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We report an exploratory study on the crystal formation behavior of CsPbI2Br perovskite films by adding excess cesium iodide (CsI). Surprisingly, facile co-crystallization of CsI and CsPbI2Br in the form of spinodal decomposition is observed. Significantly, the two phases spontaneously form morphing into a remarkably uniform bicontinuous nanoscale blend with high orientational correlation through the well-matched (110) plane of CsI and the (200) plane of CsPbI2Br. The CsPbI2Br films produced by the spinodal decomposition method not only enjoy a compact surface, low defect concentration, and long carrier lifetimes, they also retain their excellent charge transport property. By employing such a CsPbI2Br film for carbon-based perovskite solar cells, power conversion efficiency exceeding 10% is achieved with remarkable thermal stability. Our results provide valuable insight into the role of CsI in perovskite crystallization and a promising approach for designing inorganic halide perovskite-based devices.

Delicately designed dopant-free hole-transporting materials (HTMs) with ordered structure have become one of the major strategies to achieve high-performance perovskite solar cells (PSCs). In this work, we report two donor-π linker-donor (D-π-D) HTMs, N01 and N02, which consist of facilely synthesized 4,8-di(n-hexyloxy)-benzo[1,2-b:4,5-b']dithiophene as a π linker, with 10-bromohexyl-10H-phenoxazine and 10-hexyl-10H-phenoxazine as donors, respectively. The N01 molecules form a two-dimensional conjugated network governed by C-H⋅⋅⋅O and C-H⋅⋅⋅Br interaction between phenoxazine donors, and synchronously construct a three-dimension lamellar structure with the aid of interlaminar π-π interaction. Consequently, N01 as a dopant-free small-molecule HTM exhibits a higher intrinsic hole mobility and more favorable interfacial properties for hole transport, hole extraction and perovskite growth, enabling an inverted PSC to achieve a very impressive power conversion efficiency of 21.85 %.

The prevalence of COVID‐19 has caused global dysfunction in terms of public health, sustainability, and socio‐economy. While vaccination shows potential in containing the spread, the development of surfaces that effectively reduces virus transmission and infectivity is also imperative, especially amid the early stage of the pandemic. However, most virucidal surfaces are operated under harsh conditions, making them impractical or potentially unsafe for long‐term use. Here, it is reported that laser‐induced graphene (LIG) without any metal additives shows marvelous antiviral capacities for coronavirus. Under low solar irradiation, the virucidal efficacy of the hydrophobic LIG (HLIG) against HCoV‐OC43 and HCoV‐229E can achieve 97.5% and 95%, respectively. The photothermal effect and the hydrophobicity of the HLIG synergistically contribute to the superior inactivation capacity. The stable antiviral performance of HLIG enables its multiple uses, showing advantages in energy saving and environmental protection. This work discloses a potential method for antiviral applications and has implications for the future development of antiviral materials., The hydrophobic laser‐induced graphene (HLIG) enables effective inactivation of coronavirus from the synergy of photothermal effect and hydrophobicity. The non‐metal HLIG achieves a 97.5% and 95% virucidal efficacy for HCoV‐OC43 and HCoV‐229E in 15 min under solar irradiation. In addition, the antiviral performance of HLIG is stable after multiple uses.

Solution-processed organic solar cells (OSCs) are a promising candidate for next-generation photovoltaic technologies. However, the short exciton diffusion length of the bulk heterojunction active layer in OSCs strongly hampers the full potential to be realized in these bulk heterojunction OSCs. Herein, we report high-performance OSCs with a pseudo-bilayer architecture, which possesses longer exciton diffusion length benefited from higher film crystallinity. This feature ensures the synergistic advantages of efficient exciton dissociation and charge transport in OSCs with pseudo-bilayer architecture, enabling a higher power conversion efficiency (17.42%) to be achieved compared to those with bulk heterojunction architecture (16.44%) due to higher short-circuit current density and fill factor. A certified efficiency of 16.31% is also achieved for the ternary OSC with a pseudo-bilayer active layer. Our results demonstrate the excellent potential for pseudo-bilayer architecture to be used for future OSC applications., The so-called pseudo-bilayer (PB) organic solar cell (OSC) device architecture can promote enhanced exciton dissociation and charge transport, leading to improved device performance. Here, the authors report high-efficiency OSCs that features a PB architecture and optimized ternary system.

