-containing defects additionally generated shallow traps below the band-edge of Y6,causing an additional loss in the open-circuit voltage.The suppression of interfacial defects by chemical modification effectively improved the PCE and long-term stability of i-OPV.The modified i-OPV(mi-OPV)achieved a PCE of 17.42%,which is the highest value among the reported PM6:Y6-based i-OPV devices.Moreover,long-term stability was significantly improved:~90%and~80%retention of its initial PCE after 1200 h of air storage and illumination,respectively.

14.46% Efficiency small molecule organic photovoltaics enabled by the well trade-off between phase separation and photon harvesting

Small molecule organic photovoltaics(SMPVs) were prepared by utilizing liquid crystalline donor material BTR-Cl and two similar optical bandgap non-fullerene acceptor materials BTP-BO-4 F and Y6.The BTPBO-4 F and Y6 have the similar optical bandgap and different absorption coefficients.The corresponding binary SMPVs exhibit different short circuit current density(/sc)(20.38 vs.23.24 mA cm^(-2)),and fill factor(FF)(70.77% vs.67.21%).A 14.46% power conversion efficiency(PCE) is acquired in ternary SMPVs with 30 wt% Y6,companied with a JSC of 24.17 mA cm^(-2) a FF of 68.78% and an open circuit voltage(Voc) of 0.87 V.The improvement on PCE of ternary SMPVs should originate from the well trade-off between phase separation and photon harvesting of ternary active layers by incorporating 30 wt% Y6 in acceptors.This work may deliver insight onto the improved performance of SMPVs by superposing the superiorities of binary SMPVs with similar optical bandgap acceptors into one ternary cell.

Non-fused medium bandgap electron acceptors for efficient organic photovoltaics

The cost-effective organic semiconductors are strongly needed in organic photovoltaics(OPVs). Herein,two medium bandgap(MBG) electron acceptors, TPT4F and TPT4Cl are developed via the new design of multi-noncovalent interaction assisted unfused core, flanked with two electron withdrawing end groups. These fullly non-fused MBG acceptors adapt the planar and rigid conformation in solid, therefore exhibiting the ordered face-on stacking and strong photoluminescence in films. As results, TPT4Cl^(-)based OPVs, upon blending with the PBDB-TF polymer donor, have achieved a power conversion efficiency of 10.16% with a low non-radiative loss of 0.27 e V, representing one of the best fullly non-fused medium bandgap acceptors with desirable cost-efficiency balance.

Recent Advances to Understand Morphology Stability of Organic Photovoltaics

Organic photovoltaic devices are on the verge of commercialization with power conversion efficiencies exceeding 10 % in laboratory cells and above 8.5 % in modules. However, one of the main limitations hindering their mass scale production is the debatable inferior stability of organic photovoltaic devices in comparison to other technologies.Adequate donor/acceptor morphology of the active layer is required to provide carrier separation and transport to the electrodes. Unfortunately, the beneficial morphology for device performance is usually a kinetically frozen state which has not reached thermodynamic equilibrium. During the last 5 years, special efforts have been dedicated to isolate the effects related to morphology changes taking place within the active layer and compare to those affecting the interfaces with the external electrodes. The current review discusses some of the factors affecting the donor/acceptor morphology evolution as one of the major intrinsic degradation pathways. Special attention is paid to factors in the nano- and microscale domain.For example, phase segregation of the polymer and fullerene domains due to Ostwald ripening is a major factor in the microscale domain and is affected by the presence of additives, glass transition temperature of the polymers or use of crosslinkers in the active layer. Alternatively, the role of vertical segregation profile toward the external electrodes is key for device operation, being a clear case of nanoscale morphology evolution. For example, donor and acceptor molecules actually present at the external interfaces will determine the leakage current of the device, energy-level alignment, and interfacial recombination processes. Different techniques have been developed over the last few years to understand its relationship with the device efficiency. Of special interest are those techniques which enable in situ analysis being nondestructive as they can be used to study accelerated degradation experiments and some will be discussed here.

