Surface doping of rubrene single crystals by molecular electron donors and acceptors.

The surface molecular doping of organic semiconductors can play an important role in the development of organic electronic or optoelectronic devices. Single-crystal rubrene remains a leading molecular candidate for applications in electronics due to its high hole mobility. In parallel, intensive research into the fabrication of flexible organic electronics requires the careful design of functional interfaces to enable optimal device characteristics. To this end, the present work seeks to understand the effect of surface molecular doping on the electronic band structure of rubrene single crystals. Our angle-resolved photoemission measurements reveal that the Fermi level moves in the band gap of rubrene depending on the direction of surface electron-transfer reactions with the molecular dopants, yet the valence band dispersion remains essentially unperturbed. This indicates that surface electron-transfer doping of a molecular single crystal can effectively modify the near-surface charge density, while retaining good charge-carrier mobility.

Electronic properties of metal halide perovskites and their interfaces: the basics.

We have witnessed tremendous progress of metal halide perovskite (MHP)-based optoelectronic devices, especially in the field of photovoltaics. Despite intensive research in the past few years, questions still remain regarding their fundamental optoelectronic properties, among which the electronic properties exhibit an interplay of numerous phenomena that deserve serious scrutiny. In this Focus article, we aim to provide a contemporary understanding of the unique electronic properties that has been resolved by the community. First introducing some of the basic concepts established in semiconductor physics, the intrinsic and extrinsic electronic properties of the MHPs are disentangled and explained. With this, the complex interplay of interface-, dopant-, and surface state-induced electronic states in determining the electrostatic landscape in the material can be comprehended, and the energy level alignment in device architectures more reliably assessed.

Photoinduced Energy-Level Realignment at Interfaces between Organic Semiconductors and Metal-Halide Perovskites.

In contrast to the common conception that the interfacial energy-level alignment is affixed once the interface is formed, we demonstrate that heterojunctions between organic semiconductors and metal-halide perovskites exhibit huge energy-level realignment during photoexcitation. Importantly, the photoinduced level shifts occur in the organic component, including the first molecular layer in direct contact with the perovskite. This is caused by charge-carrier accumulation within the organic semiconductor under illumination and the weak electronic coupling between the junction components.

The Schottky-Mott Rule Expanded for Two-Dimensional Semiconductors: Influence of Substrate Dielectric Screening.

A comprehensive understanding of the energy level alignment mechanisms between two-dimensional (2D) semiconductors and electrodes is currently lacking, but it is a prerequisite for tailoring the interface electronic properties to the requirements of device applications. Here, we use angle-resolved direct and inverse photoelectron spectroscopy to unravel the key factors that determine the level alignment at interfaces between a monolayer of the prototypical 2D semiconductor MoS2 and conductor, semiconductor, and insulator substrates. For substrate work function (Φsub) values below 4.5 eV we find that Fermi level pinning occurs, involving electron transfer to native MoS2 gap states below the conduction band. For Φsub above 4.5 eV, vacuum level alignment prevails but the charge injection barriers do not strictly follow the changes of Φsub as expected from the Schottky-Mott rule. Notably, even the trends of the injection barriers for holes and electrons are different. This is caused by the band gap renormalization of monolayer MoS2 by dielectric screening, which depends on the dielectric constant (εr) of the substrate. Based on these observations, we introduce an expanded Schottky-Mott rule that accounts for band gap renormalization by εr -dependent screening and show that it can accurately predict charge injection barriers for monolayer MoS2. It is proposed that the formalism of the expanded Schottky-Mott rule should be universally applicable for 2D semiconductors, provided that material-specific experimental benchmark data are available.

Type-I Energy Level Alignment at the PTCDA-Monolayer MoS2 Interface Promotes Resonance Energy Transfer and Luminescence Enhancement.

Van der Waals heterostructures consisting of 2D semiconductors and conjugated molecules are of increasing interest because of the prospect of a synergistic enhancement of (opto)electronic properties. In particular, perylenetetracarboxylic dianhydride (PTCDA) on monolayer (ML)-MoS2 has been identified as promising candidate and a staggered type-II energy level alignment and excited state interfacial charge transfer have been proposed. In contrast, it is here found with inverse and direct angle resolved photoelectron spectroscopy that PTCDA/ML-MoS2 supported by insulating sapphire exhibits a straddling type-I level alignment, with PTCDA having the wider energy gap. Photoluminescence (PL) and sub-picosecond transient absorption measurements reveal that resonance energy transfer, i.e., electron-hole pair (exciton) transfer, from PTCDA to ML-MoS2 occurs on a sub-picosecond time scale. This gives rise to an enhanced PL yield from ML-MoS2 in the heterostructure and an according overall modulation of the photoresponse. These results underpin the importance of a precise knowledge of the interfacial electronic structure in order to understand excited state dynamics and to devise reliable design strategies for optimized optoelectronic functionality in van der Waals heterostructures.

