Low-loss contacts on textured substrates for inverted perovskite solar cells.

Inverted perovskite solar cells (PSCs) promise enhanced operating stability compared to their normal-structure counterparts1-3. To improve efficiency further, it is crucial to combine effective light management with low interfacial losses4,5. Here we develop a conformal self-assembled monolayer (SAM) as the hole-selective contact on light-managing textured substrates. Molecular dynamics simulations indicate that cluster formation during phosphonic acid adsorption leads to incomplete SAM coverage. We devise a co-adsorbent strategy that disassembles high-order clusters, thus homogenizing the distribution of phosphonic acid molecules, and thereby minimizing interfacial recombination and improving electronic structures. We report a laboratory-measured power conversion efficiency (PCE) of 25.3% and a certified quasi-steady-state PCE of 24.8% for inverted PSCs, with a photocurrent approaching 95% of the Shockley-Queisser maximum. An encapsulated device having a PCE of 24.6% at room temperature retains 95% of its peak performance when stressed at 65 °C and 50% relative humidity following more than 1,000 h of maximum power point tracking under 1 sun illumination. This represents one of the most stable PSCs subjected to accelerated ageing: achieved with a PCE surpassing 24%. The engineering of phosphonic acid adsorption on textured substrates offers a promising avenue for efficient and stable PSCs. It is also anticipated to benefit other optoelectronic devices that require light management.

All-perovskite tandem solar cells with improved grain surface passivation.

All-perovskite tandem solar cells hold the promise of surpassing the efficiency limits of single-junction solar cells1-3; however, until now, the best-performing all-perovskite tandem solar cells have exhibited lower certified efficiency than have single-junction perovskite solar cells4,5. A thick mixed Pb-Sn narrow-bandgap subcell is needed to achieve high photocurrent density in tandem solar cells6, yet this is challenging owing to the short carrier diffusion length within Pb-Sn perovskites. Here we develop ammonium-cation-passivated Pb-Sn perovskites with long diffusion lengths, enabling subcells that have an absorber thickness of approximately 1.2 µm. Molecular dynamics simulations indicate that widely used phenethylammonium cations are only partially adsorbed on the surface defective sites at perovskite crystallization temperatures. The passivator adsorption is predicted to be enhanced using 4-trifluoromethyl-phenylammonium (CF3-PA), which exhibits a stronger perovskite surface-passivator interaction than does phenethylammonium. By adding a small amount of CF3-PA into the precursor solution, we increase the carrier diffusion length within Pb-Sn perovskites twofold, to over 5 µm, and increase the efficiency of Pb-Sn perovskite solar cells to over 22%. We report a certified efficiency of 26.4% in all-perovskite tandem solar cells, which exceeds that of the best-performing single-junction perovskite solar cells. Encapsulated tandem devices retain more than 90% of their initial performance after 600 h of operation at the maximum power point under 1 Sun illumination in ambient conditions.

A Pyrrole Modified 3,4-Propylenedioxythiophene Conjugated Polymer as Hole Transport Layer for Efficient and Stable Perovskite Solar Cells.

Despite the outstanding electric properties and cost-effectiveness of poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives, their performance as hole transport layer (HTL) materials in conventional perovskite solar cells (PSCs) has lagged behind that of widely used spirobifluorene-based molecules or poly(triaryl amine). This gap is mainly from their poor solubility and energy alignment mismatch. In this work, the design and synthesis of a pyrrole-modified HTL (PPr) based on 3,4-propylenedioxythiophene (ProDOT) are presented for efficient and stable PSCs. As a result of the superior defects passivation ability, excellent contact with perovskite, enhanced hole extraction, and high hydrophobicity, the unencapsulated PPr-based PSCs showed the peak PCE of 21.49% and outstanding moisture stability (over 4000 h). This work highlights the potential application of ProDOT-based materials as HTL for PSCs and underscores the importance of the rational design of PEDOT and its derivatives.

Highly Conductive and Solution-Processable n-Doped Transparent Organic Conductor.

