Tantalum Nitride Electron‐Selective Contact for Crystalline Silicon Solar Cells

Minimizing carrier recombination at contact regions by using carrier‐selective contact materials, instead of heavily doping the silicon, has attracted considerable attention for high‐efficiency, low‐cost crystalline silicon (c‐Si) solar cells. A novel electron‐selective, passivating contact for c‐Si solar cells is presented. Tantalum nitride (TaN _x ) thin films deposited by atomic layer deposition are demonstrated to provide excellent electron‐transporting and hole‐blocking properties to the silicon surface, due to their small conduction band offset and large valence band offset. Thin TaN_x interlayers provide moderate passivation of the silicon surfaces while simultaneously allowing a low contact resistivity to n‐type silicon. A power conversion efficiency (PCE) of over 20% is demonstrated with c‐Si solar cells featuring a simple full‐area electron‐selective TaN_x contact, which significantly improves the fill factor and the open circuit voltage (V_oc) and hence provides the higher PCE. The work opens up the possibility of using metal nitrides, instead of metal oxides, as carrier‐selective contacts or electron transport layers for photovoltaic devices.     

The Importance of Fullerene Percolation in the Mixed Regions of Polymer–Fullerene Bulk Heterojunction Solar Cells

Most optimized donor‐acceptor (D‐A) polymer bulk heterojunction (BHJ) solar cells have active layers too thin to absorb greater than ～80% of incident photons with energies above the polymer's band gap. If the thickness of these devices could be increased without sacrificing internal quantum efficiency, the device power conversion efficiency (PCE) could be significantly enhanced. We examine the device characteristics of BHJ solar cells based on poly(di(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐octylthieno[3,4‐c]pyrrole‐4,6‐dione) (PBDTTPD) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) with 7.3% PCE and find that bimolecular recombination limits the active layer thickness of these devices. Thermal annealing does not mitigate these bimolecular recombination losses and drastically decreases the PCE of PBDTTPD BHJ solar cells. We characterize the morphology of these BHJs before and after thermal annealing and determine that thermal annealing drastically reduces the concentration of PCBM in the mixed regions, which consist of PCBM dispersed in the amorphous portions of PBDTTPD. Decreasing the concentration of PCBM may reduce the number of percolating electron transport pathways within these mixed regions and create morphological electron traps that enhance charge‐carrier recombination and limit device quantum efficiency. These findings suggest that (i) the concentration of PCBM in the mixed regions of polymer BHJs must be above the PCBM percolation threshold in order to attain high solar cell internal quantum efficiency, and (ii) novel processing techniques, which improve polymer hole mobility while maintaining PCBM percolation within the mixed regions, should be developed in order to limit bimolecular recombination losses in optically thick devices and maximize the PCE of polymer BHJ solar cells.     

Charge Transport and Recombination in Low‐Bandgap Bulk Heterojunction Solar Cell using Bis‐adduct Fullerene

Charge transport and recombination are studied for organic solar cells fabricated using blends of polymer poly[(4,4′‐bis(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]silole)‐2,6‐diyl‐alt‐(4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole)‐5,5′‐diyl] (Si‐PCPDTBT) with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (mono‐PCBM) and the bis‐adduct analogue of mono‐PCBM (bis‐PCBM). The photocurrent of Si‐PCPDTBT:bis‐PCBM devices shows a strong square root dependence on the effective applied voltage. From the relationship between the photocurrent and the light intensity, we found that the square‐root dependence of the photocurrent is governed by the mobility‐lifetime (μτ) product of charge carriers while space‐charge field effects are insignificant. The fill factor (FF) and short circuit current density (J_sc) of bis‐PCBM solar cells show a considerable increase with temperature as compared to mono‐PCBM solar cells. SCLC analysis of single carrier devices proofs that the mobility of both electrons and holes is significantly lowered when replacing mono‐PCBM with bis‐PCBM. The increased recombination in Si‐PCPDTBT:bis‐PCBM solar cells is therefore attributed to the low carrier mobilities, as the transient photovoltage measurements show that the carrier lifetime of devices are not significantly altered by using bis‐PCBM instead of mono‐PCBM.     