Mechanism and Timescales of Reversible p-Doping of Methylammonium Lead Triiodide by Oxygen.

Understanding and controlling the energy level alignment at interfaces with metal halide perovskites (MHPs) is essential for realizing the full potential of these materials for use in optoelectronic devices. To date, however, the basic electronic properties of MHPs are still under debate. Particularly, reported Fermi level positions in the energy gap vary from indicating strong n- to strong p-type character for nominally identical materials, raising serious questions about intrinsic and extrinsic defects as dopants. ​In this work, photoemission experiments demonstrate that thin films of the prototypical methylammonium lead triiodide (MAPbI3 ) behave like an intrinsic semiconductor in the absence of oxygen. Oxygen is then shown to be able to reversibly diffuse into and out of the MAPbI3 bulk, requiring rather long saturation timescales of ≈1 h (in: ambient air) and over 10 h (out: ultrahigh vacuum), for few 100 nm thick films. Oxygen in the bulk leads to pronounced p-doping, positioning the Fermi level universally ≈0.55 eV above the valence band maximum. The key doping mechanism is suggested to be molecular oxygen substitution of iodine vacancies, supported by density functional theory calculations. This insight rationalizes previous and future electronic property studies of MHPs and calls for meticulous oxygen exposure protocols.

Temperature-Dependent Electronic Ground-State Charge Transfer in van der Waals Heterostructures.

Electronic charge rearrangement between components of a heterostructure is the fundamental principle to reach the electronic ground state. It is acknowledged that the density of state distribution of the components governs the amount of charge transfer, but a notable dependence on temperature is not yet considered, particularly for weakly interacting systems. Here, it is experimentally observed that the amount of ground-state charge transfer in a van der Waals heterostructure formed by monolayer MoS2 sandwiched between graphite and a molecular electron acceptor layer increases by a factor of 3 when going from 7 K to room temperature. State-of-the-art electronic structure calculations of the full heterostructure that accounts for nuclear thermal fluctuations reveal intracomponent electron-phonon coupling and intercomponent electronic coupling as the key factors determining the amount of charge transfer. This conclusion is rationalized by a model applicable to multicomponent van der Waals heterostructures.

Position-locking of volatile reaction products by atmosphere and capping layers slows down photodecomposition of methylammonium lead triiodide perovskite.

The remarkable progress of metal halide perovskites in photovoltaics has led to the power conversion efficiency approaching 26%. However, practical applications of perovskite-based solar cells are challenged by the stability issues, of which the most critical one is photo-induced degradation. Bare CH3NH3PbI3 perovskite films are known to decompose rapidly, with methylammonium and iodine as volatile species and residual solid PbI2 and metallic Pb, under vacuum under white light illumination, on the timescale of minutes. We find, in agreement with previous work, that the degradation is non-uniform and proceeds predominantly from the surface, and that illumination under N2 and ambient air (relative humidity 20%) does not induce substantial degradation even after several hours. Yet, in all cases the release of iodine from the perovskite surface is directly identified by X-ray photoelectron spectroscopy. This goes in hand with a loss of organic cations and the formation of metallic Pb. When CH3NH3PbI3 films are covered with a few nm thick organic capping layer, either charge selective or non-selective, the rapid photodecomposition process under ultrahigh vacuum is reduced by more than one order of magnitude, and becomes similar in timescale to that under N2 or air. We conclude that the light-induced decomposition reaction of CH3NH3PbI3, leading to volatile methylammonium and iodine, is largely reversible as long as these products are restrained from leaving the surface. This is readily achieved by ambient atmospheric pressure, as well as a thin organic capping layer even under ultrahigh vacuum. In addition to explaining the impact of gas pressure on the stability of this perovskite, our results indicate that covalently "locking" the position of perovskite components at the surface or an interface should enhance the overall photostability.

