Two strategies to enhance efficiency of PbS quantum dot solar cells: Removing surface organic ligands and configuring a bilayer heterojunction with a new conjugated polymer

We present two novel techniques for improving the efficiency of PbS quantum dot (QD) solar cells. First, plasma was applied to QD film with the aim of removing surface organic ligands, and then the chemical and optical properties of the QDs were investigated. Second, a thin layer of conjugated polymer was then deposited on top of the plasma-treated PbS QD film as a transportation layer for holes. The charge separation and subsequent transfer dynamics were examined, as were the resultant photovoltaic characteristics, according to the kind of polymer used. The developed device, which comprises a bilayer heterojunction of plasma-treated PbS QDs and poly[2,6-(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-alt-4,7(2,1,3-benzothiadiazole)] (PSBTBT), showed not only broad-range absorption of the solar spectrum, but also high charge transfer efficiency prior to recombination. This results in a largely increased power conversion efficiency (PCE) of 1.76%, compared to the 0.7% value of a PbS QD-only device not subjected to plasma treatment. This indicates that the proposed techniques are very useful for improving the efficiency of inorganic QD-based solar cells.     

Overcoming the Cut‐Off Charge Transfer Bandgaps at the PbS Quantum Dot Interface

Light harvesting from large size of semiconductor PbS quantum dots (QDs) with a bandgap of less than 1 eV is one of the greatest challenges precluding the development of PbS QD‐based solar cells because the interfacial charge transfer (CT) from such QDs to the most commonly used electron acceptor materials is very inefficient, if it occurs at all. Thus, an alternative electron‐accepting unit with a new driving force for CT is urgently needed to harvest the light from large‐sized PbS QDs. Here, a cationic porphyrin is utilized as a new electron acceptor unit with unique features that bring the donor–acceptor components into close molecular proximity, allowing ultrafast and efficient electron transfer for QDs of all sizes, as inferred from the drastic photoluminescence quenching and the ultrafast formation of the porphyrin anionic species. The time‐resolved results clearly demonstrate the possibility of modulating the electron transfer process between PbS QDs and porphyrin moieties not only by the size quantization effect but also by the interfacial electrostatic interaction between the positively charged porphyrin and the negatively charged QDs. This approach provides a new pathway for engineering QD‐based solar cells that make the best use of the diverse photons making up the Sun's broad irradiance spectrum.     

Core/Shell PbSe/PbS QDs TiO2 Heterojunction Solar Cell

Quasi type‐II PbSe/PbS quantum dots (QDs) are employed in a solid state high efficiency QD/TiO₂ heterojunction solar cell. The QDs are deposited using layer‐by‐layer deposition on a half‐micrometer‐thick anatase TiO₂ nanosheet film with (001) exposed facets. Theoretical calculations show that the carriers in PbSe/PbS quasi type‐II QDs are delocalized over the entire core/shell structure, which results in better QD film conductivity compared to PbSe QDs. Moreover, PbS shell permits better stability and facile electron injection from the QDs to the TiO₂ nanosheets. To complete the electrical circuit of the solar cell, a Au film is evaporated as a back contact on top of the QDs. This PbSe/PbS QD/TiO₂ heterojunction solar cell produces a light to electric power conversion efficiency (η) of 4% with short circuit photocurrent (J_sc) of 17.3 mA/cm². This report demonstrates highly efficient core/shell near infrared QDs in a QD/TiO₂ heterojunction solar cell.     

Photomultiplication-Type Organic Photodetectors with Fast Response Enabled by the Controlled Charge Trapping Dynamics of Quantum Dot Interlayer

A novel photomultiplication (PM)-type organic photodiode (OPD) that responds much faster (109 kHz bandwidth) than conventional PM-type OPDs is demonstrated. This fast response is achieved by introducing quantum dots (QDs) as a PM-inducing interlayer at the interface between the electrode and the photoactive layer. When the device is illuminated, the photogenerated electrons within the photoactive layer are rapidly transferred and trapped in the trap states of the QD interlayer. The electron trapping subsequently leads to charging of the QD and a consequent shift of the QD energy levels, thereby inducing hole injection from the electrode. This PM mechanism is distinct from that of conventional PM-type OPDs, whose PM usually requires a long time to induce hole (or electron) injection because of the slow transport and accumulation of electrons (or holes) within the photoactive layer. Because of its PM mechanism, the proposed QD-interlayer PM-type OPD achieves high bandwidth and high specific detectivity. In addition, it is demonstrated that the response speed of the proposed device is closely related to the charge trapping/detrapping dynamics of the QDs. This work not only offers a new concept in the design of fast-responding PM-type OPDs but also provides comprehensive understanding of the underlying device physics.     

