Charge Extraction Layers Research Articles

Fast-Growth Polymer: Fullerene Bulk-Heterojunction Thin Films for Efficient Organic Photovoltaics.

The bulk-heterojunction (BHJ) system that uses a π-conjugated polymer as an electron donor, and a fullerene derivative as an electron acceptor, is widely used in organic solar cells (OSCs) to facilitate efficient charge separation and extraction. However, the conventional BHJ system still suffers from unwanted phase segregation caused by the existence of significant differences in surface energy between the two BHJ components and the charge extraction layer during film formation. In the present work, we demonstrate a sophisticated control of fast film-growth kinetics that can be used to achieve a uniform distribution of donor and acceptor materials in the BHJ layer of OSCs without undesirable phase separation. Our approach involves depositing the BHJ solution onto a spinning substrate, thus inducing rapid evaporation of the solvent during BHJ film formation. The fast-growth process prevents the fullerene derivative from migrating toward the charge extraction layer, thereby enabling a homogeneous distribution of the fullerene derivative within the BHJ film. The OSCs based on the fast-growth BHJ thin film are found to exhibit substantial increases in JSC, fill factor, and a PCE up to 11.27 mA/cm2, 66%, and 4.68%, respectively; this last value represents a remarkable 17% increase in PCE compared to that of conventional OSCs.

Efficient Silicon Solar Cells through Organic Self‐Assembled Monolayers as Electron Selective Contacts

AbstractEffective charge carrier‐selective contacts are a crucial component of high‐performance crystalline silicon (c‐Si) solar cells. Organic materials deposited via self‐assembly on the c‐Si surface are promising candidates for simplified, scalable, and cost‐effective processing of charge extraction layers. This study investigates the application of nPACz self‐assembled monolayers (SAMs), based on carbazole and phosphonic acid groups, where n (= 2, 4, or 6) is the aliphatic chain length, to facilitate electron extraction in c‐Si solar cells by tuning the work function of aluminum (Al) at the rear contact. So far, these SAM molecules are mainly applied as the hole‐selective layer in state‐of‐the‐art perovskite and organic solar cells, via anchoring on a metal oxide electrode. Here, by inserting 2PACz between amorphous silicon passivated c‐Si and Al, an electron‐selective contact with a contact resistivity of 65 mΩ cm2 is achieved and a power conversion efficiency of 21.4% with an open‐circuit voltage of 725 mV and a fill factor of 79.2% is demonstrated. Although the 2PACz displays some instability in this study, its initial performance is comparable to those achieved with conventionally used n‐type amorphous silicon. This study highlights the potential of solution‐processable organic SAMs in forming carrier‐selective contacts for c‐Si heterojunction solar cells.

Doping of Mesoscopic Charge Extraction Layers Enables the Design of Long-Time Stable Organic Solar Cells

Doping of Mesoscopic Charge Extraction Layers Enables the Design of Long-Time Stable Organic Solar Cells

Stabilized hole-selective layer for high-performance inverted p-i-n perovskite solar cells.

P-i-n geometry perovskite solar cells (PSCs) offer simplified fabrication, greater amenability to charge extraction layers, and low-temperature processing over n-i-p counterparts. Self-assembled monolayers (SAMs) can enhance the performance of p-i-n PSCs but ultrathin SAMs can be thermally unstable. We report a thermally robust hole-selective layer comprised of nickel oxide (NiOx) nanoparticle film with a surface-anchored (4-(3,11-dimethoxy-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonic acid (MeO-4PADBC) SAM that can improve and stabilize the NiOx/perovskite interface. The energetic alignment and favorable contact and binding between NiOx/MeO-4PADBC and perovskite reduced the voltage deficit of PSCs with various perovskite compositions and led to strong interface toughening effects under thermal stress. The resulting 1.53-electron-volt devices achieved 25.6% certified power conversion efficiency and maintained >90% of their initial efficiency after continuously operating at 65 degrees Celsius for 1200 hours under 1-sun illumination.

Characterizing the Influence of Charge Extraction Layers on the Performance of Triple‐Cation Perovskite Solar Cells

AbstractSelecting suitable charge transport layers and suppressing non‐radiative recombination at interfaces with the absorber layer is vital for maximizing the efficiency of halide perovskite solar cells. In this study, high‐quality perovskite thin films and devices are fabricated with different fullerene‐based electron transport layers and different self‐assembled monolayers as hole transport layers. Then, a comparative study of a significant variety of different electrical, optical, and photoemission‐based characterization techniques is performed to quantify the properties of the solar cells, individual layers, and, importantly, the interfaces between them. In addition, the limitations and problems of the different measurements, the insights gained by combining different methods, and the different strategies for extracting information from the experimental raw data, are highlighted.