Ternary blend strategy in benzotriazole-based organic photovoltaics for indoor application

Organic photovoltaics(OPVs)suitable for application in indoor lighting environments can power a wide range of internet of things(Io T)related electronic devices.The ternary structure has huge advantages in improving the photovoltaic performance of OPVs,including broadening the light absorption,improving the charge transport,manipulating the energy loss(E_(loss))and so on.Herein,we use wide-bandgap photo-active materials,including the benzotriazole-based polymer donor(J52-F),chlorinated polymer donor(PM7)and A_(2)-A_1-D-A_1-A_(2)-structured acceptor(BTA3),to construct ternary OPVs for indoor light applications.Benefitting from the introduction of PM7 as the third component in J52-F:BTA3-based blend,a gratifying PCE of 20.04%with a high V_(OC)of 1.00 V can be obtained under the test conditions with an illumination of 300 lx from an LED lighting source with a color temperature of 3000 K.The excellent device performance is inseparable from the matched spectrum,enhanced light absorption and the reduced E_(loss),while the improved charge transport capability and suppression of carrier recombination also play an indelible role.Our work shows a potential material system to meet the requirement of devices applied under indoor light.Moreover,these findings demonstrate that designing multi-component OPVs is indeed a feasible way to further improve the performances of the photovoltaic energy conversion system for indoor applications.

Organic Photovoltaic Properties Based on Oligothiophenes

The ITO/5T/PCH/Al1 device has a short circuit current of 3.4 mA/cm^2, an open circuit voltage of 2.1 V, fill fact of 27.5 % and photoelectric conversion efficiency of 2.5 %.

Organic photovoltaic cells with copper(Ⅱ) tetra-methyl substituted phthalocyanine

Efficient heterojunction organic photovoltaic （OPV） cells are fabricated based on copper tetra-methyl phthalocyanine （CuMePc） as donor and fullerene （C60） as acceptor. The power conversion efficiency of CuMePc/C60 OPV cell （2.52%） is increased by 88% compared with that of the non-peripheral substituted copper phthalocyanine （CuPc）/C60 OPV cell （1.34%）. The introduction of methyl substituent leads to stronger π–π interaction of CuMePc （～ 3.5 ？） than that of CuPc （～ 3.8 ？）. The efficiency improvement is attributed to the enhanced carrier mobility of CuMePc thin film （1.1×10-3 cm2/V·s） and better film morphology by introducing methyl groups into the periphery of CuPc molecule.

Optical management in organic photovoltaic devices

Due to their potentials in light‐weight,flexible,and semitransparent devices,organic photovoltaics are of great significance in the field of renewable energy.However,the narrow intrinsic absorption spectrum of organic materials hinders the full utilization of solar energy.To fabricate a highly efficient opaque solar cell,it is greatly necessary to modify the optical properties of the device to improve light absorption.In addition,the growing interest in building‐integrated photovoltaics drives the development of semitransparent devices.The preparation of semitransparent solar cells with excellent performance imposes high requirements on the high efficiency and appropriate visible light transmittance of effective optical management.In this review,the recent research progress of optical management in organic photovoltaics is reviewed,including the design of light‐absorbing materials,the modification of different layers,adding a lighttrapping structure,and changing the light absorption capabilities of specific materials,so as to provide strategies of how to improve the performance of organic photovoltaic devices and present the prospect of the area.

Detailed analysis of ultrathin fluorescent red dye interlayer for organic photovoltaic cells

The influence of an ultrathin 4-（dicyanomethylene）-2-t-butyl-6-（1,1,7,7-tetramethyljulolidyl-9-enyl）-4H-pyran （DCJTB） fluorescent dye layer at donor/acceptor heterojunction on the performance of small-molecule organic photovoltaic （OPV） cell is studied. The structure of OPV cell is of indium-tin oxide （ITO）/copper phthalocyanine （CuPc）/DCJTB/fullerene （C60）/bathophenantbroline （Bphen）/Ag. The results show that open circuit voltage （Voc） increases to 0.57 V as the film thickness of DCJTB layer increases from 0.2 to 2.0 nm. By using an equivalent circuit model, the enhancement of VOC is found to be attributed to the reduced reverse saturation current density （Js） which is due to the lower highest occupied molecular orbital （HOMO） level in DCJTB than that in CuPc. Also, the short circuit current density （JSC） is affected when the DCJTB layer becomes thicker, resulting from the high series resistance RsA due to the low charge carrier mobility of fluorescent red dye.

