Unusually High Optical Transmission in Ca:Ag Blend Films: High‐Performance Top Electrodes for Efficient Organic Solar Cells

Highly transparent electrodes are demonstrated based on thermally evaporated calcium:silver blend thin–films, which show unusually high transmission well above the expectations from bulk material properties and thin film optics. These electrodes exhibit a low sheet resistance of 27.3 Ω/, combined with an extraordinarily high mean transmittance of 93.0% in the visible spectral range (σ_dc/σ_opt = 186.7), superior to the commonly used inorganic electrodes made from indium tin oxide (ITO). Additionally, the metal blend electrode is flexible, showing a constant sheet resistance down to a bending radius of 10 mm and can be employed on top of organic devices without causing damage to the organic material. The spontaneously formed unique microstructure of a polycrystalline Ag network with randomly distributed nanoapertures, surrounded by a calcium shell, enables broadband transmittance enhancement due to amplified plasmonic coupling. Consequently, top‐illuminated organic solar cells using such metal blend electrodes achieve a power conversion efficiency of 7.2% (which defines a new record for top illuminated organic solar cells) and even exceed the efficiency of similar bottom‐illuminated reference solar cells (6.9%) employing common ITO electrodes.     

Real‐Time Investigation of Crystallization and Phase‐Segregation Dynamics in P3HT:PCBM Solar Cells During Thermal Annealing

Crystallization and phase segregation during thermal annealing lead to the increase of power‐conversion efficiency in poly(3‐hexylthiophene) (P3HT):[6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) bulk‐heterojunction solar cells. An understanding of the length and time scale on which crystallization and phase segregation occur is important to improve control of the nanomorphology. Crystallization is monitored by means of grazing incidence X‐ray diffraction in real time during thermal annealing. Furthermore, the change in film density is monitored by means of ellipsometry and the evolution of carrier mobilities by means of field effect transistors, both during annealing. From the combination of such measurements with those of device performance as a function of annealing time, it is concluded that the evolution of microstructure involves two important time windows: i) A first one of about 5 minutes duration wherein crystallization of the polymer correlates with a major increase of photocurrent; ii) a second window of about 30 minutes during which the aggregation of PCBM continues, accompanied by an increase in the fill factor.     

Open‐Circuit Voltage and Effective Gap of Organic Solar Cells

The open‐circuit voltage (V_OC) of an organic solar cell is limited by the donor‐acceptor material system. The effective gap E_g^eff between the electron affinity of the acceptor and the ionization potential of the donor is usually regarded as the upper limit for V_OC, which is only reached for T → 0 K. This relation is confirmed for a number of small‐molecule bulk heterojunction p‐i‐n type solar cells by varying the temperature and illumination intensity. With high precision, the low temperature limit of V_OC is identical to E_g^eff. Furthermore, the influence of the hole transport material in a p‐doped hole transport layer and the donor‐acceptor mixing ratio on this limit V₀ is found to be negligible. Varying the active material system, the quantitative relation between V₀ and E_g^eff is found to be identity. A comparison of V₀ in a series of nine different donor‐acceptor material combinations opens a pathway to quantitatively determine the ionization potential of a donor material or the electron affinity of an acceptor material.     

The Origin of the High Voltage in DPM12/P3HT Organic Solar Cells

Organic solar cells made using a blend of DPM12 and P3HT are studied. The results show that higher V_oc can be obtained when using DPM12 in comparison to the usual mono‐substituted PCBM electron acceptor. Moreover, better device performances are also registered when the cells are irradiated with sun‐simulated light of 10–50 mW cm^?2 intensity. Electrochemical and time‐resolved spectroscopic measurements are compared for both devices and a 100‐mV shift in the density of states (DOS) is observed for DPM12/P3HT devices with respect to PCBM/P3HT solar cells and slow polaron‐recombination dynamics are found for the DPM12/P3HT devices. These observations can be directly correlated with the observed increase in V_oc, which is in contrast with previous results that correlated the higher V_oc with different ideality factors obtained using dark‐diode measurements. The origin for the shift in the DOS can be correlated to the crystallinity of the blend that is influenced by the properties of the included fullerene.     