Efficient Infrared Solar Cells Employing Quantum Dot Solids with Strong Inter-Dot Coupling and Efficient Passivation

Lead chalcogenide quantum dot (QD) infrared (IR) solar cells are promising devices for breaking through the theoretical efficiency limit of single-junction solar cells by harvesting the low-energy IR photons that cannot be utilized by common devices. However, the device performance of QD IR photovoltaic is limited by the restrictive relation between open-circuit voltages (V_OC) and short circuit current densities (J_SC), caused by the contradiction between surface passivation and electronic coupling of QD solids. Here, a strategy is developed to decouple this restriction via epitaxially coating a thin PbS shell over the PbSe QDs (PbSe/PbS QDs) combined with in situ halide passivation. The strong electronic coupling from the PbSe core gives rise to significant carrier delocalization, which guarantees effective carrier transport. Benefited from the protection of PbS shell and in situ halide passivation, excellent trap-state control of QDs is eventually achieved after the ligand exchange. By a fine control of the PbS shell thickness, outstanding IR J_SC of 6.38 mA cm⁻² and IR V_OC of 0.347 V are simultaneously achieved under the 1100 nm-filtered solar illumination, providing a new route to unfreeze the trade-off between V_OC and J_SC limited by the photoactive layer with a given bandgap.     

PbS and CdS Quantum Dot‐Sensitized Solid‐State Solar Cells: “Old Concepts,New Results”

Lead sulfide (PbS) and cadmium sulfide (CdS) quantum dots (QDs) are prepared over mesoporous TiO₂ films by a successive ionic layer adsorption and reaction (SILAR) process. These QDs are exploited as a sensitizer in solid‐state solar cells with 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) as a hole conductor. High‐resolution transmission electron microscopy (TEM) images reveal that PbS QDs of around 3 nm in size are distributed homogeneously over the TiO₂ surface and are well separated from each other if prepared under common SILAR deposition conditions. The pore size of the TiO₂ films and the deposition medium are found to be very critical in determining the overall performance of the solid‐state QD cells. By incorporating promising inorganic QDs (PbS) and an organic hole conductor spiro‐OMeTAD into the solid‐state cells, it is possible to attain an efficiency of over 1% for PbS‐sensitized solid‐state cells after some optimizations. The optimized deposition cycle of the SILAR process for PbS QDs has also been confirmed by transient spectroscopic studies on the hole generation of spiro‐OMeTAD. In addition, it is established that the PbS QD layer plays a role in mediating the interfacial recombination between the spiro‐OMeTAD⁺ cation and the TiO₂ conduction band electron, and that the lifetime of these species can change by around 2 orders of magnitude by varying the number of SILAR cycles used. When a near infrared (NIR)‐absorbing zinc carboxyphthalocyanine dye (TT1) is added on top of the PbS‐sensitized electrode to obtain a panchromatic response, two signals from each component are observed, which results in an improved efficiency. In particular, when a CdS‐sensitized electrode is first prepared, and then co‐sensitized with a squarine dye (SQ1), the resulting color change is clearly an addition of each component and the overall efficiencies are also added in a more synergistic way than those in PbS/TT1‐modified cells because of favorable charge‐transfer energetics.     

Controlled Fabrication of PbS Quantum‐Dot/Carbon‐Nanotube Nanoarchitecture and its Significant Contribution to Near‐Infrared Photon‐to‐Current Conversion

