Study of Glass Formation and Crystallization Kinetics in a 2D Metal Halide Perovskite Using Ultrafast Calorimetry.

While crystalline 2D metal halide perovskites (MHPs) represent a well-celebrated semiconductor class, supporting applications in the fields of photovoltaics, emitters, and sensors, the recent discovery of glass formation in an MHP opens many new opportunities associated with reversible glass-crystalline switching, with each state offering distinct optoelectronic properties. However, the previously reported [S-(-)-1-(1-naphthyl)ethylammonium]2PbBr4 perovskite is a strong glass former with sluggish glass-crystal transformation time scales, pointing to a need for glassy MHPs with a broader range of compositions and crystallization kinetics. Herein we report glass formation for low-melting-temperature 1-MeHa2PbI4 (1-MeHa = 1-methyl-hexylammonium) using ultrafast calorimetry, thereby extending the range of MHP glass formation across a broader range of organic (fused ring to branched aliphatic) and halide (bromide to iodide) compositions. The importance of a slight loss of organic and hydrogen iodide components from the MHP in stabilizing the glassy state is elucidated. Furthermore, the underlying kinetics of glass-crystal transformation, including activation energies, crystal growth rate, Angell plot, and fragility index, is studied using a combination of kinetic, thermodynamic, and rheological modeling techniques. An inferred fast crystal growth rate of 0.21 m/s for 1-MeHa2PbI4 shows promise toward suitability in extended application spaces, for example, in metamaterials, nonvolatile memory, and optical and neuromorphic computing devices.

Color-neutral, semitransparent organic photovoltaics for power window applications.

Semitransparent organic photovoltaic cells (ST-OPVs) are emerging as a solution for solar energy harvesting on building facades, rooftops, and windows. However, the trade-off between power-conversion efficiency (PCE) and the average photopic transmission (APT) in color-neutral devices limits their utility as attractive, power-generating windows. A color-neutral ST-OPV is demonstrated by using a transparent indium tin oxide (ITO) anode along with a narrow energy gap nonfullerene acceptor near-infrared (NIR) absorbing cell and outcoupling (OC) coatings on the exit surface. The device exhibits PCE = 8.1 ± 0.3% and APT = 43.3 ± 1.2% that combine to achieve a light-utilization efficiency of LUE = 3.5 ± 0.1%. Commission Internationale d'eclairage chromaticity coordinates of (0.38, 0.39), a color-rendering index of 86, and a correlated color temperature of 4,143 K are obtained for simulated AM1.5 illumination transmitted through the cell. Using an ultrathin metal anode in place of ITO, we demonstrate a slightly green-tinted ST-OPV with PCE = 10.8 ± 0.5% and APT = 45.7 ± 2.1% yielding LUE = 5.0 ± 0.3% These results indicate that ST-OPVs can combine both efficiency and color neutrality in a single device.

A molecular interaction-diffusion framework for predicting organic solar cell stability.

Rapid increase in the power conversion efficiency of organic solar cells (OSCs) has been achieved with the development of non-fullerene small-molecule acceptors (NF-SMAs). Although the morphological stability of these NF-SMA devices critically affects their intrinsic lifetime, their fundamental intermolecular interactions and how they govern property-function relations and morphological stability of OSCs remain elusive. Here, we discover that the diffusion of an NF-SMA into the donor polymer exhibits Arrhenius behaviour and that the activation energy Ea scales linearly with the enthalpic interaction parameters χH between the polymer and the NF-SMA. Consequently, the thermodynamically most unstable, hypo-miscible systems (high χ) are the most kinetically stabilized. We relate the differences in Ea to measured and selectively simulated molecular self-interaction properties of the constituent materials and develop quantitative property-function relations that link thermal and mechanical characteristics of the NF-SMA and polymer to predict relative diffusion properties and thus morphological stability.

Optimized Active Layer Morphologies via Ternary Copolymerization of Polymer Donors for 17.6 % Efficiency Organic Solar Cells with Enhanced Fill Factor.