State-of-art Y-series polymer acceptors are typically based on a mono-thiophene linker, which can cause some twisted molecular conformations and thus limit the performance of all-polymer solar cells (all-PSCs). Here, a high-performance polymer acceptor based on vinylene linkers is reported, which leads to surprising changes in the polymers' molecular conformations, optoelectronic properties, and enhanced photovoltaic performance. It is found that the polymer acceptors based on thiophene or bithiophene linkers (PY-T-γ and PY-2T-γ) display significant molecular twisting between end-groups and linker units, while the vinylene-based polymer (PY-V-γ) exhibits a more coplanar and rigid molecular conformation. As a result, PY-V-γ demonstrates a better conjugation and tighter interchain stacking, which results in higher mobility and a reduced energetic disorder. Furthermore, detailed morphology investigations reveal that the PY-V-γ-based blend exhibits high domain purity and thus a better fill factor in its all-PSCs. With these, a higher efficiency of 17.1% is achieved in PY-V-γ-based all-PSCs, which is the highest efficiency reported for binary all-PSCs to date. This work demonstrates that the vinylene-linker is a superior unit to build polymer acceptors with more coplanar and rigid chain conformation, which is beneficial for polymer aggregation and efficient all-PSCs.

Electrocatalytic carbon dioxide reduction reaction (CO

Passivating surface and bulk defects of perovskite films has been proven to be an effective way to minimize nonradiative recombination losses in perovskite solar cells (PVSCs). The lattice interference and perturbation of atomic periodicity at the perovskite surfaces often significantly affect the material properties and device efficiencies. By tailoring the terminal groups on the perovskite surface and modifying the surface chemical environment, the defects can be reduced to enhance the photovoltaic performance and stability of derived PVSCs. Here, we report a rationally designed bifunctional molecule, piperazinium iodide (PI), containing both R2NH and R2NH2+ groups on the same six-membered ring, behaving both as an electron donor and an electron acceptor to react with different surface-terminating ends on perovskite films. The resulting perovskite films after defect passivation show released surface residual stress, suppressed nonradiative recombination loss, and more n-type characteristics for sufficient energy transfer. Consequently, charge recombination is significantly suppressed to result in a high open-circuit voltage (VOC) of 1.17 V and a reduced VOC loss of 0.33 V. A very high power conversion efficiency (PCE) of 23.37% (with 22.75% certified) could be achieved, which is the highest value reported for inverted PVSCs. Our work reveals a very effective way of using rationally designed bifunctional molecules to simultaneously enhance the device performance and stability.

Bacteria detection and toxicity measurement are essential in many aspects. Becoming increasingly popular in recent years, paper-based analytical devices (PADs) have proven to be cost-effective, portable and eco-friendly with quantitative diagnostic results. In this work, by a straightforward soaking-drying method, a resazurin-deposited PAD has been developed for rapid bacteria detection and biotoxicity measurement. The colorimetric response on the PAD was generated from metabolic reduction of resazurin by Enterococcus faecalis, a facultative anaerobic bacterial strain. After recording and quantifying the colorimetric response with Hue value by a smartphone, the bioassay on PAD enables the detection of resazurin reduction kinetics difference among bacteria at various densities in 10 min. Thereby, the bioassay on PAD was applied to study the toxicity of two chlorophenols, i.e. pentachlorophenol (PCP) and 4-chlorophenol (4-CP), to E. faecalis. Compared to growth-based inhibition test, which takes 5 h, this assay shows higher efficiency, i.e. in 30 min, the biotoxicity difference between PCP and 4-CP can be identified.