A solution‐processed nanoarchitecture based on PbS quantum dots (QDs) and multi‐walled carbon nanotubes (MWCNTs) is synthesized by simply mixing the pre‐synthesized high‐quality PbS QDs and oleylamine (OLA) pre‐functionalized MWCNTs. Pre‐functionalization of MWCNTs with OLA is crucial for the attachment of PbS QDs and the coverage of QDs on the surface of MWCNTs can be tuned by varying the ratio of PbS QDs to MWCNTs. The apparent photoluminescence (steady‐state emission and fluorescence lifetime) “quenching” effect indicates efficient charge transfer from photo‐excited PbS QDs to MWCNTs. The as‐synthesized PbS‐QD/MWCNT nanoarchitecture is further incorporated into a hole‐conducting polymer poly(3‐hexylthiophene)‐(P3HT), forming the P3HT:PbS‐QD/MWCNT nanohybrid, in which the PbS QDs act as a light harvester for absorbing irradiation over a wide wavelength range of the solar spectrum up to near infrared (NIR, ≈1430 nm) range; whereas, the one‐dimensional MWCNTs and P3HT are used to collect and transport photoexcited electrons and holes to the cathode and anode, respectively. Even without performing the often required “ligand exchange” to remove the long‐chained OLA ligands, the built nanohybrid photovoltaic (PV) device exhibits a largely enhanced power conversion efficiency (PCE) of 3.03% as compared to 2.57% for the standard bulk hetero‐junction PV cell made with P3HT and [6,6]‐Phenyl‐C₆₁‐Butyric Acid Methyl Ester (PCBM) mixtures. The improved performance of P3HT:PbS‐QD/MWCNT nanohybrid PV device is attributed to the significantly extended absorption up to NIR by PbS QDs as well as the effectively enhanced charge separation and transportation due to the integrated MWCNTs and P3HT. Our research results suggest that properly integrating QDs, MWCNTs, and polymers into nanohybrid structures is a promising approach for the development of highly efficient PV devices.     

Vacuum deposited ternary mixture organic solar cells

Ternary mixtures of photo-active organic materials are an intuitive approach to achieve enhanced photocurrent in organic solar cells (OSCs). In this work, we study ternary mixtures of vacuum deposited small molecules, complementing the recent surge of interest in solution processed ternary OSCs. The mixed layer composition is systematically varied to study all possible film configurations, and the resulting OSCs are successful in harvesting photocurrent from all three components to grant broad spectral photoresponse. However, the performance of the ternary OSC is generally less than the binary OSC, largely due to reduced fill factors. By examining ternary OSC transient photocurrents and multi-donor planar heterojunction devices, we demonstrate that the ternary OSC is strongly affected by the energy levels of its constituent materials, with small differences in the two donor materials’ highest occupied molecular orbitals degrading hole transport. The results stress the importance of fine molecular engineering for ternary OSCs, and further hint that the enhancements commonly observed in solution processed ternary OSCs may in part be associated with morphological variations that are not present in vacuum deposited OSCs. The research verifies that, by designing small molecules with specific energy levels, ternary OSCs provide an alternative pathway to low cost, high efficiency photovoltaics in lieu of more complicated device architectures.     

Multiple Function Synchronous Optimization by PbS Quantum Dots for Highly Stable Planar Perovskite Solar Cells with Efficiency Exceeding 23%

Colloidal lead sulfide (PbS) quantum dots (QDs), which possess quantum confinement effect and processing compatibility with perovskite, are regarded as an excellent material for optimizing perovskite solar cells (PSCs). However, the existing PSCs optimized by PbS QDs are still facing the challenges of poor performance of the charge transport layers, low utilization in the near-infrared (NIR) region, and unsuitable energy level alignment, which limit the improvement of power conversion efficiency (PCE). Herein, a synchronous optimization strategy is realized via simultaneously introducing PbS QDs into SnO₂ electron transport layer and employing rare-earth-doped PbS QDs (Eu:PbS QDs) film with hydrophobic chain ligands as the NIR light-absorping layer and hole transport layer (HTL) of devices. PbS QDs effectively decrease the density of trap states by passivating defects. Eu:PbS QDs film with adjustable bandgap is employed as an absorption layer to broaden the NIR spectral absorption. The well-matched energy level between Eu:PbS QDs layer and perovskite layer implies efficient hole transfer at the interface. The successful synchronous optimization greatly elevates all photovoltaic parameters, reaching a maximum PCE of 23.27%. This PCE is the highest for PSCs utilizing PbS QDs material in recent years. The optimized PSCs retain long-term moisture and light stability.     