Ionic Accumulation as a Diagnostic Tool in Perovskite Solar Cells: Characterizing Band Alignment with Rapid Voltage Pulses.

Despite record-breaking devices, interfaces in perovskite solar cells are still poorly understood, inhibiting further progress. Their mixed ionic-electronic nature results in compositional variations at the interfaces, depending on the history of externally applied biases. This makes it difficult to measure the band energy alignment of charge extraction layers accurately. As a result, the field often resorts to a trial-and-error process to optimize these interfaces. Current approaches are typically carried out in a vacuum and on incomplete cells, hence values may not reflect those found in working devices. To address this, a pulsed measurement technique characterizing the electrostatic potential energy drop across the perovskite layer in a functioning device is developed. This method reconstructs the current-voltage (JV) curve for a range of stabilization biases, holding the ion distribution "static" during subsequent rapid voltage pulses. Two different regimes are observed: at low biases, the reconstructed JV curve is "s-shaped", whereas, at high biases, typical diode-shaped curves are returned. Using drift-diffusion simulations, it is demonstrated that the intersection of the two regimes reflectsthe band offsets at the interfaces. This approach effectively allows measurements of interfacial energy level alignment in a complete device under illumination and without the need for expensive vacuum equipment.

Nanodiamonds as Charge Extraction Layer in Organic Solar Cells: The Impact of the Nanodiamond Surface Chemistry

Diamond nanoparticles so‐called nanodiamonds (NDs) have recently experienced raising scientific interest due to interesting optical and electronic properties, nontoxicity, biocompatibility, and large surface area. Another significant feature of NDs is the versatility of the surface chemistry, where various functional groups can be attached. This provides an excellent platform for adjusting NDs properties and functions for many applications including in photovoltaic devices. Herein, high‐pressure high‐temperature (HPHT) NDs are tested as charge extraction material in organic solar cells using various surface chemistries: as‐received (HPHT ND‐ar), oxidized (HPHT ND‐O), and hydrogenated (HPHT ND‐O‐H) NDs. Despite the high work function values (≈5.3 eV) of HPHT ND‐ar and HPHT ND‐O, which make these materials normally suitable for hole extraction, devices made with them failed. In contrast, the work function decreases upon hydrogenation (≈4.5 eV) of the beforehand oxidized NDs, making them interesting for electron extraction. By employing such HPHT ND‐O‐H for electron extraction layers, PBDB‐T:ITIC‐based devices reach 77%, while PM6:Y6‐based devices reach even 85% of the performance when process on standard ZnO electron transport layers. Improvement of the film‐forming qualities of this new electron extraction material is expected to further improve the performance.

Prospects for Tin-Containing Halide Perovskite Photovoltaics.

Tin-containing metal halide perovskites have enormous potential as photovoltaics, both in narrow band gap mixed tin-lead materials for all-perovskite tandems and for lead-free perovskites. The introduction of Sn(II), however, has significant effects on the solution chemistry, crystallization, defect states, and other material properties in halide perovskites. In this perspective, we summarize the main hurdles for tin-containing perovskites and highlight successful attempts made by the community to overcome them. We discuss important research directions for the development of these materials and propose some approaches to achieve a unified understanding of Sn incorporation. We particularly focus on the discussion of charge carrier dynamics and nonradiative losses at the interfaces between perovskite and charge extraction layers in p-i-n cells. We hope these insights will aid the community to accelerate the development of high-performance, stable single-junction tin-containing perovskite solar cells and all-perovskite tandems.

Effect of ground state charge transfer and photoinduced charge separation on the energy level alignment at metal halide perovskite/organic charge transport layer interfaces

One of the most promising routes for the future fabrication of solution-processable high-performance solar cells is to employ metal halide perovskites as photoactive material combined with organic semiconductors as charge extraction layers. An essential requirement to obtain high device performance is a proper energy level alignment across the device interfaces. Here, we investigate the interface between a triple cation perovskite and a prototypical electron acceptor molecule. Photoemission spectroscopy reveals a ground state charge transfer induced band bending on either side of the junction, which significantly alters the charge extraction barriers as compared to assumed vacuum level alignment and flat-band conditions. In addition, we demonstrate that upon white light illumination, the energy levels of the organic layer exhibit rigid shifts by up to 0.26 eV with respect to those of the perovskite, revealing a non-constant energy offset between the frontier energy levels of the two materials. Such level shifts of the organic transport layer are fully reversible upon switching on/off the light, indicating an electrostatic origin of this phenomenon caused by unbalanced distribution of photogenerated charge carriers. We therefore stress the importance of determining the energy level alignment at perovskite-based interfaces not only in the electronic ground state (dark) but also under device operating conditions (operando) to enable for a reliable correlation with the device performance.