Regulating molecular structure to optimize the active layer morphology is of considerable significance for improving the power conversion efficiencies (PCEs) in organic solar cells (OSCs). Herein, we demonstrated a simple ternary copolymerization approach to develop a terpolymer donor PM6-Tz20 by incorporating the 5,5'-dithienyl-2,2'-bithiazole (DTBTz, 20 mol%) unit into the backbone of PM6 (PM6-Tz00). This method can effectively tailor the molecular orientation and aggregation of the polymer, and then optimize the active layer morphology and the corresponding physical processes of devices, ultimately boosting FF and then PCE. Hence, the PM6-Tz20: Y6-based OSCs achieved a PCE of up to 17.1% with a significantly enhanced FF of 0.77. Using Ag (220 nm) instead of Al (100 nm) as cathode, the champion PCE was further improved to 17.6%. This work provides a simple and effective molecular design strategy to optimize the active layer morphology of OSCs for improving photovoltaic performance.

Regio-Regular Polymer Acceptors Enabled by Determined Fluorination on End Groups for All-Polymer Solar Cells with 15.2 % Efficiency.

Polymerization sites of small molecule acceptors (SMAs) play vital roles in determining device performance of all-polymer solar cells (all-PSCs). Different from our recent work about fluoro- and bromo- co-modified end group of IC-FBr (a mixture of IC-FBr1 and IC-FBr2), in this paper, we synthesized and purified two regiospecific fluoro- and bromo- substituted end groups (IC-FBr-o & IC-FBr-m), which were then employed to construct two regio-regular polymer acceptors named PYF-T-o and PYF-T-m, respectively. In comparison with its isomeric counterparts named PYF-T-m with different conjugated coupling sites, PYF-T-o exhibits stronger and bathochromic absorption to achieve better photon harvesting. Meanwhile, PYF-T-o adopts more ordered inter-chain packing and suitable phase separation after blending with the donor polymer PM6, which resulted in suppressed charge recombination and efficient charge transport. Strikingly, we observed a dramatic performance difference between the two isomeric polymer acceptors PYF-T-o and PYF-T-m. While devices based on PM6:PYF-T-o can yield power conversion efficiency (PCE) of 15.2 %, devices based on PM6:PYF-T-m only show poor efficiencies of 1.4 %. This work demonstrates the success of configuration-unique fluorinated end groups in designing high-performance regular polymer acceptors, which provides guidelines towards developing all-PSCs with better efficiencies.

Morphological-Electrical Property Relation in Cu(In,Ga)(S,Se)2 Solar Cells: Significance of Crystal Grain Growth and Band Grading by Potassium Treatment.

Solution-processed Cu(In,Ga)(S,Se)2  (CIGS) has a great potential for the production of large-area photovoltaic devices at low cost. However, CIGS solar cells processed from solution exhibit relatively lower performance compared to vacuum-processed devices because of a lack of proper composition distribution, which is mainly instigated by the limited Se uptake during chalcogenization. In this work, a unique potassium treatment method is utilized to improve the selenium uptake judiciously, enhancing grain sizes and forming a wider bandgap minimum region. Careful engineering of the bandgap grading structure also results in an enlarged space charge region, which is favorable for electron-hole separation and efficient charge carrier collection. Besides, this device processing approach has led to a linearly increasing electron diffusion length and carrier lifetime with increasing the grain size of the CIGS film, which is a critical achievement for enhancing photocurrent yield. Overall, 15% of power conversion efficiency is achieved in solar cells processed from environmentally benign solutions. This approach offers critical insights for precise device design and processing rules for solution-processed CIGS solar cells.

High-Performance All-Polymer Solar Cells: Synthesis of Polymer Acceptor by a Random Ternary Copolymerization Strategy.