High‐Resolution Near‐Field Optical Investigation of Crystalline Domains in Oligomeric PQT‐12 Thin Films

The structure and morphology on different length scales dictate both the electrical and optical properties of organic semiconductor thin films. Using a combination of spectroscopic methods, including scanning near‐field optical microscopy, we study the domain structure and packing quality of highly crystalline thin films of oligomeric PQT‐12 with 100 nanometer spatial resolution. The pronounced optical anisotropy of these layers measured by polarized light microscopy facilitates the identification of regions with uniform molecular orientation. We find that a hierarchical order on three different length scales exists in these layers, made up of distinct well‐ordered dichroic areas at the ten‐micrometer‐scale, which are sub‐divided into domains with different molecular in‐plane orientation. These serve as a template for the formation of smaller needle‐like crystallites at the layer surface. A high degree of crystalline order is believed to be the cause of the rather high field‐effect mobility of these layers of 10^?3 cm² V^?1 s^?1, whereas it is limited by the presence of domain boundaries at macroscopic distances.     

Band‐Tail Recombination in Hybrid Lead Iodide Perovskite

Traps limit the photovoltaic efficiency and affect the charge transport of optoelectronic devices based on hybrid lead halide perovskites. Understanding the nature and energy scale of these trap states is therefore crucial for the development and optimization of solar cell and laser technology based on these materials. Here, the low‐temperature photoluminescence of formamidinium lead triiodide (HC(NH₂)₂PbI₃) is investigated. A power‐law time dependence in the emission intensity and an additional low‐energy emission peak that exhibits an anomalous relative Stokes shift are observed. Using a rate‐equation model and a Monte Carlo simulation, it is revealed that both phenomena arise from an exponential trap‐density tail with characteristic energy scale of ≈3 meV. Charge‐carrier recombination from sites deep within the tail is found to cause emission with energy downshifted by up to several tens of meV. Hence, such phenomena may in part be responsible for open‐circuit voltage losses commonly observed in these materials. In this high‐quality hybrid perovskite, trap states thus predominantly comprise a continuum of energetic levels (associated with disorder) rather than discrete trap energy levels (associated, e.g., with elemental vacancies). Hybrid perovskites may therefore be viewed as classic semiconductors whose band‐structure picture is moderated by a modest degree of energetic disorder.     

P3HT/PCBM Bulk Heterojunction Solar Cells: Impact of Blend Composition and 3D Morphology on Device Performance

The performance of polymer solar cells (PSC) strongly depends on the 3D morphological organization of the donor and acceptor compounds within the bulk heterojunction active layer. The technique of electron tomography is a powerful tool for studying 3D morphology of the layers composed of poly(3‐hexylthiophene) (P3HT) and a fullerene derivative ([6,6]‐phenyl‐C61‐butyric acid methyl ester; PCBM), especially to quantify the amount and distribution of fibrillar P3HT nanocrystals throughout the volume of the active layer. In this study, electron tomography is used to characterize P3HT/PCBM layers with different blend compositions, both before and after thermal annealing. The power conversion efficiency of the corresponding PSCs is strongly dependent on the overall crystallinity of P3HT and the way P3HT crystals are distributed throughout the thickness of the active layer.     

胆甾液晶应用于P3HT∶PCBM聚合物光伏器件研究

本研究利用液晶材料的自组装特性,将胆甾醇油酸酯3β-Hydroxy-5-cholestene 3-oleate掺杂有机聚合物太阳能电池活性层P3HT:PC61BM内,制备出不同掺杂比例的光伏器件。实验结果表明,液晶掺杂质量比为0.3%时,器件的光电转换效率最高。说明液晶分子可诱导活性层材料分子在结晶过程中有序排列,减少层内分子团簇,减少活性层薄膜缺陷,形成有效的载流子传输通道。适当的掺杂比例,增大了器件并联电阻和填充因子,器件性能得到改善。     