Investigations on photovoltaic material absorptivity using hyperspectral photoluminescence excitation imaging

Photoluminescence imaging has become a standard method to characterize solar cells. However, performing some quantitative analysis of this technique requires the assumption of uniform local absorptivity, which cannot be directly measured using traditional methods. This study presents a novel approach to measure the local relative absorptivity over a broad spectral range for a perovskite absorber deposited on a charge extraction layer and an electrode. By analyzing the photoluminescence intensity as a function of the incident photon energy, we were able to determine the relative absorptivity of the incident light above the bandgap energy. Additionally, luminescence spectra allow us to accurately assess the absorptivity near the bandgap energy from the reciprocity between absorption and emission. Reflectivity measurements were also performed to further understand the possible limitations of our experiment and to discuss our results. Finally, this method was able to distinguish between variations in the photoluminescence response caused by slight differences in the local film thickness and changes in the local carrier lifetime.

Complex refractive indices of Spiro-TTB and C60 for optical analysis of perovskite silicon tandem solar cells.

Evaporated charge extraction layers from organic molecular materials are vital in perovskite-based solar cells. For opto-electronic device optimization their complex refractive indices must be known for the visible and near infrared wavelength regime; however, accurate determination from thin organic films below 50 nm can be challenging. By combining spectrophotometry, variable angle spectroscopic ellipsometry, and X-ray reflectivity with an algorithm that simultaneously fits all available spectra, the complex refractive index of evaporated Spiro-TTB and C60 layers is determined with high accuracy. Based on that, an optical losses analysis for perovskite silicon solar cells shows that 15 nm of Spiro-TTB in the front of a n-i-p device reduces current by only 0.1 mA/cm2, compared to a substantial loss of 0.5 mA/cm2 due to 15 nm of C60 in a p-i-n device. Optical device simulation predicts high optical generation current densities of 19.7 and 20.1 mA/cm2 for the fully-textured, module-integrated p-i-n and n-i-p devices, respectively.

Flash‐Lamp Processing of Charge Extraction Layers for Polymer Solar Cells

AbstractThermal annealing (TA) is one of the most used processing techniques for the fabrication of polymer solar cells. The method is not only used to dry solution‐processed films but also for improving the electrical conductivity and the optical absorption of the materials after coating as films. Its use is questionable in combination with high throughput manufacturing techniques such as roll‐to‐roll large‐scale production since annealing times of several minutes already put up high demands on oven lengths. Furthermore, the commonly used flexible substrates are not compatible with high processing temperatures. Therefore, there is a need for more rapid treatment techniques, which do not negatively affect the plastic substrate. Herein, it is successfully demonstrated that flash lamp annealing (FLA) can be a valid alternative to TA. The FLA technique is applied at various pulse durations and thus energy doses to PEDOT:PSS and SnO2 films used as charge extraction layers in conventional and inverted solar cells architectures. In combination with PM6:Y6 photoactive layer, the obtained device's performances are comparable or even better than the devices treated with the classical TA on a hotplate. In terms of energy efficiency, the FLA is clearly more efficient than the TA, even at the size of prototypes.

Dipole Formation at Active Materials/P(NDI3N‐T‐Br) Interface in Organic‐Based Photovoltaic

AbstractIn this work, a new potential electron transport material, poly[(N,N'‐bis(3‐(N,N‐dimethyl)‐N‐ethylammonium)propyl)naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl)‐alt‐2,5‐thiophene)]dibromide P(NDI3N‐T‐Br), is studied in conjunction with active layers formed by poly[2,3‐bis(3‐octyloxyphenyl)quinoxaline‐5,8‐diyl‐alt‐thiophene‐2,5‐diyl] (TQ1) and poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)] (N2200). The energy levels of the active layer TQ1 and N2200 in contact with P(NDI3N‐T‐Br) have been determined by photoelectron spectroscopy. The dipole formed at the interface of the active layer and P(NDI3N‐T‐Br) is significantly different to the dipole formed at the respective interface with ITO. The dipole between the active layer and P(NDI3N‐T‐Br) blocks the transfer of holes from TQ1 to P(NDI3N‐T‐Br) which is desired, but the hole still transfers from the N2200 to P(NDI3N‐T‐Br) due to N2200 being an electron acceptor. This energy level alignment meets the expectation of using P(NDI3N‐T‐Br) as an interface layer in blocking the hole transfer to the interface layer when TQ1:N2200 is used in the active layer. The present work provides an understanding of P(NDI3N‐T‐Br) as charge extraction layer and indicates its potential to be used in organic photovoltaics.