Demonstrated in this work is a simple random ternary copolymerization strategy to synthesize a series of polymer acceptors, PTPBT-ETx , by polymerizing a small-molecule acceptor unit modified from Y6 with a thiophene connecting unit and a controlled amount of an 3-ethylesterthiophene (ET) unit. Compared to PTPBT of only Y6-like units and thiophene units, PTPBT-ETx (where x represents the molar ratio of the ET unit) with an incorporated ET unit in the ternary copolymers show up-shifted LUMO energy levels, increased electron mobilities, and improved blend morphologies in the blend film with the polymer donor PBDB-T. And the all-polymer solar cell (all-PSC) based on PBDB-T:PTPBT-ET0.3 achieved a high power conversion efficiency over 12.5 %. In addition, the PTPBT-ET0.3 -based all-PSC also exhibits long-term photostability over 300 hours.

Conjugation-Curtailing of Benzodithionopyran-Cored Molecular Acceptor Enables Efficient Air-Processed Small Molecule Solar Cells.

Small molecule solar cells (SMSCs) lag a long way behind polymer solar cells. A key limit is the less controllable morphology of small molecule materials, which can be aggravated when incorporating anisotropic nonfullerene acceptors. To fine-tune the blending morphology within SMSCs, a π-conjunction curtailing design is applied, which produces a efficient benzodithionopyran-cored molecular acceptor for nonfullerene SMSCs (NF-SMSCs). When blended with a molecular donor BDT3TR-SF to fabricate NF-SMSCs, the π-conjunction curtailed molecular acceptor NBDTP-M obtains an optimal power conversion efficiency (PCE) of up to 10.23%, which is much higher than that of NBDTTP-M of longer π-conjunction. It retains 93% of the PCE of devices fabricated in a glove box when all spin-coating and post-treating procedures are conducted in ambient air with relative humidity of 25%, which suggests the good air-processing capability of π-conjunction curtailed molecules. Detailed X-ray scattering investigations indicate that the BDT3TR-SF:NBDTP-M blend exhibits a blend morphology featuring fine interpenetrating networks with smaller domains and higher phase purity, which results in more efficient charge generation, more balanced charge transport, and less recombination compared to the low-performance BDT3TR-SF:NBDTTP-M blend. This work provides a guideline for molecular acceptors' design toward efficient, low-cost, air-processed NF-SMSCs.

Isomery-Dependent Miscibility Enables High-Performance All-Small-Molecule Solar Cells.

Nonfullerene polymer solar cells develop quickly. However, nonfullerene small-molecule solar cells (NF-SMSCs) still show relatively inferior performance, attributing to the lack of comprehensive understanding of the structure-performance relationship. To address this issue, two isomeric small-molecule acceptors, NBDTP-Fout and NBDTP-Fin , with varied oxygen position in the benzodi(thienopyran) (BDTP) core are designed and synthesized. When blended with molecular donor BDT3TR-SF, devices based on the two isomeric acceptors show disparate photovoltaic performance. Fabricated with an eco-friendly processing solvent (tetrahydrofuran), the BDT3TR-SF:NBDTP-Fout blend delivers a high power conversion efficiency of 11.2%, ranked to the top values reported to date, while the BDT3TR-SF:NBDTP-Fin blend almost shows no photovoltaic response (0.02%). With detailed investigations on inherent optoelectronic processes as well as morphological evolution, this performance disparity is correlated to the interfacial tension of the two combinations and concludes that proper interfacial tension is a key factor for effective phase separation, optimal blend morphology, and superior performance, which can be achieved by the "isomerization" design on molecular acceptors. This work reveals the importance of modulating the materials miscibility by interfacial-tension-oriented molecular design, which provides a general guideline toward efficient NF-SMSCs.

Quantitative relations between interaction parameter, miscibility and function in organic solar cells.