Effects of Thermal Annealing Upon the Morphology of Polymer–Fullerene Blends

Grazing incidence X‐ray scattering (GIXS) is used to characterize the morphology of poly(3‐hexylthiophene) (P3HT)–phenyl‐C61‐butyric acid methyl ester (PCBM) thin film bulk heterojunction (BHJ) blends as a function of thermal annealing temperature, from room temperature to 220 °C. A custom‐built heating chamber for in situ GIXS studies allows for the morphological characterization of thin films at elevated temperatures. Films annealed with a thermal gradient allow for the rapid investigation of the morphology over a range of temperatures that corroborate the results of the in situ experiments. Using these techniques the following are observed: the melting points of each component; an increase in the P3HT coherence length with annealing below the P3HT melting temperature; the formation of well‐oriented P3HT crystallites with the (100) plane parallel to the substrate, when cooled from the melt; and the cold crystallization of PCBM associated with the PCBM glass transition temperature. The incorporation of these materials into BHJ blends affects the nature of these transitions as a function of blend ratio. These results provide a deeper understanding of the physics of how thermal annealing affects the morphology of polymer–fullerene BHJ blends and provides tools to manipulate the blend morphology in order to develop high‐performance organic solar cell devices.     

Variations of Infiltration and Electronic Contact in Mesoscopic Perovskite Solar Cells Revealed by High‐Resolution Multi‐Mapping Techniques

A combination of high‐resolution mapping techniques is developed to probe the homogeneity and defects of mesoscopic perovskite solar cells. Three types of cells using a one‐step infiltration process with methylammonium lead iodide (MAPbI₃) or 5‐ammoniumvaleric acid‐MAPbI₃ solutions, or two‐step process with MAPbI₃ solution are investigated. The correlation between photoluminescence, photocurrent, electroluminescence, and Raman maps gives a detailed understanding of the different infiltration mechanisms, electronic contact at interfaces, and effect on local photocurrent for the cells. The one‐step MAPbI₃ cell has very limited infiltration of the perovskite solution which results in poor device performance. High loading of the mesopores of the TiO₂ and ZrO₂ scaffold is observed when using 5‐ammoniumvaleric acid, but some micrometer‐sized non‐infiltrated areas remain due to dense carbon flakes hindering perovskite infiltration. The two‐step cell has a complex morphology with features having either beneficial or detrimental effects on the local photocurrent. The results not only provide key insights to achieving better infiltration and homogeneity of the perovskite film in mesoporous devices but can also aid further work on planar devices to develop efficient extraction layers. Moreover, this multi‐mapping approach allows the correlation of the local photophysical properties of full perovskite devices, which would be challenging to obtain by other techniques.     

Controlling Photoactivity in Ultrathin Hematite Films for Solar Water‐Splitting

A promising route to increase the performance of hematite (α‐Fe₂O₃) photoelectrodes for solar hydrogen production through water‐splitting is to use an extremely thin layer of this visible light absorber on a nanostructured scaffold. However, the typically poor performance of ultrathin (ca. 20 nm) films of hematite has been the limiting factor in implementing this approach. Here, the surprising effect of a substrate pretreatment using tetraethoxysilicate (TEOS) is reported; it results in drastic improvements in the photoperformance of 12.5 nm thick films of hematite. These films exhibit a water oxidation photocurrent onset potential at 1.1 V versus the reversible hydrogen electrode (vs. RHE) and a plateau current of 0.63 mA cm^?2 at 1.5 V vs. RHE under standard illumination conditions, representing the highest reported performance for ultrathin hematite films. In contrast, almost no photoactivity is observed for the photoanode with the same amount of hematite on an untreated substrate. A detailed study of the effects of the TEOS treatment shows that a monolayer of SiO_x is formed, which acts to change the hematite nucleation and growth mechanism, increases its crystallinity, reduces the concentration of carrier trapping states of the ultrathin films, and suggests its further application to quantum‐dot and extremely‐thin‐absorber (ETA)‐type solar cells.     

Copolymers of Cyclopentadithiophene and Electron‐Deficient Aromatic Units Designed for Photovoltaic Applications

Alternating copolymers based on cyclopentadithiophene (CPDT) and five different electron‐deficient aromatic units with reduced optical band gaps are synthesized via Suzuki coupling. All polymers show a significant photovoltaic response when mixed with a fullerene acceptor. The frontier orbital levels of the new polymers are designed to minimize energy losses by increasing the open‐circuit voltage with respect to the optical band gap, while maintaining a high coverage of the absorption with the solar spectrum. The best cells are obtained for a copolymer of CPDT and benzooxadiazole (BO) with a band gap of 1.47 eV. This cell gives a short‐circuit current of 5.4 mA cm^?2, an open‐circuit voltage of 0.78 V, and a fill factor of 0.6, resulting in a power conversion efficiency of about 2.5%.     