Understanding the molecular structure and self-assembly of thiadiazole-derived non-fullerene acceptors (NFAs) is very critical for elucidating the origin of their extraordinary charge generation and transport properties that enable high power conversion efficiencies to be achieved in these systems. A comprehensive crystallographic study on a state-of-the-art NFA, Y6, and its selenium analog

Recently, owing to the high energy density and excellent security, wearable Zn-air batteries (ZABs) have been known as one of the most prominent wearable energy storage devices. However, sluggish oxygen reaction kinetics of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in the air-breathe cathode seriously has limited further practical applications. In this work, we synthesize a NiCo

Designing new hole-transporting materials (HTMs) with desired chemical, electrical, and electronic properties is critical to realize efficient and stable inverted perovskite solar cells (PVSCs) with a p-i-n structure. Herein, the synthesis of a novel 3D small molecule named TPE-S and its application as an HTM in PVSCs are shown. The all-inorganic inverted PVSCs made using TPE-S, processed without any dopant or post-treatment, are highly efficient and stable. Compared to control devices based on the commonly used HTM, PEDOT:PSS, devices based on TPE-S exhibit improved optoelectronic properties, more favorable interfacial energetics, and reduced recombination due to an improved trap passivation effect. As a result, the all-inorganic CsPbI2 Br PVSCs based on TPE-S demonstrate a remarkable efficiency of 15.4% along with excellent stability, which is the one of the highest reported values for inverted all-inorganic PVSCs. Meanwhile, the TPE-S layer can also be generally used to improve the performance of organic/inorganic hybrid inverted PVSCs, which show an outstanding power conversation efficiency of 21.0%, approaching the highest reported efficiency for inverted PVSCs. This work highlights the great potential of TPE-S as a simple and general dopant-free HTM for different types of high-performance PVSCs.

The bulk-heterojunction blend of an electron donor and an electron acceptor material is the key component in a solution-processed organic photovoltaic device. In the past decades, a p-type conjugated polymer and an n-type fullerene derivative have been the most commonly used electron donor and electron acceptor, respectively. While most advances of the device performance come from the design of new polymer donors, fullerene derivatives have almost been exclusively used as electron acceptors in organic photovoltaics. Recently, nonfullerene acceptor materials, particularly small molecules and oligomers, have emerged as a promising alternative to replace fullerene derivatives. Compared to fullerenes, these new acceptors are generally synthesized from diversified, low-cost routes based on building block materials with extraordinary chemical, thermal, and photostability. The facile functionalization of these molecules affords excellent tunability to their optoelectronic and electrochemical properties. Within the past five years, there have been over 100 nonfullerene acceptor molecules synthesized, and the power conversion efficiency of nonfullerene organic solar cells has increased dramatically, from ∼2% in 2012 to13% in 2017. This review summarizes this progress, aiming to describe the molecular design strategy, to provide insight into the structure-property relationship, and to highlight the challenges the field is facing, with emphasis placed on most recent nonfullerene acceptors that demonstrated top-of-the-line photovoltaic performances. We also provide perspectives from a device point of view, wherein topics including ternary blend device, multijunction device, device stability, active layer morphology, and device physics are discussed.

The mixed metal Pb/Sn halide perovskites have drawn significant attentions in perovskite photovoltaics due to their broad absorption spectra and tunable band gaps. To obtain a deeper understanding of these materials properties, single crystals are regarded as the best platform among various building blocks for fundamental study. Here, we report the mixed-metal MAPbxSn1–xBr3 (MA = CH3NH3) perovskite single crystals grown by top seeded solution growth (TSSG) method. Systematical characterizations were applied to investigating their structures and optoelectronic properties. These single crystals kept higher stability even exposed to air over one month than that of MASnBr3. The outstanding electrical properties, such as lower trap-state density and higher carrier mobility, were investigated by space charge-limited current (SCLC) and the Hall Effect measurements. More importantly, these perovskite single crystals exhibited much narrower optical band gap (1.77 eV) and longer carrier lifetime (∼2 μs) than those ...