Interface engineering of antimony selenide solar cells: a review on the optimization of energy band alignments

Earth-abundant and environmentally benign antimony selenide (Sb2Se3) has emerged as a promising light-harvesting absorber for thin-film photovoltaic (PV) devices due to its high absorption coefficient, nearly ideal bandgap for PV applications, excellent long-term stability, and intrinsically benign boundaries if properly aligned on the substrate. The record power conversion efficiency of Sb2Se3 solar cells has currently reached 9.2%, however, it is far lower than the champion efficiencies of other chalcogenide thin-film solar cells such as CdTe (22.1%) and Cu(In,Ga)Se2 (23.35%). The inferior device performance of Sb2Se3 thin-film solar cells mainly results from a large open-circuit voltage deficit, which is strongly related to the interface recombination loss. Accordingly, constructing proper band alignments between Sb2Se3 and neighboring charge extraction layers through interface engineering to reduce carrier recombination losses is one of the key strategies to achieving high-efficiency Sb2Se3 solar cells. In this review, the fundamental properties of Sb2Se3 thin films, and the recent progress made in Sb2Se3 solar cells are outlined, with a special emphasis on the optimization of energy band alignments through the applications of electron-transporting layers and hole-transporting layers. Furthermore, the potential research directions to overcome the bottlenecks of Sb2Se3 thin-film solar cell performance are also presented.

Revealing fundamentals of charge extraction in photovoltaic devices through potentiostatic photoluminescence imaging

Revealing fundamentals of charge extraction in photovoltaic devices through potentiostatic photoluminescence imaging

Probing Ultrafast Interfacial Carrier Dynamics in Metal Halide Perovskite Films and Devices by Transient Reflection Spectroscopy.

Interfaces in metal halide perovskite (MHP) solar cells cause carrier recombination and thereby reduce their power conversion efficiency. Here, ultrafast (picosecond to nanosecond) transient reflection (TR) spectroscopy has been used to probe interfacial carrier dynamics in thin films of the reference MHP MAPbI3 and state-of-the-art (Cs0.15MA0.15FA0.70)Pb(Br0.20I0.80)3 (CsFAMA). First, MAPbI3 films in contact with fullerene-based charge extraction layers (CTLs) in the presence and absence of LiF used as an interlayer (ITL) were studied. To quantify and discriminate between interface-induced and bulk carrier recombination, we employed a one-dimensional diffusion and recombination model. The interface-induced carrier recombination velocity was found to be 1229 ± 78 cm s-1 in nonpassivated MAPbI3 films, which was increased to 2248 ± 75 cm s-1 when MAPbI3 interfaced directly with C60, whereas it was reduced to 145 ± 63 cm s-1 when inserting a 1 nm thin LiF interlayer between MAPbI3 and C60, in turn improving the open-circuit voltage of devices by 33 mV. Second, the effect of surface and grain boundary passivation by PhenHCl in CsFAMA was revealed. Here, the recombination velocity decreased from 605 ± 52 to 0.16 ± 5.28 and 7.294 ± 34.5 cm s-1, respectively. The approach and data analysis presented here are immediately applicable to other perovskite/interlayer/CTL interfaces and passivation protocols, and they add to our understanding of the impact of surfaces and interfaces in MHP-based thin films on carrier recombination and device efficiency.

Perovskite-organic tandem solar cells with indium oxide interconnect.

Multijunction solar cells can overcome the fundamental efficiency limits of single-junction devices. The bandgap tunability of metal halide perovskite solar cells renders them attractive for multijunction architectures1. Combinations with silicon and copper indium gallium selenide (CIGS), as well as all-perovskite tandem cells, have been reported2-5. Meanwhile, narrow-gap non-fullerene acceptors have unlocked skyrocketing efficiencies for organic solar cells6,7. Organic and perovskite semiconductors are an attractive combination, sharing similar processing technologies. Currently, perovskite-organic tandems show subpar efficiencies and are limited by the low open-circuit voltage (Voc) of wide-gap perovskite cells8 and losses introduced by the interconnect between the subcells9,10. Here we demonstrate perovskite-organic tandem cells with an efficiency of 24.0per cent (certified 23.1per cent) and a high Voc of 2.15 volts. Optimized charge extraction layers afford perovskite subcells with an outstanding combination of high Voc and fill factor. The organic subcells provide a high external quantum efficiency in the near-infrared and, in contrast to paradigmatic concerns about limited photostability of non-fullerene cells11, show an outstanding operational stability if excitons are predominantly generated on the non-fullerene acceptor, which is the case in our tandems. The subcells are connected by an ultrathin (approximately 1.5 nanometres) metal-like indium oxide layer with unprecedented low optical/electrical losses. This work sets a milestone for perovskite-organic tandems, which outperform the best p-i-n perovskite single junctions12 and are on a par with perovskite-CIGS and all-perovskite multijunctions13.