Understanding the Doping Effect on NiO: Toward High‐Performance Inverted Perovskite Solar Cells

High‐quality hole transport layers are prepared by spin‐coating copper doped nickel oxide (Cu:NiO) nanoparticle inks at room temperature without further processing. In agreement with theoretical calculations predicting that Cu doping results in acceptor energy levels closer to the valence band maximum compared to gap states of nickel vacancies in undoped NiO, an increase in the conductivity in Cu:NiO films compared to NiO is observed. Cu in Cu:NiO can be found in both Cu⁺ and Cu²⁺ states, and the substitution of Ni²⁺ with Cu⁺ contributes to both increased carrier concentration and carrier mobility. In addition, the films exhibit increased work function, which together with the conductivity increase, enables improved charge transfer and extraction. Furthermore, recombination losses due to lower monomolecular Shockley‐Read‐Hall recombination are reduced. These factors result in an improvement of all photovoltaic performance parameters and consequently an increased efficiency of the inverted planar perovskite solar cells. A power conversion efficiency (PCE) exceeding 20% could be achieved for small‐area devices, while PCE values of 17.41 and 18.07% are obtained for flexible devices and large area (1 cm²) devices on rigid substrates, respectively.     

Trade‐Off between Trap Filling,Trap Creation,and Charge Recombination Results in Performance Increase at Ultralow Doping Levels in Bulk Heterojunction Solar Cells

Doping of organic bulk heterojunction solar cells has the potential to improve their power conversion efficiency (PCE). Deconvoluting the effect of doping on charge transport, recombination, and energetic disorder remains challenging. It is demonstrated that molecular doping has two competing effects: on one hand, dopant ions create additional traps while on the other hand free dopant‐induced charges fill deep states possibly leading to V _OC and mobility increases. It is shown that molar dopant concentrations as low as a few parts per million can improve the PCE of organic bulk heterojunctions. Higher concentrations degrade the performance of the cells. In doped cells where PCE is observed to increase, such improvement cannot be attributed to better charge transport. Instead, the V _OC increase in unannealed P3HT:PCBM cells upon doping is indeed due to trap filling, while for annealed P3HT:PCBM cells the change in V _OC is related to morphology changes and dopant segregation. In PCDTBT:PC70BM cells, the enhanced PCE upon doping is explained by changes in the thickness of the active layer. This study highlights the complexity of bulk doping in organic solar cells due to the generally low doping efficiency and the constraint on doping concentrations to avoid carrier recombination and adverse morphology changes.     

Highly Reproducible Sn‐Based Hybrid Perovskite Solar Cells with 9% Efficiency

The low power conversion efficiency (PCE) of tin‐based hybrid perovskite solar cells (HPSCs) is mainly attributed to the high background carrier density due to a high density of intrinsic defects such as Sn vacancies and oxidized species (Sn⁴⁺) that characterize Sn‐based HPSCs. Herein, this study reports on the successful reduction of the background carrier density by more than one order of magnitude by depositing near‐single‐crystalline formamidinium tin iodide (FASnI₃) films with the orthorhombic a‐axis in the out‐of‐plane direction. Using these highly crystalline films, obtained by mixing a very small amount (0.08 m ) of layered (2D) Sn perovskite with 0.92 m (3D) FASnI₃, for the first time a PCE as high as 9.0% in a planar p–i–n device structure is achieved. These devices display negligible hysteresis and light soaking, as they benefit from very low trap‐assisted recombination, low shunt losses, and more efficient charge collection. This represents a 50% improvement in PCE compared to the best reference cell based on a pure FASnI₃ film using SnF₂ as a reducing agent. Moreover, the 2D/3D‐based HPSCs show considerable improved stability due to the enhanced robustness of the perovskite film compared to the reference cell.     

Hot‐Substrate Deposition of Hole‐ and Electron‐Transport Layers for Enhanced Performance in Perovskite Solar Cells

Charge transport layers play an important role in determining the power conversion efficiencies (PCEs) of perovskite solar cells (PSCs). However, it has proven challenging to produce thin and compact charge transport layers via solution processing techniques. Herein, a hot substrate deposition method capable of improving the morphology of high‐coverage hole‐transport layers (HTLs) and electron‐transport layers (ETLs) is reported. PSC devices using HTLs deposited on a hot substrate show improvement in the open‐circuit voltage (V_oc) from 1.041 to 1.070 V and the PCE from 17.00% to 18.01%. The overall device performance is then further enhanced with the hot substrate deposition of ETLs as the V_oc and PCE reach 1.105 V and 19.16%, respectively. The improved performance can be explained by the decreased current leakage and series resistance, which are present in PSCs with rough and discontinuous HTLs and ETLs.     