Transparent InP Quantum Dot Light‐Emitting Diodes with ZrO2 Electron Transport Layer and Indium Zinc Oxide Top Electrode

Because of outstanding optical properties and non‐vacuum solution processability of colloidal quantum dot (QD) semiconductors, many researchers have developed various light emitting diodes (LEDs) using QD materials. Until now, the Cd‐based QD‐LEDs have shown excellent properties, but the eco‐friendly QD semiconductors have attracted many attentions due to the environmental regulation. And, since there are many issues about the reliability of conventional QD‐LEDs with organic charge transport layers, a stable charge transport layer in various conditions must be developed for this reason. This study proposes the organic/inorganic hybrid QD‐LEDs with Cd‐free InP QDs as light emitting layer and inorganic ZrO₂ nanoparticles as electron transport layer. The QD‐LED with bottom emission structure shows the luminescence of 530 cd m^?2 and the current efficiency of 1 cd/A. To realize the transparent QD‐LED display, the two‐step sputtering process of indium zinc oxide (IZO) top electrode is applied to the devices and this study could fabricate the transparent QD‐LED device with the transmittance of more than 74% for whole device array. And when the IZO top electrode with high work‐function is applied to top transparent anode, the device could maintain the current efficiency within the driving voltage range without well‐known roll‐off phenomenon in QD‐LED devices.     

Facet Control for Trap‐State Suppression in Colloidal Quantum Dot Solids

Trap states in colloidal quantum dot (QD) solids significantly affect the performance of QD solar cells, because they limit the open‐circuit voltage and short circuit current. The {100} facets of PbS QDs are important origins of trap states due to their weak or missing passivation. However, previous investigations focused on synthesis, ligand exchange, or passivation approaches and ignored the control of {100} facets for a given dot size. Herein, trap states are suppressed from the source via facet control of PbS QDs. The {100} facets of ≈3 nm PbS QDs are minimized by tuning the balance between the growth kinetics and thermodynamics in the synthesis. The PbS QDs synthesized at a relatively low temperature with a high oversaturation follow a kinetics‐dominated growth, producing nearly octahedral nanoparticles terminated mostly by {111} facets. In contrast, the PbS QDs synthesized at a relatively high temperature follow a thermodynamics‐dominated growth. Thus, a spherical shape is preferred, producing truncated octahedral nanoparticles with more {100} facets. Compared to PbS QDs from thermodynamics‐dominated growth, the PbS QDs with less {100} facets show fewer trap states in the QD solids, leading to a better photovoltaic device performance with a power conversion efficiency of 11.5%.     

Light‐Emitting Electrochemical Cells Based on Color‐Tunable Inorganic Colloidal Quantum Dots

Large‐area, ultrathin light‐emitting devices currently inspire architects and interior and automotive designers all over the world. Light‐emitting electrochemical cells (LECs) and quantum dot light‐emitting diodes (QD‐LEDs) belong to the most promising next‐generation device concepts for future flexible and large‐area lighting technologies. Both concepts incorporate solution‐based fabrication techniques, which makes them attractive for low cost applications based on, for example, roll‐to‐roll fabrication or inkjet printing. However, both concepts have unique benefits that justify their appeal. LECs comprise ionic species in the active layer, which leads to the omission of additional organic charge injection and transport layers and reactive cathode materials, thus LECs impress with their simple device architecture. QD‐LEDs impress with purity and opulence of available colors: colloidal quantum dots (QDs) are semiconducting nanocrystals that show high yield light emission, which can be easily tuned over the whole visible spectrum by material composition and size. Emerging technologies that unite the potential of both concepts (LEC and QD‐LED) are covered, either by extending a typical LEC architecture with additional QDs, or by replacing the entire organic LEC emitter with QDs or perovskite nanocrystals, still keeping the easy LEC setup featured by the incorporation of mobile ions.     

Matrix Manipulation of Directly-Synthesized PbS Quantum Dot Inks Enabled by Coordination Engineering

The direct-synthesis of conductive PbS quantum dot (QD) ink is facile, scalable, and low-cost, boosting the future commercialization of optoelectronics based on colloidal QDs. However, manipulating the QD matrix structures still is a challenge, which limits the corresponding QD solar cell performance. Here, for the first time a coordination-engineering strategy to finely adjust the matrix thickness around the QDs is presented, in which halogen salts are introduced into the reaction to convert the excessive insulating lead iodide into soluble iodoplumbate species. As a result, the obtained QD film exhibits shrunk insulating shells, leading to higher charge carrier transport and superior surface passivation compared to the control devices. A significantly improved power-conversion efficiency from 10.52% to 12.12% can be achieved after the matrix engineering. Therefore, the work shows high significance in promoting the practical application of directly synthesized PbS QD inks in large-area low-cost optoelectronic devices.     