Although it is known that molecular interactions govern morphology formation and purity of mixed domains of conjugated polymer donors and small-molecule acceptors, and thus largely control the achievable performance of organic solar cells, quantifying interaction-function relations has remained elusive. Here, we first determine the temperature-dependent effective amorphous-amorphous interaction parameter, χaa(T), by mapping out the phase diagram of a model amorphous polymer:fullerene material system. We then establish a quantitative 'constant-kink-saturation' relation between χaa and the fill factor in organic solar cells that is verified in detail in a model system and delineated across numerous high- and low-performing materials systems, including fullerene and non-fullerene acceptors. Our experimental and computational data reveal that a high fill factor is obtained only when χaa is large enough to lead to strong phase separation. Our work outlines a basis for using various miscibility tests and future simulation methods that will significantly reduce or eliminate trial-and-error approaches to material synthesis and device fabrication of functional semiconducting blends and organic blends in general.

A Wide Band Gap Polymer with a Deep Highest Occupied Molecular Orbital Level Enables 14.2% Efficiency in Polymer Solar Cells.

To simultaneously achieve low photon energy loss ( Eloss) and broad spectral response, the molecular design of the wide band gap (WBG) donor polymer with a deep HOMO level is of critical importance in fullerene-free polymer solar cells (PSCs). Herein, we developed a new benzodithiophene unit, i.e., DTBDT-EF, and conducted systematic investigations on a WBG DTBDT-EF-based donor polymer, namely, PDTB-EF-T. Due to the synergistic electron-withdrawing effect of the fluorine atom and ester group, PDTB-EF-T exhibits a higher oxidation potential, i.e., a deeper HOMO level (ca. -5.5 eV) than most well-known donor polymers. Hence, a high open-circuit voltage of 0.90 V was obtained when paired with a fluorinated small molecule acceptor (IT-4F), corresponding to a low Eloss of 0.62 eV. Furthermore, side-chain engineering demonstrated that subtle side-chain modulation of the ester greatly influences the aggregation effects and molecular packing of polymer PDTB-EF-T. With the benefits of the stronger interchain π-π interaction, the improved ordering structure, and thus the highest hole mobility, the most symmetric charge transport and reduced recombination are achieved for the linear decyl-substituted PDTB-EF-T (P2)-based PSCs, leading to the highest short-circuit current density and fill factor (FF). Due to the high Flory-Huggins interaction parameter (χ), surface-directed phase separation occurs in the P2:IT-4F blend, which is supported by X-ray photoemission spectroscopy results and cross-sectional transmission electron microscope images. By taking advantage of the vertical phase distribution of the P2:IT-4F blend, a high power conversion efficiency (PCE) of 14.2% with an outstanding FF of 0.76 was recorded for inverted devices. These results demonstrate the great potential of the DTBDT-EF unit for future organic photovoltaic applications.

Long-Lived, Non-Geminate, Radiative Recombination of Photogenerated Charges in a Polymer/Small-Molecule Acceptor Photovoltaic Blend.

Minimization of open-circuit-voltage ( VOC) loss is required to transcend the efficiency limitations on the performance of organic photovoltaics (OPV). We study charge recombination in an OPV blend comprising a polymer donor with a small molecule nonfullerene acceptor that exhibits both high photovoltaic internal quantum efficiency and relatively high external electroluminescence quantum efficiency. Notably, this donor/acceptor blend, consisting of the donor polymer commonly referred to as PCE10 with a pseudoplanar small molecule acceptor (referred to as FIDTT-2PDI) exhibits relatively bright delayed photoluminescence on the microsecond time scale beyond that observed in the neat material. We study the photoluminescence decay kinetics of the blend in detail and conclude that this long-lived photoluminescence arises from radiative nongeminate recombination of charge carriers, which we propose occurs via a donor/acceptor CT state located close in energy to the singlet state of the polymer donor. Additionally, crystallographic and spectroscopic studies point toward low subgap disorder, which could be beneficial for low radiative and nonradiative losses. These results provide an important demonstration of photoluminescence due to nongeminate charge recombination in an efficient OPV blend, a key step in identifying new OPV materials and materials-screening criteria if OPV is to approach the theoretical limits to efficiency.

Competition between exceptionally long-range alkyl sidechain ordering and backbone ordering in semiconducting polymers and its impact on electronic and optoelectronic properties.