Optimizing side chains on different nitrogen aromatic rings achieving 17% efficiency for organic photovoltaics

Balancing charge generation and low energy loss(E_(loss)), especially in the wide spectral absorption region is critical to obtain high-performance organic photovoltaics(OPVs). Therefore, Y11-M and Y11-EB are designed and synthesized through modifying alkyl chains on different nitrogen aromatic rings of the reported non-fullerene acceptor Y11. Although all the molecules have almost similar low band-gap(around 1.30 e V), Y11-M and Y11-EB exhibit wider absorption in 410–870 nm region. Eventually, the conventional devices based on Y11-M and Y11-EB possess more efficient charge generation with low Eloss(around 0.44 e V). In addition, outstanding efficiencies of 16.64% and 17.15% with the fill factor of 76.15% and 74.73% are obtained in PM6:Y11-M and PM6:Y11-EB-based devices, both higher than Y11:PM6. The results highlight the importance of rational alkyl chains optimization, and a good structureproperty relationship is established as well.

Photocurrent analysis of organic photovoltaic cells based on CuPc/C_(60) with Alq_3 as a buffer layer

The performance of an organic photovoltaic （OPV） cell based on copper phthatocyanine CuPc/C60 with a tris- （8-hydroxyquinolinato） aluminum （Alq3） buffer layer has been investigated. It was found that the power conversion efficiency of the device was 1.51% under illumination with an intensity of 100 mW/cm^2, which was limited by a squareroot dependence of the photocurrent on voltage. The photocurrent optical power density characteristics showed that the OPV cell had a significant space-charge limited photocurrent with a varied saturation voltage and a three quarters power dependence on optical power density. Also, the absorption spectrum was measured by a spectrophotometer, and the results showed that the additional Alq3 layer has a minor effect on photocurrent generation.

Enhanced performance in organic photovoltaic devices with a KMnO_4 solution treated indium tin oxide anode modification

The properties of poly（3-hexylthiophene）：（6,6）-phenyl C61 butyric acid methyl ester （P3HT：PCBM） organic pho- tovoltaic devices （OPVs） with an indium tin oxide （ITO） anode treated by a KMnO4 solution are investigated. The optimized KMnO4 solution has a concentration of 50 rag/L, and ITO is treated for 15 min. The modification of ITO anode results in an enhancement of the power conversion efficiency （PCE） of the device, which is responsible for the increase of the photocurrent. The performance enhancement is attributed to the work function modification of the ITO substrate through the strong oxygenation of KMnO4, and then the charge collection efficiency is improved.

Organic photovoltaic devices with high open-circuit voltage based on oligothiophene derivatives

For the purpose of developing organic photovoltaic devices with good performance characteristics, we have fabricated two devices using 4T-CHO, 5T-CHO and PTCDA. The ITO/4T-CHO/PTCDA/Al device has a Voc of 2.45 V and photoelectric conversion efficiency of 2.76%. The ITO/ST-CHO/PTCDA/Al device has a Voc of 2.1 3V and photoelectric conversion efficiency of 2.90%. The two devices have higher Voc （2.45 and 2.13 V）. It is possible that intennolecular hydrogen bonding between -CHO group of nT-CHO and carboxylic dianhydride of PTCDA contribute to enhance the efficiency by promoting interracial electron transfer and eliminating the subconducting band trap sites.

Flexible organic photovoltaic devices based on oligothiophene derivatives

For the purpose of developing flexible organic photovoltaic devices, we have fabricated two flexible devices using 5-formyl- 2,2′：5′,2″：5″,2′″-quaterthiophene （4T-CHO）, 5-formyl-2,2′：5′, 2″：5″,2′″：5′″,2″″-quinquethiophene （5T-CHO） and 3,4,9,10-perylenetertracarboxylic dianhydride （PTCDA）. The PET-ITO/4T-CHO/PTCDA/A1 device has an open circuit voltage （Voc） of 1.56 V, photoelectric conversion efficiency of 0.77%. The PET-ITO/5T-CHO/PTCDA/A1 device has a Voc of 1.70 V, photoelectric conversion efficiency of 0.84%. The two flexible devices have high Voc （1.56 and 1.70 V）. It is possible that intermolecular hydrogen bonding between -CHO group of nT-CHO and carboxylic dianhydride of PTCDA contributes to enhancing the efficiency by promoting interfacial electron transfer and eliminating the subconducting band trap sites.