Transparent conductors (TCs) play a vital role in displays, solar cells, and emerging printed electronics. Here, we report a solution-processable n-doped organic conductor from copper-catalyzed cascade reactions in the air, which involves oxidative polymerization and reductive doping in one pot. The formed polymer ink is shelf-stable over 20 days and can endure storage temperatures from -20 to 65 °C. The optimized n-doped thin-film TC exhibits a low sheet resistance of 45 Ω/sq and a high transmittance (T550 > 80%), which can rival indium tin oxide. The transparent organic conductor exhibits excellent durability under accelerated weathering tests (85 °C/85% RH). Furthermore, the n-doped polymer film can also function as an electrode material with a high volumetric capacity. When it is paired with p-doped PEDOT:PSS, a record-high coloration efficiency is obtained in a dual-polymer electrochromic device.

Metal Halide Perovskite Heterostructures: Blocking Anion Diffusion with Single-Layer Graphene.

The development of metal halide perovskite/perovskite heterostructures is hindered by rapid interfacial halide diffusion leading to mixed alloys rather than sharp interfaces. To circumvent this outcome, we developed an ion-blocking layer consisting of single-layer graphene (SLG) deposited between the metal halide perovskite layers and demonstrated that it effectively blocks anion diffusion in a CsPbBr3/SLG/CsPbI3 heterostructure. Spatially resolved elemental analysis and spectroscopic measurements demonstrate the halides do not diffuse across the interface, whereas control samples without the SLG show rapid homogenization of the halides and loss of the sharp interface. Ultraviolet photoelectron spectroscopy, DFT calculations, and transient absorbance spectroscopy indicate the SLG has little electronic impact on the individual semiconductors. In the CsPbBr3/SLG/CsPbI3, we find a type I band alignment that supports transfer of photogenerated carriers across the heterointerface. Light-emitting diodes (LEDs) show electroluminescence from both the CsPbBr3 and CsPbI3 layers with no evidence of ion diffusion during operation. Our approach provides opportunities to design novel all-perovskite heterostructures to facilitate the control of charge and light in optoelectronic applications.

n-type charge transport in heavily p-doped polymers.

It is commonly assumed that charge-carrier transport in doped π-conjugated polymers is dominated by one type of charge carrier, either holes or electrons, as determined by the chemistry of the dopant. Here, through Seebeck coefficient and Hall effect measurements, we show that mobile electrons contribute substantially to charge-carrier transport in π-conjugated polymers that are heavily p-doped with strong electron acceptors. Specifically, the Seebeck coefficient of several p-doped polymers changes sign from positive to negative as the concentration of the oxidizing agents FeCl3 or NOBF4 increase, and Hall effect measurements for the same p-doped polymers reveal that electrons become the dominant delocalized charge carriers. Ultraviolet and inverse photoelectron spectroscopy measurements show that doping with oxidizing agents results in elimination of the transport gap at high doping concentrations. This approach of heavy p-type doping is demonstrated to provide a promising route to high-performance n-type organic thermoelectric materials.

Towards understanding the doping mechanism of organic semiconductors by Lewis acids.

Precise doping of organic semiconductors allows control over the conductivity of these materials, an essential parameter in electronic applications. Although Lewis acids have recently shown promise as dopants for solution-processed polymers, their doping mechanism is not yet fully understood. In this study, we found that B(C6F5)3 is a superior dopant to the other Lewis acids investigated (BF3, BBr3 and AlCl3). Experiments indicate that Lewis acid-base adduct formation with polymers inhibits the doping process. Electron-nuclear double-resonance and nuclear magnetic resonance experiments, together with density functional theory, show that p-type doping occurs by generation of a water-Lewis acid complex with substantial Brønsted acidity, followed by protonation of the polymer backbone and electron transfer from a neutral chain segment to a positively charged, protonated one. This study provides insight into a potential path for protonic acid doping and shows how trace levels of water can transform Lewis acids into powerful Brønsted acids.

Enhanced Near-Infrared-to-Visible Upconversion by Synthetic Control of PbS Nanocrystal Triplet Photosensitizers.

Photon upconversion employing semiconductor nanocrystals (NCs) makes use of their large and tunable absorption to harvest light in the near-infrared (NIR) wavelengths as well as their small gap between singlet and triplet excited states to reduce energy losses. Here, we report the highest QY (11.8%) thus far for the conversion of NIR to yellow photons by improving the quality of the PbS NC. This high QY was achieved by using highly purified lead and thiourea precursors. This QY is 2.6 times higher than from NCs prepared with commercially available lead and sulfide precursors. Transient absorption spectroscopy reveals two reasons for the enhanced QY: longer intrinsic exciton lifetimes of PbS NCs and the ability to support a longer triplet lifetime for the surface-bound transmitter molecule. Overall, this results in a higher efficiency of triplet exciton transfer from the PbS NC light absorber to the emitter and thus a higher photon upconversion QY.