Band Alignment Engineering between Planar SnO2 and Halide Perovskites via Two-Step Annealing.

Managing defects in SnO2 is critical for improving the power conversion efficiency (PCE) of halide perovskite-based solar cells. However, typically reported SnO2-based perovskite solar cells have inherent defects in the SnO2 layer, which lead to a lower PCE and hysteresis. Here, we report that a dual-coating approach for SnO2 with different annealing temperatures can simultaneously form a SnO2 layer with high crystallinity and uniform surface coverage. Along with these enhanced physical properties, the dual-coated SnO2 layer shows favorable band alignment with a mixed halide perovskite. After careful optimization of the dual-coating method, the average PCE of the perovskite solar cell based on the dual-coated SnO2 layer increases from 18.07 to 19.23% with a best-performing cell of 20.03%. Note that a facile two-step coating and annealing method can open new avenues to develop SnO2-based perovskite solar cells with stabilized and improved photovoltaic performances.

Electronic Structure of Nonionic Surfactant-Modified PEDOT:PSS and Its Application in Perovskite Solar Cells with Reduced Interface Recombination.

The interfacial properties of organolead halide perovskite solar cells (PSCs) affect the exciton and charge-transport dynamics significantly. Thus, proper modification of the interfaces between perovskite and charge-transport layers is an efficient method to increase the power conversion efficiency (PCE) of PSCs. In this work, we explore the effect of a nonionic surfactant, that is, Triton X-100 (TX) additive, in the poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) hole-transport layer. The electronic structure of TX-modified PEDOT:PSS is investigated with ultraviolet/X-ray photoelectron spectroscopy and X-ray absorption spectroscopy with various TX concentrations. The surface of the TX-modified PEDOT:PSS layer showed high TX content, and thus the semimetallic properties of PEDOT:PSS were suppressed conspicuously by its insulating nature. With the TX-modified PEDOT:PSS, the PCE of methylammonium lead iodide (MAPbI3) PSCs increased significantly. To elucidate the origin of the improved device performance, the electrical properties and photoluminescence were investigated comprehensively. Consequently, it was found that the TX additive inhibits interface recombination between PEDOT:PSS and MAPbI3, which is caused by the suppression of semimetallic properties of the PEDOT:PSS surface. Hence, we fabricated flexible PSCs successfully using a graphene electrode and TX-modified PEDOT:PSS.

Improved Stability of Interfacial Energy-Level Alignment in Inverted Planar Perovskite Solar Cells.

Even though poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been commonly used as a hole extraction layer (HEL) for p-i-n perovskite solar cells (PSCs), the cells' photovoltaic performance deteriorates because of the low and unstable work functions (WFs) of PEDOT:PSS versus those of a perovskite layer. To overcome this drawback, we synthesized a copolymer (P(SS- co-TFPMA)) ionomer consisting of PSS and tetrafluoropropylmethacrylate (TFPMA) as an alternative to conventional PEDOT:PSS. The PEDOT:P(SS- co-TFPMA) copolymer solution and its film exhibited excellent homogeneity and high phase stability compared with a physical mixture of TFPMA with PEDOT:PSS solution. During spin coating, a self-organized conducting PEDOT:P(SS- co-TFPMA) HEL evolved and the topmost PEDOT:P(SS- co-TFPMA) film showed a hydrophobic surface with a higher WF compared to that of the pristine PEDOT:PSS film because of its chemically bonded electron-withdrawing fluorinated functional groups. Interestingly, the WF of the conventional PEDOT:PSS film dramatically deteriorated after being coated with a perovskite layer, whereas the PEDOT:P(SS- co-TFPMA) film represented a relatively small influence. Because of the superior energy-level alignment between the HEL and a perovskite layer even after the contact, the open-circuit voltage, short-circuit current, and fill factor of the inverted planar p-i-n PSCs (IP-PSCs) with PEDOT:P(SS- co-TFPMA) were improved from 0.92 to 0.98 V, 18.96 to 19.66 mA/cm2, and 78.96 to 82.43%, respectively, resulting in a 15% improvement in the power conversion efficiency vs that of IP-PSCs with conventional PEDOT:PSS. Moreover, the IP-PSCs with PEDOT:P(SS- co-TFPMA) layer showed not only improved photovoltaic performance but also enhanced device stability due to hydrophobic surface of PEDOT:P(SS- co-TFPMA) film.