The Effect of Energy Levels of the Electron Acceptor Materials on Organic Photovoltaic Cells

Organic photovoltaic cells have been fabricated using copper phthalocyanine CuPc as electron donor and C60 or PCBM as electron acceptor. We have investigated the I-V measurements of two different structures: ITO/PEDOT: PSS/(CuPc:C60 or CuPc:PCBM)/BCP/Al. We have observed that the substitution of PCBM by C60 scales up the photocurrent and the efficiency of the devices. As for the open-circuit voltage and the fill factor, we have seen that Voc and FF depend on the energy difference between the highest occupied molecular orbital (HOMO) of CuPc and the lowest unoccupied molecular orbital (LUMO)of C60 or PCBM.

Manipulating Film Formation Kinetics Enables Organic Photovoltaic Cells with 19.5%Efficiency

Organic photovoltaic(OPV)cells have demonstrated remarkable performance in small,spin-coated areas.Nevertheless significant challenges persist in the form of large efficiency losses due to the fact that the ideal morphology cannot be preserved in the transition of small-area cells to large-scale panels.Herein,the ternary strategy of incorporating the third component FTCC-Br into the active layer of PB2:BTP-eC9 is employed to improve absorption response,optimize morphology,and reduce charge recombination,leading to a power conversion efficiency(PCE)of 19.5%(certified as 19.1%by the National Institute of Metrology,China).Moreover,the addition of FTCC-Br can control the aggregation kinetics of the active layer during the film formation process,transferring the optimal morphology to the blade-coated large-area films.Based on the highly efficient ternary bulk heterojunction,the 50 cm^(2) OPVmodules exhibited a PCE of 15.2%with respect to the active area.Importantly,the ternary OPV cells retain 80%of its initial PCE after 4000 h under continuous illumination.Our work demonstrates that the addition of a third component has the potential to improve the efficiency and stability of large-area organic solar cells.

Near-infrared non-fused electron acceptors for efficient organic photovoltaics

Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have been developed with A-π_A-π_D-D-π_D-π_A-A non-fused structures. It is revealed that the introduction of electron deficient π-bridge(π_A) and multiple intramolecular noncovalent interactions effectively retained the structural planarity and intramolecular charge transfer of NFRAs, extending strong NIR photon absorption up to 950 nm. Further, the chlorinated acceptor, with the enlarged π-surface compared to the fluorinated counterpart, promoted not only molecular stacking in solid, but also the desirable photochemical stability in ambient, which are helpful to thereby improve the exciton and charge dynamics for the corresponding OPVs. Overall, this work provides valuable insights into the design of NIR organic semiconductors.

Progress of additives for morphology control in organic photovoltaics

The microstructure of the active layer in organic photovoltaics(OPVs),such as the size of phase separation,purity of the phases,and molecular packing within each phase,plays a crucial role in influencing the behavior of excitons and charge carriers within the active layer.It is also a key determinant of the photovoltaic performance of the device.During the optimization of OPV devices,the use of additives has been demonstrated to be an effective strategy in microstructure control,leading to enhanced performance.Therefore,the quest for stable and efficient novel additives,along with an exploration and summarization of the mechanisms underlying additive-induced microstructure control,is essential for a better understanding of the developmental trends of high-performance additives.In this review,we categorize additives based on their chemical structures and discuss their effects on the microstructure of the active layer from both thermodynamic and kinetic perspectives.Furthermore,we elaborate on the working mechanisms and their impact on the photovoltaic performance of the devices.This review provides an overview of recent advances in additives for OPVs,offering potential guidance for the future development of additives and further optimization of the active layer in photovoltaic devices.

Highly efficient solution-processed organic photovoltaics enabled by improving packing behavior of organic semiconductors

Solution processability is a unique property of organic semiconductors. The compact and regular π-π stacking between molecules is paramount in the performance of organic optoelectronic devices. However, it is still a challenge to improve their stacking quality without sacrificing the solution-processability from the aspect of materials design. Here, delicately engineered additives are presented to promote the formation of ordered aggregation of conjugated molecules by regulating their nucleation and growth dynamics. Intriguingly, the long-chain BTP-eC9-4F molecules can realize ordered aggregation comparable to short-chain ones without sacrificing processability. The domain size of BTP-eC9-4F aggregation is enlarged from 24.2 to 32.2 nm in blend films.Thereby exciton diffusion and charge transport become faster, contributing to the suppression of recombination losses. As a result, a power conversion efficiency of 19.2% is achieved in D18:BTP-eC9-4F based organic photovoltaics. Our findings demonstrate a facile strategy to improve the packing quality of solution-processed organic semiconductors for high-efficiency photovoltaics and beyond photovoltaics.