Vacuum‐Assisted Growth of Low‐Bandgap Thin Films (FA0.8MA0.2Sn0.5Pb0.5I3) for All‐Perovskite Tandem Solar Cells

All‐perovskite multijunction photovoltaics, combining a wide‐bandgap (WBG) perovskite top solar cell (E_G ≈1.6–1.8 eV) with a low‐bandgap (LBG) perovskite bottom solar cell (E_G < 1.3 eV), promise power conversion efficiencies (PCEs) >33%. While the research on WBG perovskite solar cells has advanced rapidly over the past decade, LBG perovskite solar cells lack PCE as well as stability. In this work, vacuum‐assisted growth control (VAGC) of solution‐processed LBG perovskite thin films based on mixed Sn–Pb perovskite compositions is reported. The reported perovskite thin films processed by VAGC exhibit large columnar crystals. Compared to the well‐established processing of LBG perovskites via antisolvent deposition, the VAGC approach results in a significantly enhanced charge‐carrier lifetime. The improved optoelectronic characteristics enable high‐performance LBG perovskite solar cells (1.27 eV) with PCEs up to 18.2% as well as very efficient four‐terminal all‐perovskite tandem solar cells with PCEs up to 23%. Moreover, VAGC leads to promising reproducibility and potential in the fabrication of larger active‐area solar cells up to 1 cm².     

Fusing Nanowires into Thin Films: Fabrication of Graded‐Heterojunction Perovskite Solar Cells with Enhanced Performance

Perovskite solar cells (PSCs) have recently experienced a rapid rise in power conversion efficiency (PCE), but the prevailing PSCs with conventional mesoscopic or planar device architectures still contain nonideal perovskite/hole‐transporting‐layer (HTL) interfaces, limiting further enhancement in PCE and device stability. In this work, CsPbBr₃ perovskite nanowires are employed for modifying the surface electronic states of bulk perovskite thin films, forming compositionally‐graded heterojunction at the perovskite/HTL interface of PSCs. The nanowire morphology is found to be key to achieving lateral homogeneity in the perovskite film surface states resulting in a near‐ideal graded heterojunction. The hidden role of such lateral homogeneity on the performance of graded‐heterojunction PSCs is revealed for the first time. The resulting PSCs show high PCE up to 21.4%, as well as high operational stability, which is superior to control PSCs fabricated without CsPbBr₃‐nanocrystals modification and with CsPbBr₃‐nanocubes modification. This study demonstrates the promise of controlled hybridization of perovskite nanowires and bulk thin films for more efficient and stable PSCs.     

Solution‐Processed TiO2 Nanoparticles as the Window Layer for CuIn(S,Se)2 Devices

As a wide‐bandgap semiconductor, titanium dioxide (TiO₂) with a porous structure has proven useful in dye‐sensitized solar cells, but its application in low‐cost, high‐efficiency inorganic photovoltaic devices based on materials such as Cu(InGa)Se₂ or Cu₂ZnSnS₄ is limited. Here, a thin film made from solution‐processed TiO₂ nanocrystals is demonstrated as an alternative to intrinsic zinc oxide (i‐ZnO) as the window layer of CuInS_xSe_1?x solar cells. The as‐synthesized, well‐dispersed, 6 nm TiO₂ nanocrystals are assembled into thin films with controllable thicknesses of 40, 80, and 160 nm. The TiO₂ nanocrystal films with thicknesses of 40 and 80 nm exhibit conversion efficiencies (6.2% and 6.33%, respectively) that are comparable to that of a layer of the typical sputtered i‐ZnO (6.42%). The conversion efficiency of the devices with a TiO₂ thickness of 160 nm decreases to 2.2%, owing to the large series resistance. A 9‐hour reaction time leads to aggregated nanoparticles with a much‐lower efficiency (2%) than that of the well‐dispersed TiO₂ nanoparticles prepared using a 15‐hour reaction time. Under optimized conditions, the champion TiO₂ nanocrystal‐film‐based device shows even higher efficiency (9.2%) than a control device employing a typical i‐ZnO film (8.6%).     