Rapid Formation of a Disordered Layer on Monoclinic BiVO4 : Co-Catalyst-Free Photoelectrochemical Solar Water Splitting.

A surface disordered layer is a plausible approach to improve the photoelectrochemical performance of TiO2 . However, the formation of a crystalline disordered layer in BiVO4 and its effectiveness towards photoelectrochemical water splitting has remained a big challenge. Here, we report a rapid solution process (within 5 s) that is able to form a disordered layer of a few nanometers thick on the surface of BiVO4 nanoparticles using a specific solution with a controllable reducing power. The disordered layer on BiVO4 alleviates charge recombination at the electrode-electrolyte interface and reduces the onset potential greatly, which in turn results in a photocurrent density of approximately 2.3 mA cm-2 at 1.23 V versus the reversible hydrogen electrode (RHE). This value is 2.1 times higher than that of bare BiVO4 . The enhanced photoactivity is attributed to the increased charge separation and transfer efficiencies, which resolve the intrinsic drawbacks of bare BiVO4 such as the short hole diffusion length of around 100 nm and poor surface oxygen evolution reactivity.

Unraveling the Charge Extraction Mechanism of Perovskite Solar Cells Fabricated with Two-Step Spin Coating: Interfacial Energetics between Methylammonium Lead Iodide and C60.

In organolead halide perovskite solar cells (PSCs), interfacial properties between the perovskite and charge transport layers are the critical factors governing charge extraction efficiency. In this study, the effect of interfacial energetics between two-step spin-coated methylammonium lead iodide (MAPbI3) with different methylammonium iodide (MAI) concentrations and C60 on the charge extraction efficiency is investigated. The electronic structures of perovskite films are significantly varied by the MAI concentrations due to the changes in the residual precursor and MA+ defect content. As compared to the optimum PSCs with 25 mg mL-1 MAI, PSCs with other MAI concentrations show significantly lower power conversion efficiencies and severe hysteresis. The energy level alignment at the C60/MAPbI3 interface determined by ultraviolet and inverse photoelectron spectroscopy measurements reveals the origin of distinct differences in device performances. The conduction band offset at the C60/MAPbI3 interface plays a crucial role in efficient charge extraction in PSCs.

Band-Tail Transport of CuSCN: Origin of Hole Extraction Enhancement in Organic Photovoltaics.

Copper thiocyanate (CuSCN) is known as a promising hole transport layer in organic photovoltaics (OPVs) due to its good hole conduction and exciton blocking abilities with high transparency. Despite its successful device applications, the origin of its hole extraction enhancement in OPVs has not yet been understood. Here, we investigated the electronic structure of CuSCN and the energy level alignment at the poly(3-hexylthiophene-2,5-diyl) (P3HT)/CuSCN/ITO interfaces using ultraviolet photoelectron spectroscopy. The band-tail states of CuSCN close to the Fermi level (EF) were observed at 0.25 eV below the EF, leading to good hole transport. The CuSCN interlayer significantly reduces the hole transport barrier between ITO and P3HT due to its high work function and band-tail states. The barrier reduction leads to enhanced current density-voltage characteristics of hole-dominated devices. These results provide the origin of hole-extraction enhancement by CuSCN and insights for further application.

Electron transport mechanism of bathocuproine exciton blocking layer in organic photovoltaics.

Efficient exciton management is a key issue to improve the power conversion efficiency of organic photovoltaics (OPVs). It is well known that the insertion of an exciton blocking layer (ExBL) having a large band gap promotes the efficient dissociation of photogenerated excitons at the donor-acceptor interface. However, the large band gap induces an energy barrier which disrupts the charge transport. Therefore, building an adequate strategy based on the knowledge of the true charge transport mechanism is necessary. In this study, the true electron transport mechanism of a bathocuproine (BCP) ExBL in OPVs is comprehensively investigated by in situ ultraviolet photoemission spectroscopy, inverse photoemission spectroscopy, density functional theory calculation, and impedance spectroscopy. The chemical interaction between deposited Al and BCP induces new states within the band gap of BCP, so that electrons can transport through these new energy levels. Localized trap states are also formed upon the Al-BCP interaction. The activation energy of these traps is estimated with temperature-dependent conductance measurements to be 0.20 eV. The Al-BCP interaction induces both transport and trap levels in the energy gap of BCP and their interplay results in the electron transport observed.