Heterojunction Engineering of CdTe and CdSe Quantum Dots on TiO2 Nanotube Arrays: Intricate Effects of Size‐Dependency and Interfacial Contact on Photoconversion Efficiencies

The quality of heterojunctions at the quantum dot (QD)‐TiO₂ nanotube (TNT) interface has important implications on the efficiencies of photoelectrochemical solar cells. Here, it is shown that electrophoretic deposition of pre‐synthesized thioacid‐capped CdTe QDs results in relatively poor charge transfer across the heterojunctions. This is likely due to the intermediate layer of bifunctional linkers (S‐R‐COOH) in between the QDs and TNT. On the other hand, CdTe QD‐sensitized TNT prepared by in situ deposition in aqueous medium provides direct QD‐TNT contact, and hence more favorable heterojunction for charge transfer. This is exemplified not only by the drastic improvement in photocurrent efficiencies, but also provides clear difference on the size‐dependent electron injection efficiencies from the CdTe QDs of different sizes. By extending the system further to CdSe QDs, drastic enhancement is found when carrying out the in situ deposition in an organic medium. The results are discussed in terms of the nature of deposition and the corresponding charge transport characteristics. More importantly, the work reflects the intricacy of the effects of QD size and the quality of the heterojunctions on the overall photoconversion efficiencies.     

Molecular Packing and Dielectric Property Optimization through Peripheral Halogen Swapping Enables Binary Organic Solar Cells with an Efficiency of 18.77%

Peripheral halogen regulations can endow non-fullerene acceptors (NFAs) with enhanced features as organic semi-conductors and further boost efficient organic solar cells (OSCs). Herein, based on a remarkable molecular platform of CH14 with more than six halogenation positions, a preferred NFA of CH23 is constructed by synergetic halogen swapping on both central and end units, rendering the overall enlarged molecular dipole moment, packing density and thus relative dielectric constant. Consequently, the CH23-based binary OSC reaches an excellent efficiency of 18.77% due to its improved charge transfer/transport dynamics, much better than that of 17.81% for the control OSC of CH14. This work demonstrates the great potential for further achieving state-of-the-art OSCs by delicately regulating the halogen formula on these newly explored CH-series NFAs.     

Vertical Phase Separation in Small Molecule:Polymer Blend Organic Thin Film Transistors Can Be Dynamically Controlled

Blending of small‐molecule organic semiconductors (OSCs) with amorphous polymers is known to yield high performance organic thin film transistors (OTFTs). Vertical stratification of the OSC and polymer binder into well‐defined layers is crucial in such systems and their vertical order determines whether the coating is compatible with a top and/or a bottom gate OTFT configuration. Here, we investigate the formation of blends prepared via spin‐coating in conditions which yield bilayer and trilayer stratifications. We use a combination of in situ experimental and computational tools to study the competing effects of formulation thermodynamics and process kinetics in mediating the final vertical stratification. It is shown that trilayer stratification (OSC/polymer/OSC) is the thermodynamically favored configuration and that formation of the buried OSC layer can be kinetically inhibited in certain conditions of spin‐coating, resulting in a bilayer stack instead. The analysis reveals here that preferential loss of the OSC, combined with early aggregation of the polymer phase due to rapid drying, inhibit the formation of the buried OSC layer. The fluid dynamics and drying kinetics are then moderated during spin‐coating to promote trilayer stratification with a high quality buried OSC layer which yields unusually high mobility >2 cm² V^?1 s^?1 in the bottom‐gate top‐contact configuration.     

Oxide Sandwiched Metal Thin‐Film Electrodes for Long‐Term Stable Organic Solar Cells

Oxide/silver/oxide multilayers as semitransparent top electrode for small molecule organic solar cells (OSCs) are presented. It is shown that two oxide layers sandwiching a central metal layer greatly improve the stability and lifetime of the organic solar cell. Thermally evaporated MoO₃, WO₃, or V₂O₅ layers are employed as an interlayer for subsequent silver deposition and significantly change the morphology of the ultrathin silver layer, improving charge extraction and electrodes series resistance. The transmittance of the electrode is increased by introducing oxide or oxide and organic multilayers as capping layer, which leads to higher photocurrent generation in the absorber layer. Application of 1 nm MoO₃/11 nm Ag/10 nm MoO₃/50 nm Alq₃ multilayer electrodes in OSCs lead to an efficiency of 2.6% for a standard ZnPc:C60 cell, showing superior performance compared to devices with pure silver top contacts. The device lifetime is also strongly increased. MoO₃ layers can saturate and stabilize the inner and outer metal surface, passivating it against most of the degradation mechanisms. With such an oxide/silver/oxide multilayer electrode, the time until the glass encapsulated OSC is degraded to 80% of its starting efficiency is enhanced from 86 h to approximately 4500 h compared to an OSC without an oxide interlayer.     