Slot‐Die and Roll‐to‐Roll Processed Single Junction Organic Photovoltaic Cells with the Highest Efficiency

The record efficiency of the state‐of‐the‐art polymer solar cells (PSCs) is rapidly increasing, due to the discovery of high‐performance photoactive donor and acceptor materials. However, strong questions remain as to whether such high‐efficiency PSCs can be produced by scalable processes. This paper reports a high power conversion efficiency (PCE) of 13.5% achieved with single‐junction ternary PSCs based on PTB7‐Th, PC₇₁BM, and COi8DFIC fabricated by slot‐die coating, which shows the highest PCE ever reported in PSCs fabricated by a scalable process. To understand the origin of the high performance of the slot‐die coated device, slot‐die coated photoactive films and devices are systematically investigated. These results indicate that the good performance of the slot‐die PSCs can be due to a favorable molecule‐structure and film‐morphology change by introducing 1,8‐diiodooctane and heat treatment, which can lead to improved charge transport with reduced carrier recombination. The optimized condition is then used for the fabrication of large‐area modules and also for roll‐to‐roll fabrication. The slot‐die coated module with 30 cm² active‐area and roll‐to‐roll produced flexible PSC has shown 8.6% and 9.6%, respectively. These efficiencies are the highest in each category and demonstrate the strong potential of the slot‐die coated ternary system for commercial applications.     

Unraveling Charge Separation and Transport Mechanisms in Aqueous‐Processed Polymer/CdTe Nanocrystal Hybrid Solar Cells

Recently great progress has been achieved in highly effective hybrid solar cells fabricated using aqueous materials. The state‐of‐the‐art energy conversion efficiency has been close to 5% with high photocurrent. However, charge separation and transport mechanism in the aqueous‐processed hybrid solar cells are rarely reported and are usually assumed to be similar to oil‐phase processed systems; that is, self‐assembly polymers are mainly responsible for charge separation and carrier transport. To date, this assumption has prohibited further improvement of the conversion efficiency in aqueous‐processed hybrid systems by adopting any appropriate technique routes. Here, ultrafast carrier dynamics in these hybrid solar cells consisting of poly(p‐phenylenevinylene) (PPV)‐based aqueous polymers and water‐solution CdTe nanocrystals (NCs) are investigated in detail. Self‐charge separation in grown CdTe NC partly capped CdS shell layers after anneal treatment is unambiguously identified. Different from their oil‐soluble counterparts, these core/shell nanocrystals do not have the restrictions of quantum confinement and surface ligands, form effective charge transport networks, and play a dominant role in the charge separation and carrier transport processes. These findings provide a greater understanding on the fundamental photophysics in aqueous‐processed hybrid systems.     

Charge‐Carrier Mobility Requirements for Bulk Heterojunction Solar Cells with High Fill Factor and External Quantum Efficiency >90%

To increase the efficiency of bulk heterojunction (BHJ) solar cells beyond 15%, 300 nm thick devices with 0.8 fill factor (FF) and external quantum efficiency (EQE) >90% are likely needed. This work demonstrates that numerical device simulators are a powerful tool for investigating charge‐carrier transport in BHJ devices and are useful for rapidly determining what semiconductor pro­perties are needed to reach these performance milestones. The electron and hole mobility in a BHJ must be ≈10^?2 cm² V^?1 s^?1 in order to attain a 0.8 FF in a 300 nm thick device with the recombination rate constant of poly(3‐hexyl­thiophene):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM). Thus, the hole mobility of donor polymers needs to increase from ≈10^?4 to ≈10^?2 cm² V^?1 s^?1 in order to significantly improve device performance. Furthermore, the charge‐carrier mobility required for high FF is directly proportional to the BHJ recombination rate constant, which demonstrates that decreasing the recombination rate constant could dramatically improve the efficiency of optically thick devices. These findings suggest that researchers should prioritize improving charge‐carrier mobility when synthesizing new materials for BHJ solar cells and highlight that they should aim to understand what factors affect the recombination rate constant in these devices.     