In Situ Ethanolamine ZnO Nanoparticle Passivation for Perovskite Interface Stability and Highly Efficient Solar Cells.

Zinc oxide (ZnO) has interesting optoelectronic properties, but suffers from chemical instability when in contact with perovskite interfaces; hence, the perovskite deposited on the top degrades promptly. Surface passivation strategies alleviate this instability issue; however, synthesis to passivate ZnO nanoparticles (NPs) in situ has received less attention. Here, a new synthesis at low temperatures with an ethanolamine post treatment has been developed. By using ZnO NPs prepared with ethanolamine and butanol (BuOH), (E-ZnO), the stability of the FA0.9Cs0.1PbI3 (FACsPI)–ZnO interface was achieved, with a photoconversion efficiency of >18%. Impedance spectroscopy demonstrates that the recombination at the interface was reduced in the system with E-ZnO/perovskite compared to common SnO2/perovskite and that the quality of the perovskite on the top is clearly due to the ZnO in situ passivation with ethanolamine. This work extends the use of E-ZnO as an n-type charge extraction layer and demonstrates its feasibility with methylammonium perovskite. Moreover, this study paves the way for other in situ passivation methods with different target molecules, along with new insights regarding the perovskite interface rearrangement when in contact with the modified electron transport layer (ETL).

Decomposition of Organic Perovskite Precursors on MoO3: Role of Halogen and Surface Defects.

Despite the rapid progress in perovskite solar cells, their commercialization is still hindered by issues regarding long-term stability, which can be strongly affected by metal oxide-based charge extraction layers next to the perovskite material. With MoO3 being one of the most successful hole transport layers in organic photovoltaics, the disastrous results of its combination with perovskite films came as a surprise but was soon attributed to severe chemical instability at the MoO3/perovskite interface. To discover the atomistic origin of this instability, we combine density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) measurements to investigate the interaction of MoO3 with the perovskite precursors MAI, MABr, FAI, and FABr. From DFT calculations we suggest a scenario that is based upon oxygen vacancies playing a key role in interface degradation reactions. Not only do these vacancies promote decomposition reactions of perovskite precursors, but they also constitute the reaction centers for redox reactions leading to oxidation of the halides and reduction of Mo. Specifically iodides are proposed to be reactive, while bromides do not significantly affect the oxide. XPS measurements reveal a severe reduction of Mo and a loss of the halide species when the oxide is interfaced with I-containing precursors, which is consistent with the proposed scenario. In line with the latter, experimentally observed effects are much less pronounced in case of Br-containing precursors. We further find that the reactivity of the MoO3 substrate can be moderated by reducing the number of oxygen vacancies through a UV/ozone treatment, though it cannot be fully eliminated.

Oxygen-induced degradation in AgBiS2 nanocrystal solar cells.

AgBiS2 nanocrystal solar cells are among the most sustainable emerging photovoltaic technologies. Their environmentally-friendly composition and low energy consumption during fabrication make them particularly attractive for future applications. However, much remains unknown about the stability of these devices, in particular under operational conditions. In this study, we explore the effects of oxygen and light on the stability of AgBiS2 nanocrystal solar cells and identify its dependence on the charge extraction layers. Normally, the rate of oxygen-induced degradation of nanocrystals is related to their ligands, which determine the access sites by steric hindrance. We demonstrate that the ligands, commonly used in AgBiS2 solar cells, also play a crucial chemical role in the oxidation process. Specifically, we show that the tetramethylammonium iodide ligands enable their oxidation, leading to the formation of bismuth oxide and silver sulphide. Additionally, the rate of oxidation is impacted by the presence of water, often present at the surface of the ZnO electron extraction layer. Moreover, the degradation of the organic hole extraction layer also impacts the overall device stability and the materials' photophysics. The understanding of these degradation processes is necessary for the development of mitigation strategies for future generations of more stable AgBiS2 nanocrystal solar cells.