Intra- and intermolecular ordering greatly impact the electronic and optoelectronic properties of semiconducting polymers. Despite much prior efforts regarding molecular packing, the interrelationship between ordering of alkyl sidechains and conjugated backbones has not been fully detailed. We report here the discovery of a highly ordered alkyl sidechain phase in six representative semiconducting polymers, determined from distinct spectroscopic and diffraction signatures. The sidechain ordering exhibits unusually large coherence lengths of at least 70 nm, induces torsional/twisting backbone disorder, and results in a vertically layered multilayer nanostructure with ordered sidechain layers alternating with disordered backbone layers. Calorimetry and in-situ variable temperature scattering measurements in a model system PBnDT-FTAZ clearly delineate this competition of ordering that prevents the simultaneous long-range order of both moieties. The long-range sidechain ordering can be exploited as a transient state to fabricate PBnDT-FTAZ films with an atypical edge-on texture and 2.5x improved OFET mobility. The observed influence of ordering between the moieties implies that improved molecular design could produce synergistic rather than destructive ordering effects. Given the large sidechain coherence lengths observed, such synergistic ordering should greatly improve the coherence length of backbone ordering and thereby improve electronic and optoelectronic properties such as charge transport and exciton diffusion lengths.

The Role of FRET in Non-Fullerene Organic Solar Cells: Implications for Molecular Design.

Non-fullerene acceptors (NFAs) have been demonstrated to be promising candidates for highly efficient organic photovoltaic (OPV) devices. The tunability of absorption characteristics of NFAs can be used to make OPVs with complementary donor-acceptor absorption to cover a broad range of the solar spectrum. However, both charge transfer from donor to acceptor moieties and energy (energy) transfer from high-bandgap to low-bandgap materials are possible in such structures. Here, we show that when charge transfer and exciton transfer processes are both present, the coexistence of excitons in both domains can cause a loss mechanism. Charge separation of excitons in a low-bandgap material is hindered due to exciton population in the larger bandgap acceptor domains. Our results further show that excitons in low-bandgap material should have a relatively long lifetime compared to the transfer time of excitons from higher bandgap material in order to contribute to the charge separation. These observations provide significant guidance for design and development of new materials in OPV applications.

Monitoring Charge Separation Processes in Quasi-One-Dimensional Organic Crystalline Structures.

We perform the transient absorption spectroscopy experiments to investigate the dynamics of the low-energy collective electron-hole excitations in α-copper phthalocyanine thin films. The results are interpreted in terms of the third-order nonlinear polarization response function. It is found that, initially excited in the molecular plane, the intramolecular Frenkel exciton polarization reorients with time to align along the molecular chain direction to form coupled Frenkel-charge-transfer exciton states, the eigenstates of the one-dimensional periodic molecular lattice. The process pinpoints the direction of the charge separation in α-copper phthalocyanine and similar organic molecular structures. Being able to observe and monitor such processes is important both for understanding the physical principles of organic thin film solar energy conversion device operation and for the development of organic optoelectronics in general.

Ring-Fusion of Perylene Diimide Acceptor Enabling Efficient Nonfullerene Organic Solar Cells with a Small Voltage Loss.

We report a novel small molecule acceptor (SMA) named FTTB-PDI4 obtained via ring-fusion between the thiophene and perylene diimide (PDI) units of a PDI-tetramer with a tetrathienylbezene (TTB) core. A small voltage loss of 0.53 V and a high power conversion efficiency of 10.58% were achieved, which is the highest value reported for PDI-based devices to date. By comparing the fused and nonfused SMAs, we show that the ring-fusion introduces several beneficial effects on the properties and performances of the acceptor material, including more favorable energy levels, enhanced light absorption and stronger intermolecular packing. Interestingly, morphology data reveal that the fused molecule yields higher domain purity and thus can better maintain its molecular packing and electron mobility in the blend. Theoretical calculations also demonstrate that FTTB-PDI4 exhibits a "double-decker" geometry with two pairs of mostly parallel PDI units, which is distinctively different from reported PDI-tetramers with highly twisted geometries and can explain the better performance of the material. This work highlights the promising design of PDI-based acceptors by the ring-fusion strategy.