Effect of Trace Solvent on the Morphology of P3HT:PCBM Bulk Heterojunction Solar Cells

The performance of bulk‐heterojunction (BHJ) solar cells is strongly correlated with the nanoscale structure of the active layer. Various processing techniques have been explored to improve the nanoscale morphology of the BHJ layer, e.g., by varying the casting solvent, thermal annealing, solvent annealing, and solvent additives. This paper highlights the role of residual solvent in the “dried” BHJ layer, and the effect of residual solvents on PCBM diffusion and ultimately the stability of the morphology. We show that solvent is retained within the BHJ film despite prolonged heat treatment, leading to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM agglomerates. The addition of a small volume fraction of nitrobenzene to the casting solution inhibits the diffusion of PCBM in the dry film, resulting in smaller PCBM agglomerates, and improves the fill factor of the BHJ device to 0.61 without further tempering. The addition of nitrobenzene also increases the P3HT crystalline content, while increasing the onset temperature for melting of P3HT side chains and backbone. The melting temperature for PCBM is also higher with the nitrobenzene additive present.     

The Energy of Charge‐Transfer States in Electron Donor–Acceptor Blends: Insight into the Energy Losses in Organic Solar Cells

Here, a general experimental method to determine the energy E_CT of intermolecular charge‐transfer (CT) states in electron donor–acceptor (D–A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D–A blends to correct for a constant Coulombic term. It is shown that E_CT correlates linearly with the open‐circuit voltage (V_oc) of photovoltaic devices in D–A blends via eV_oc = E_CT ? 0.5 eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S₁ with energy E_g) in the blend to the CT state (S₁ → CT) occurs when E_g ? E_CT > 0.1 eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (E_T) of D or A (CT → T₁) can occur when E_CT ? E_T > 0.1 eV. From these relations, it is concluded that in D–A blends optimized for photovoltaic action: i) the maximum attainable V_oc is ultimately set by the optical band gap (eV_oc = E_g ? 0.6 eV) and ii) the singlet–triplet energy gap should be ΔE_ST < 0.2 eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area.     

Ternary Blend Strategy for Achieving High‐Efficiency Organic Solar Cells with Nonfullerene Acceptors Involved

Nonfullerene acceptors have recently drawn considerable attention in bulk heterojunction organic solar cells (OSCs). The power conversion efficiency (PCE) over 14% is achieved in single‐junction fullerene‐free OSCs, which has surpassed that of fullerene‐based counterparts. For future commercial applications, however, a high and stable PCE > 15% is required, which entails rational material design and device optimization. In this context, three approaches are generally utilized—the synthesis of novel nonfullerene acceptors and the selection of suitable polymer donors to pair with them, the tandem or multijunction device architecture, and the ternary blend strategy. Compared to the former two methods, the ternary strategy allows to employ the existing photovoltaic materials and the single‐junction device. Therefore, an exploration of nonfullerene acceptor–based ternary blend OSCs (NFTSCs) has shown unprecedented progress since 2016. This review summarizes and classifies the photovoltaic materials utilized in NFTSCs, aiming to not only exhibit the recent development of NFTSCs but also elucidate the correlation among donor/acceptor materials, film morphology, transport dynamics, and device fabrication toward high‐efficiency OSCs. Lastly, the above key advances are highlighted along with the existing issues and insights into the viable path for the further research thrusts are offered.     