Efficient charge generation by relaxed charge-transfer states at organic interfaces.

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.

Importance of the donor:fullerene intermolecular arrangement for high-efficiency organic photovoltaics.

The performance of organic photovoltaic (OPV) material systems are hypothesized to depend strongly on the intermolecular arrangements at the donor:fullerene interfaces. A review of some of the most efficient polymers utilized in polymer:fullerene PV devices, combined with an analysis of reported polymer donor materials wherein the same conjugated backbone was used with varying alkyl substituents, supports this hypothesis. Specifically, the literature shows that higher-performing donor-acceptor type polymers generally have acceptor moieties that are sterically accessible for interactions with the fullerene derivative, whereas the corresponding donor moieties tend to have branched alkyl substituents that sterically hinder interactions with the fullerene. To further explore the idea that the most beneficial polymer:fullerene arrangement involves the fullerene docking with the acceptor moiety, a family of benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione polymers (PBDTTPD derivatives) was synthesized and tested in a variety of PV device types with vastly different aggregation states of the polymer. In agreement with our hypothesis, the PBDTTPD derivative with a more sterically accessible acceptor moiety and a more sterically hindered donor moiety shows the highest performance in bulk-heterojunction, bilayer, and low-polymer concentration PV devices where fullerene derivatives serve as the electron-accepting materials. Furthermore, external quantum efficiency measurements of the charge-transfer state and solid-state two-dimensional (2D) (13)C{(1)H} heteronuclear correlation (HETCOR) NMR analyses support that a specific polymer:fullerene arrangement is present for the highest performing PBDTTPD derivative, in which the fullerene is in closer proximity to the acceptor moiety of the polymer. This work demonstrates that the polymer:fullerene arrangement and resulting intermolecular interactions may be key factors in determining the performance of OPV material systems.

Characterization of the polymer energy landscape in polymer:fullerene bulk heterojunctions with pure and mixed phases.

Theoretical and experimental studies suggest that energetic offsets between the charge transport energy levels in different morphological phases of polymer:fullerene bulk heterojunctions may improve charge separation and reduce recombination in polymer solar cells (PSCs). In this work, we use cyclic voltammetry, UV-vis absorption, and ultraviolet photoelectron spectroscopy to characterize hole energy levels in the polymer phases of polymer:fullerene bulk heterojunctions. We observe an energetic offset of up to 150 meV between amorphous and crystalline polymer due to bandgap widening associated primarily with changes in polymer conjugation length. We also observe an energetic offset of up to 350 meV associated with polymer:fullerene intermolecular interactions. The first effect has been widely observed, but the second effect is not always considered despite being larger in magnitude for some systems. These energy level shifts may play a major role in PSC performance and must be thoroughly characterized for a complete understanding of PSC function.

Defect Modulation via SnX2 Additives in FASnI3 Perovskite Solar Cells.

Tin halide perovskites suffer from high defect densities compared with their lead counterparts. To decrease defect densities, SnF2 is commonly used as an additive in tin halide perovskites. Herein, we investigate how SnF2 compares to other SnX2 additives (X = F, Cl, Br) in terms of electronic and ionic defect properties in FASnI3. We find that FASnI3 films with SnF2 show the lowest Urbach energies (EU) of 19 meV and a decreased p-type character, as probed with ultraviolet photoemission spectroscopy. The activation energy of ion migration, as probed with thermal admittance spectroscopy, for FASnI3 with SnF2 is 1.33 eV, which is higher than with SnCl2 and SnBr2, which are 1.22 and 0.79 eV, respectively, resulting in less ion migration. Because of improved defect passivation, the champion power conversion efficiency of FASnI3 with SnF2 is 7.47% and only 1.84% and 1.20% with SnCl2 and SnBr2, respectively.

Combination of Counterion Size and Doping Concentration Determines the Electronic and Thermoelectric Properties of Semiconducting Polymers.