Electron‐Beam‐Evaporated Nickel Oxide Hole Transport Layers for Perovskite‐Based Photovoltaics

High‐quality charge carrier transport materials are of key importance for stable and efficient perovskite‐based photovoltaics. This work reports on electron‐beam‐evaporated nickel oxide (NiO_x) layers, resulting in stable power conversion efficiencies (PCEs) of up to 18.5% when integrated into solar cells employing inkjet‐printed perovskite absorbers. By adding oxygen as a process gas and optimizing the layer thickness, transparent and efficient NiO_x hole transport layers (HTLs) are fabricated, exhibiting an average absorptance of only 1%. The versatility of the material is demonstrated for different absorber compositions and deposition techniques. As another highlight of this work, all‐evaporated perovskite solar cells employing an inorganic NiO_x HTL are presented, achieving stable PCEs of up to 15.4%. Along with good PCEs, devices with electron‐beam‐evaporated NiO_x show improved stability under realistic operating conditions with negligible degradation after 40 h of maximum power point tracking at 75 °C. Additionally, a strong improvement in device stability under ultraviolet radiation is found if compared to conventional perovskite solar cell architectures employing other metal oxide charge transport layers (e.g., titanium dioxide). Finally, an all‐evaporated perovskite solar mini‐module with a NiO_x HTL is presented, reaching a PCE of 12.4% on an active device area of 2.3 cm².     

Surface Engineering of TiO2 ETL for Highly Efficient and Hysteresis‐Less Planar Perovskite Solar Cell (21.4%) with Enhanced Open‐Circuit Voltage and Stability

Interfacial studies and band alignment engineering on the electron transport layer (ETL) play a key role for fabrication of high‐performance perovskite solar cells (PSCs). Here, an amorphous layer of SnO₂ (a‐SnO₂) between the TiO₂ ETL and the perovskite absorber is inserted and the charge transport properties of the device are studied. The double‐layer structure of TiO₂ compact layer (c‐TiO₂) and a‐SnO₂ ETL leads to modification of interface energetics, resulting in improved charge collection and decreased carrier recombination in PSCs. The optimized device based on a‐SnO₂/c‐TiO₂ ETL shows a maximum power conversion efficiency (PCE) of 21.4% as compared to 19.33% for c‐TiO₂ based device. Moreover, the modified device demonstrates a maximum open‐circuit voltage (V_oc) of 1.223 V with 387 mV loss in potential, which is among the highest reported value for PSCs with negligible hysteresis. The stability results show that the device on c‐TiO₂/a‐SnO₂ retains about 91% of its initial PCE value after 500 h light illumination, which is higher than pure c‐TiO₂ (67%) based devices. Interestingly, using a‐SnO₂/c‐TiO₂ ETL the PCE loss was only 10% of initial value under continuous UV light illumination after 30 h, which is higher than that of c‐TiO₂ based device (28% PCE loss).     

Spatial Distribution Recast for Organic Bulk Heterojunctions for High‐Performance All‐Inorganic Perovskite/Organic Integrated Solar Cells

All‐inorganic CsPbIBr₂ perovskite solar cells (pero‐SCs) exhibit excellent overall stability, but their power conversion efficiencies (PCEs) are greatly limited by their wide bandgaps. Integrated solar cells (ISCs) are considered to be an emergent technology that could extend their photoresponse by directly stacking two distinct photoactive layers with complementary bandgaps. However, rising photocurrents always sacrifice other photovoltaic parameters, thereby leading to an unsatisfactory PCE. Here, a recast strategy is proposed to optimize the spatial distribution components of low‐bandgap organic bulk‐heterojunction (BHJ) film, and is combined with an all‐inorganic perovskite to construct perovskite/BHJ ISCs. With this strategy, the integrated perovskite/BHJ film with a top‐enriched donor‐material spatial distribution is shown to effectively improve ambipolar charge transport behavior and suppress charge carrier recombination. For the first time, the ISC is not only significantly extended and enhanced the photoresponse achieving a 20% increase in current density, but also exhibits a high open‐circuit voltage and fill factor at the same time. As a result, a record PCE of 11.08% based on CsPbIBr₂ pero‐SCs is realized; it simultaneously shows excellent long‐term stability against heat and ultraviolet light.     

Improving Perovskite Solar Cells: Insights From a Validated Device Model

To improve the efficiency of existing perovskite solar cells (PSCs), a detailed understanding of the underlying device physics during their operation is essential. Here, a device model has been developed and validated that describes the operation of PSCs and quantitatively explains the role of contacts, the electron and hole transport layers, charge generation, drift and diffusion of charge carriers and recombination. The simulation to the experimental data of vacuum‐deposited CH₃NH₃PbI₃ solar cells over multiple thicknesses has been fit and the device behavior under different operating conditions has been studied to delineate the influence of the external bias, charge‐carrier mobilities, energetic barriers for charge injection/extraction and, different recombination channels on the solar cell performance. By doing so, a unique set of material parameters and physical processes that describe these solar cells is identified. Trap‐assisted recombination at material interfaces is the dominant recombination channel limiting device performance and passivation of traps increases the power conversion efficiency (PCE) of these devices by 40%. Finally, guidelines to increase their performance have been issued and it is shown that a PCE beyond 25% is within reach.     