Incorporation of SiO2 dielectric nanoparticles for performance enhancement in P3HT:PCBM inverted organic solar cells

It is well known that organic solar cells (OSCs) with inverted geometry have not only demonstrated a better stability and longer device life time but also have shown improved power conversion efficiency (PCE). Recent studies exhibit that incorporation of metal and/or semiconducting nanoparticles (NPs) can further increase the PCE for OSCs. In this present work, we have synthesized SiO₂ NPs of various sizes (25, 50, 75 and 100 nm) using the modified Stober method and incorporated them into P3HT:PCBM photoactive layer and ZnO based electron transport layer (ETL) in order to investigate the light trapping effects in an OSC. Absorption studies have shown a considerable increase in photo absorption in both cases. The fabricated devices demonstrated 13% increase in the PCE when SiO₂ NPs are incorporated in P3HT:PCBM photoactive layer, whereas PCE was increased by 20% when SiO₂ NPs are incorporated in ZnO based ETL. Mott–Schottky analysis and impedance spectroscopy measurements have been carried out to determine the depletion width and global mobility for both the devices. The possible reason for PCE enhancement and the role of SiO₂ NPs in active layer and ZnO ETL are explained on the basis of the results obtained from Mott–Schottky analysis and impedance spectroscopy measurements.     

Controlling the morphology of nanofiber-P3HT:PCBM blends for organic bulk heterojunction solar cells

Within the field of organic bulk heterojunction solar cells, the morphology of the active layer has a key role in obtaining high power conversion efficiencies. P3HT nanofibers, obtained in highly concentrated solutions, are able to give controlled morphologies directly upon deposition. Since the solar cell efficiency of fiber solar cells depends on the fiber content of the casting solution, it is important to control this parameter. Here, we demonstrate an easy way to control the fiber content in the casting solution, i.e. changing the solution temperature. By using solution heating, the overall molecular weight of the polymer in the blend is kept constant, fiber isolation is not needed and the use of solvent mixtures is avoided. The obtained optimal power conversion efficiency is shown to be linked to the morphology of the active layer, which is studied with Transmission Electron Microscopy (TEM).     

Assessing Antisite Defect and Impurity Concentrations in Bi2Te3 Based Thin Films by High‐Accuracy Chemical Analysis

In Bi₂Te₃‐based materials charge‐carrier densities are determined by antisite defects and controlling these defects is a key issue for thermoelectric and topological insulator materials. Bi‐Te thin films with high‐quality thermoelectric properties are deposited using a nano‐alloying approach by molecular beam epitaxy (MBE) and sputtering. The in‐plane transport properties are measured at room temperature as a function of charge‐carrier density. High‐accuracy chemical analysis by wavelength‐dispersive X‐ray spectrometry (WDX) is applied for the first time to these Bi₂Te₃‐based thin films. The acquisition conditions for WDX spectrometry are established using Monte Carlo simulations for the electron trajectories, which guarantees a high lateral resolution and rules out stray radiation generated in the substrate of the films. In contrast to energy‐dispersive X‐ray spectrometry (EDX), which is usually applied, WDX offers unprecedented accuracy for measuring antisite defect concentrations and thus has a high impact on improving the quality of thin films. The charge‐carrier densities are calculated from the WDX results according to the point‐defect model of Miller and Li and the thermopower and electrical conductivity are calculated for different charge‐carrier densities by solving the linearized Boltzmann transport equation. A good quantitative agreement is found for the dependence of the thermopower on stoichiometry, whereas the electrical conductivity is sensitively affected by contaminants.     

Dendrimer‐Based,High‐Luminescence Conjugated Microporous Polymer Films for Highly Sensitive and Selective Volatile Organic Compound Sensor Arrays

Conjugated microporous polymers (CMPs) are attracting increasing attention in chemical sensing due to their extended π‐conjugated framework, permanent microporous structure, and large specific surface area. However, the extremely poor solubility and processability of CMPs, as well as the serious fluorescence quenching caused by aggregation, restrict their practical applications. Herein, a high‐luminescence CMP film is constructed based on a novel dendrimer (TPETCz) featured by its central tetraphenylethylene “core” with aggregation‐induced emission effect and its highly electro‐active “branches.” High specific surface area CMP films for analyte diffusion are fabricated by a facile in situ electropolymerization method. These dendrimer‐based CMP films exhibit superior sensitivity to volatile organic compounds (VOCs). More importantly, 18 types, the most types reported, of VOC vapors are precisely distinguished by the linear discriminant analysis by establishing a 2D fluorescence sensor array based on the CMP films and the dendrimer monomer films.