Electric Field Tuning Molecular Packing and Electrical Properties of Solution‐Shearing Coated Organic Semiconducting Thin Films

Recent improvements in solution‐coated organic semiconductors (OSCs) evidence their high potential for cost‐efficient organic electronics and sensors. Molecular packing structure determines the charge transport property of molecular solids. However, it remains challenging to control the molecular packing structure for a given OSC. Here, the application of alternating electric fields is reported to fine‐tune the crystal packing of OSC solution‐shearing coated at ambient conditions. First, a theoretical model based on dielectrophoresis is developed to guide the selection of the optimal conditions (frequency and amplitude) of the electric field applied through the solution‐shearing blade during coating of OSC thin films. Next, electric field‐induced polymorphism is demonstrated for OSCs with both herringbone and 2D brick‐wall packing motifs in 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene and 6,13‐bis(triisopropylsilylethynyl) pentacene, respectively. Favorable molecular packing can be accessible in some cases, resulting in higher charge carrier mobilities. This work provides a new approach to tune the properties of solution‐coated OSCs in functional devices for high‐performance printed electronics.     

Delayed Fluorescence Emitter Enables Near 17% Efficiency Ternary Organic Solar Cells with Enhanced Storage Stability and Reduced Recombination Energy Loss

Charge transfer state (CT) plays an important role in exciton diffusion, dissociation, and charge recombination mechanisms. Enhancing the utilization and suppressing the recombination process of CT excitons is a promising way to improve the performance of organic solar cells (OSCs). Here, an effective method is presented via introducing a delayed fluorescence (DF) emitter 3,4‐bis(4‐(diphenylamino)phenyl)acenaphtho[1,2‐b]pyrazine‐8,9‐dicarbonitrile (APDC‐TPDA) in OSCs. The long‐lifetime singlet excitons on APDC‐TPDA can transfer to polymer donors to prolong exciton lifetime, which ensures sufficient time for diffusion and dissociation. Concurrently, the high triplet energy level (T₁) of the DF material can also prevent the reverse energy transfer from CT to T₁. APDC‐TPDA‐containing ternary OSCs shows a high PCE of 16.96% with a reduced recombination energy loss of 0.46 eV. It is noteworthy that the ternary OSC also exhibits superior storage stability. After 55 days of storage, the PCE of the ternary OSC still retains about 96% of its primitive state. Furthermore, this ternary strategy is efficient and universally applicable to OSCs, and positive results can be obtained in different systems with different DF emitters. These results indicate that the ternary strategy provides a new design idea to realize high performance OSCs.     

Doping of Organic Semiconductors Using Molybdenum Trioxide: a Quantitative Time‐Dependent Electrical and Spectroscopic Study

Doping of organic semiconductors (OSCs) with transition metal oxides such as molybdenum trioxide (MoO₃) has been used as a powerful method to overcome common issues such as contact resistance and low conductivity, which are limiting factors in organic optoelectronic devices. In this study, the mechanism and efficiency of MoO₃‐induced p‐type doping in OSCs are investigated by means of simultaneous electrical and spectroscopic measurements on lateral diodes. It is demonstrated that energetic changes in the MoO₃ energy levels outside vacuum can limit charge‐transfer doping and device performance. It is shown and investigated that these changes crucially depend on the OSC. The time evolution of important OSC parameters such as induced charge density, doping concentration and efficiency, conductivity and mobility, is deduced. Moreover, the energetic and chemical changes in MoO₃ are investigated via ultraviolet and x‐ray photoemission spectroscopy. Combining these experiments, important conclusions are drawn on the time‐dependence and stability of MoO₃‐doping of OSCs, as well as on the processing conditions and device architectures suitable for high‐performance devices.