TiO2 Nanocrystals Synthesized by Laser Pyrolysis for the Up‐Scaling of Efficient Solid‐State Dye‐Sensitized Solar Cells

A crucial issue regarding emerging nanotechnologies remains the up‐scaling of new functional nanostructured materials towards their implementation in high performance applications on a large scale. In this context, we demonstrate high efficiency solid‐state dye‐sensitized solar cells prepared from new porous TiO₂ photoanodes based on laser pyrolysis nanocrystals. This strategy exploits a reduced number of processing steps as well as non‐toxic chemical compounds to demonstrate highly porous TiO₂ films. The possibility to easily tune the TiO₂ nanocrystal physical properties allows us to demonstrate all solid‐state dye‐sensitized devices based on a commercial benchmark materials (organic indoline dye and molecular hole transporter) presenting state‐of‐the‐art performance comparable with reference devices based on a commercial TiO₂ paste. In particular, a drastic improvement in pore infiltration, which is found to balance a relatively lower surface area compared to the reference electrode, is evidenced using laser‐synthesized nanocrystals resulting in an improved short‐circuit current density under full sunlight. Transient photovoltage decay measurements suggest that charge recombination kinetics still limit device performance. However, the proposed strategy emphasizes the potentialities of the laser pyrolysis technique for up‐scaling nanoporous TiO₂ electrodes for various applications, especially for solar energy conversion.     

Ultrathin Perovskite Monocrystals Boost the Solar Cell Performance

Grains and grain boundaries play key roles in determining halide perovskite‐based optoelectronic device performance. Halide perovskite monocrystalline solids with large grains, smaller grain boundaries, and uniform surface morphology improve charge transfer and collection, suppress recombination loss, and thus are highly favorable for developing efficient solar cells. To date, strategies of synthesizing high‐quality thin monocrystals (TMCs) for solar cell applications are still limited. Here, by combining the antisolvent vapor‐assisted crystallization and space‐confinement strategies, high‐quality millimeter sized TMCs of methylammonium lead iodide (MAPbI₃) perovskites with controlled thickness from tens of nanometers to several micrometers have been fabricated. The solar cells based on these MAPbI₃ TMCs show power conversion efficiency (PCE) of 20.1% which is significantly improved compared to their polycrystalline counterparts (PCE) of 17.3%. The MAPbI₃ TMCs show large grain size, uniform surface morphology, high hole mobility (up to 142 cm² V^?1 s^?1), as well as low trap (defect) densities. These properties suggest that TMCs can effectively suppress the radiative and nonradiative recombination loss, thus provide a promising way for maximizing the efficiency of perovskite solar cells.     

Graded Bandgap Perovskite with Intrinsic n–p Homojunction Expands Photon Harvesting Range and Enables All Transport Layer‐Free Perovskite Solar Cells

Organic–inorganic halide perovskites are promising materials for next‐generation photovoltaic device due to their attractive photoelectrical properties such as strong light absorption, high carrier mobility, and tunable bandgap. Generally, perovskite solar cells require carrier transport layers (CTL) to provide a built‐in electric field and reduce the recombination rate. However, the construction of suitable electron‐ and hole‐transport layers is not cost effective, impairing the commercial application of the devices. An n–p perovskite homojunction absorber with a graded bandgap is developed by introducing a three‐step dynamic spin‐coating strategy and variable valence Sn elements. The bandgap of the perovskite absorber is gradually manipulated from 1.53 eV (the bottom) to 1.27 eV (the top). The electronic behavior is also transformed from n‐type (excess PbI₂, the bottom) to p‐type (Sn vacancy, the top) in a very short distance (50 nm). This designed perovskite homojunction electronic structure not only expands the light harvesting range from 800 to 970 nm which provides potential to break the PCE limits, but also promotes oriented carrier transportation and weakens the dependence on CTL. The demonstrated asymmetrical active layer shows a brand‐new approach to simplify the device structure and boost the performance of CTL‐free perovskite solar cells.