In both chemical and electrochemical doping of organic semiconductors (OSCs), a counterion, either from the electrolyte or ionized dopant, balances the charge introduced to the OSC. Despite the large influence of this counterion on OSC optical and electronic response, there remains substantial debate on how a fundamental parameter, ion size, impacts these properties. This work resolves much of this debate by accounting for two doping regimes. In the low-doping regime, the Coulomb binding energies between charge carriers on the OSC and the counterions are significant, and larger counterions lead to decreased Coulomb interactions, more delocalized charge carriers, and higher electrical conductivities. In the high-doping regime, the Coulomb binding energies become negligible due to the increased dielectric constant of the films and a smoothing of the energy landscape; thereby, the electrical conductivities depend primarily on the extent of morphological disorder in the OSC. Moreover, in regioregular poly(3-hexylthiophene), rr-P3HT, smaller counterions lead to greater bipolaron concentrations in the low-doping regime due to the increased Coulomb interactions. Emphasizing the impact of the counterion size, it is shown that larger counterions can lead to increased thermoelectric power factors for rr-P3HT.

Enhancing Thermal Stability of Perovskite Solar Cells through Thermal Transition and Thin Film Crystallization Engineering of Polymeric Hole Transport Layers.

Organic hole transport layers (HTLs) have been known to be susceptible to thermal stress, leading to poor long-term stability in perovskite solar cells (PSCs). We synthesized three 2,5-dialkoxy-substituted, 1,4-bis(2-thienyl)phenylene (TPT)-based conjugated polymers (CPs) linked with thiophene-based (thiophene (T) and thienothiophene (TT)) comonomers and evaluated them as HTLs in n-i-p PSCs. TPT-T (MB/C6), which has branched 2-methylbutyl and linear hexyl (MB/C6) side chains, emerged as a promising HTL candidate, enabling power conversion efficiencies (PCEs) greater than 15%. In addition, PSCs with this HTL showed an improvement in long-term stability at elevated temperatures of 65 °C when compared to those with the state-of-art HTL, 2,2',7,7'-tetrakis(N,N-p-dimethoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD). This improvement is ascribed to the lack of thermal transitions within the operational temperature range of PSCs for TPT-T (MB/C6), which is attributed to the relatively short branched side chains of this polymer. We propose that the elimination of thermal transitions below 200 °C leads to HTLs without cracking as-deposited and after conducting a stress test at 65 °C, which can serve as a new design guideline for HTL development.

Air-Stable Perylene Diimide Trimer Material for N-Type Organic Electrochemical Transistors.

A new method is reported to make air-stable n-type organic mixed ionic-electronic conductor (OMIEC) films for organic electrochemical transistors (OECTs) using a solution-processable small molecule helical perylene diimide trimer, hPDI[3]-C11. Alkyl side chains are attached to the conjugated core for processability and film making, which are then cleaved via thermal annealing. After the sidechains are removed, the hPDI[3] film becomes less hydrophobic, more ordered, and has a deeper lowest unoccupied molecular orbital (LUMO). These features provide improved ionic transport, greater electronic mobility, and increased stability in air and in aqueous solution. Subsequently, hPDI[3]-H is used as the active material in OECTs and a device with a transconductance of 44 mS, volumetric capacitance of ≈250 F cm-3, µC* value of 1 F cm-1 V-1 s-1, and excellent stability (> 5 weeks) is demonstrated. As proof of their practical applications, a hPDI[3]-H-based OECTs as a glucose sensor and electrochemical inverter is utilized. The approach of side chain removal after film formation charts a path to a wide range of molecular semiconductors to be used as stable, mixed ionic-electronic conductors.

New Chemical Dopant and Counterion Mechanism for Organic Electrochemical Transistors and Organic Mixed Ionic-Electronic Conductors.

Organic mixed ionic-electronic conductors (OMIECs) have varied performance requirements across a diverse application space. Chemically doping the OMIEC can be a simple, low-cost approach for adapting performance metrics. However, complex challenges, such as identifying new dopant materials and elucidating design rules, inhibit its realization. Here, these challenges are approached by introducing a new n-dopant, tetrabutylammonium hydroxide (TBA-OH), and identifying a new design consideration underpinning its success. TBA-OH behaves as both a chemical n-dopant and morphology additive in donor acceptor co-polymer naphthodithiophene diimide-based polymer, which serves as an electron transporting material in organic electrochemical transistors (OECTs). The combined effects enhance OECT transconductance, charge carrier mobility, and volumetric capacitance, representative of the key metrics underpinning all OMIEC applications. Additionally, when the TBA+ counterion adopts an "edge-on" location relative to the polymer backbone, Coulombic interaction between the counterion and polaron is reduced, and polaron delocalization increases. This is the first time such mechanisms are identified in doped-OECTs and doped-OMIECs. The work herein therefore takes the first steps toward developing the design guidelines needed to realize chemical doping as a generic strategy for tailoring performance metrics in OECTs and OMIECs.