9.73% Efficiency Nonfullerene All Organic Small Molecule Solar Cells with Absorption-Complementary Donor and Acceptor.

In the last two years, polymer solar cells (PSCs) developed quickly with n-type organic semiconductor (n-OSs) as acceptor. In contrast, the research progress of nonfullerene organic solar cells (OSCs) with organic small molecule as donor and the n-OS as acceptor lags behind. Here, we synthesized a D-A structured medium bandgap organic small molecule H11 with bithienyl-benzodithiophene (BDTT) as central donor unit and fluorobenzotriazole as acceptor unit, and achieved a power conversion efficiency (PCE) of 9.73% for the all organic small molecules OSCs with H11 as donor and a low bandgap n-OS IDIC as acceptor. A control molecule H12 without thiophene conjugated side chains on the BDT unit was also synthesized for investigating the effect of the thiophene conjugated side chains on the photovoltaic performance of the p-type organic semiconductors (p-OSs). Compared with H12, the 2D-conjugated H11 with thiophene conjugated side chains shows intense absorption, low-lying HOMO energy level, higher hole mobility and ordered bimodal crystallite packing in the blend films. Moreover, a larger interaction parameter (χ) was observed in the H11 blends calculated from Hansen solubility parameters and differential scanning calorimetry measurements. These special features combined with the complementary absorption of H11 donor and IDIC acceptor resulted in the best PCE of 9.73% for nonfullerene all small molecule OSCs up to date. Our results indicate that fluorobenzotriazole based 2D conjugated p-OSs are promising medium bandgap donors in the nonfullerene OSCs.

Origins of polarization-dependent anisotropic X-ray scattering from organic thin films.

Organic thin films that have no overall in-plane directional ordering often nonetheless produce anisotropic scattering patterns that rotate with the polarization of incident resonant X-rays. Isotropic symmetry is broken by local correlations between molecular orientation and domain structure. Such examples of molecular alignment at domain interfaces and within the bulk of domains, which are both critical to fields such as organic electronics, are simulated and compared with experimental scattering. Anisotropic scattering patterns are found to allow unambiguous identification of the mechanism of local molecular orientation correlations and, as such, promise to be both distinct and complementary to isotropic scattering intensity as a general measure of thin film microstructure.

Influence of Regio- and Chemoselectivity on the Properties of Fluoro-Substituted Thienothiophene and Benzodithiophene Copolymers.

By studying the regio- and chemoselectivity of fluoro-substituted thienothiophene and benzodithiophene copolymers, we found polymers made from conventional one-pot polycondensation reaction consist of two distinctly different segments with a ratio of 0.36/0.64. Through further comparative studies of neat regioregular polymers based on each individual segment, we have identified the specific segment that contributes to the superior absorption, packing order, and charge mobility in the corresponding polymers. The unique structure-property relationships are the result of cooperative molecular arrangements of the key segment and noncovalent interaction between the fluoro group and the aromatic proton on the thiophene side-chain of the polymers.

Mobility-controlled performance of thick solar cells based on fluorinated copolymers.

Developing novel materials and device architectures to further enhance the efficiency of polymer solar cells requires a fundamental understanding of the impact of chemical structures on photovoltaic properties. Given that device characteristics depend on many parameters, deriving structure-property relationships has been very challenging. Here we report that a single parameter, hole mobility, determines the fill factor of several hundred nanometer thick bulk heterojunction photovoltaic devices based on a series of copolymers with varying amount of fluorine substitution. We attribute the steady increase of hole mobility with fluorine content to changes in polymer molecular ordering. Importantly, all other parameters, including the efficiency of free charge generation and the coefficient of nongeminate recombination, are nearly identical. Our work emphasizes the need to achieve high mobility in combination with strongly suppressed charge recombination for the thick devices required by mass production technologies.