Holistic energy landscape management in 2D/3D heterojunction via molecular engineering for efficient perovskite solar cells.

Constructing two-dimensional (2D) perovskite atop of 3D with energy landscape management is still a challenge in perovskite photovoltaics. Here, we report a strategy through designing a series of π-conjugated organic cations to construct stable 2D perovskites and to realize delicate energy level tunability at 2D/3D heterojunctions. As a result, the hole transfer energy barriers can be reduced both at heterojunctions and within 2D structures, and the preferable work function shift reduces charge accumulation at interface. Leveraging these insights and also benefitted from the superior interface contact between conjugated cations and poly(triarylamine) (PTAA) hole transporting layer, a solar cell with power conversion efficiency of 24.6% has been achieved, which is the highest among PTAA-based n-i-p devices to the best of our knowledge. The devices exhibit greatly enhanced stability and reproducibility. This approach is generic to several hole transporting materials, offering opportunities to realize high efficiency without using the unstable Spiro-OMeTAD.

Tailoring Molecular-Scale Contact at the Perovskite/Polymeric Hole-Transporting Material Interface for Efficient Solar Cells.

Perovskite solar cells (PSCs) have delivered a power conversion efficiency (PCE) of more than 25% and incorporating polymers as hole-transporting layers (HTLs) can further enhance the stability of devices toward the goal of commercialization. Among the various polymeric hole-transporting materials, poly(triaryl amine) (PTAA) is one of the promising HTL candidates with good stability; however, the hydrophobicity of PTAA causes problematic interfacial contact with the perovskite, limiting the device performance. Using molecular side-chain engineering, a uniform 2D perovskite interlayer with conjugated ligands, between 3D perovskites and PTAA is successfully constructed. Further, employing conjugated ligands as cohesive elements, perovskite/PTAA interfacial adhesion is significantly improved. As a result, the thin and lateral extended 2D/3D heterostructure enables as-fabricated PTAA-based PSCs to achieve a PCE of 23.7%, improved from the 18% of reference devices. Owing to the increased ion-migration energy barrier and conformal 2D coating, unencapsulated devices with the new ligands exhibit both superior thermal stability under 60 °C heating and moisture stability in ambient conditions.

Engineering ligand reactivity enables high-temperature operation of stable perovskite solar cells.

Perovskite solar cells (PSCs) consisting of interfacial two- and three-dimensional heterostructures that incorporate ammonium ligand intercalation have enabled rapid progress toward the goal of uniting performance with stability. However, as the field continues to seek ever-higher durability, additional tools that avoid progressive ligand intercalation are needed to minimize degradation at high temperatures. We used ammonium ligands that are nonreactive with the bulk of perovskites and investigated a library that varies ligand molecular structure systematically. We found that fluorinated aniliniums offer interfacial passivation and simultaneously minimize reactivity with perovskites. Using this approach, we report a certified quasi-steady-state power-conversion efficiency of 24.09% for inverted-structure PSCs. In an encapsulated device operating at 85°C and 50% relative humidity, we document a 1560-hour T85 at maximum power point under 1-sun illumination.

Suppressing phase disproportionation in quasi-2D perovskite light-emitting diodes.

Electroluminescence efficiencies and stabilities of quasi-two-dimensional halide perovskites are restricted by the formation of multiple-quantum-well structures with broad and uncontrollable phase distributions. Here, we report a ligand design strategy to substantially suppress diffusion-limited phase disproportionation, thereby enabling better phase control. We demonstrate that extending the π-conjugation length and increasing the cross-sectional area of the ligand enables perovskite thin films with dramatically suppressed ion transport, narrowed phase distributions, reduced defect densities, and enhanced radiative recombination efficiencies. Consequently, we achieved efficient and stable deep-red light-emitting diodes with a peak external quantum efficiency of 26.3% (average 22.9% among 70 devices and cross-checked) and a half-life of ~220 and 2.8 h under a constant current density of 0.1 and 12 mA/cm2, respectively. Our devices also exhibit wide wavelength tunability and improved spectral and phase stability compared with existing perovskite light-emitting diodes. These discoveries provide critical insights into the molecular design and crystallization kinetics of low-dimensional perovskite semiconductors for light-emitting devices.