Biaxially-extended octithiophene-based conjugated polymers are demonstrated as effective polymeric hole-transporting layers (HTLs) to simultaneously enhance the efficiency and UV-photostability of perovskite solar cells (PVSCs). The intense UV absorption contributed from the conjugated side-chain groups of such polymers facilitated its function of UV filtering when serving as the bottom HTL in PVSCs. Through rationally tailoring polymer backbone structure, a highly efficient (PCE: 18.34%) PVSC with much improved UV-photostability and ambient stability was successfully achieved.

Summary Despite the demonstrated high power conversion efficiency (PCE) of perovskite solar cells (PVSC), long-term stability of the device operated in humid environments under photo- and thermal stresses is still a serious concern prior to any commercialization. To provide possible solutions to overcome this hurdle, we have synthesized an n-type conjugated molecule, c -HATNA, that can be crosslinked as an electron-transporting layer (ETL) on top of the desired perovskites. By proper doping to increase its electron-transporting property, a high PCE of 18.21% can be obtained with respectable moisture and thermal stability without encapsulation. Moreover, this c -HATNA ETL can be used in conjunction with another crosslinkable hole-transporting layer, c -TCTA-BVP, to fabricate all-crosslinked charge-transporting layers (CTLs) for PVSCs and achieve 16.08% and 13.42% PCEs on rigid and flexible substrates, respectively. More importantly, the device with all-crosslinked CTLs showed impressive thermal stability in ambient environment: almost 70% of its initial PCE after being heated at 70°C for 300 hr.

Significant efforts have been devoted to developing new dopant-free hole transporting materials (HTMs) for perovskite solar cells (PVSCs). Fluoranthene is one typical cyclopentene-fused polycyclic aromatic hydrocarbon with a rigid planarized structure, and thus could be an ideal building block to construct dopant-free HTMs, which have not been reported yet. Here, we report a new and simple synthetic method to prepare unreported 2,3-dicyano-fluoranthene through a Diels-Alder reaction between dibenzofulvene and tetracyanoethylene, and demonstrate that it can serve as an efficient electron-withdrawing unit for constructing donor-acceptor (D-A) type HTMs. This novel building block not only endows the resulting molecules with suitable energy levels, but also enables highly ordered and strong molecular packing in solid states, both of which could facilitate hole extraction and transport. Thus with dopant-free HTMs, impressive efficiencies of 18.03% and 17.01% which are associated with enhanced stability can be achieved based on conventional n-i-p and inverted p-i-n PVSCs respectively, outperforming most organic dopant-free HTMs reported so far.

Lead halide perovskite and organic solar cells (PSCs and OSCs) are considered as the prime candidates currently for clean energy applications due to their solution and low-temperature processibility. Nevertheless, the substantial photon loss in near-infrared (NIR) region and relatively large photovoltage deficit need to be improved to enable their uses in high-performance solar cells. To mitigate these disadvantages, low-bandgap organic bulk-heterojunction (BHJ) layer into inverted PSCs to construct facile hybrid solar cells (HSCs) is integrated. By optimizing the BHJ components, an excellent power conversion efficiency (PCE) of 23.80%, with a decent open-circuit voltage (Voc ) of 1.146 V and extended photoresponse over 950 nm for rigid HSCs is achieved. The resultant devices also exhibit superior long-term (over 1000 h) ambient- and photostability compared to those from single-component PSCs and OSCs. More importantly, a champion PCE of 21.73% and excellent mechanical durability can also be achieved in flexible HSCs, which is the highest efficiency reported for flexible solar cells to date. Taking advantage of these impressive device performances, flexible HSCs into a power source for wearable sensors to demonstrate real-time temperature monitoring are successfully integrated.

Asymmetric isomerization from BP6T‐4F to ABP6T‐4F not only lowers the exciton bonding energy but also optimizes the crystallization performance, achieving a pronounced isomer effect with 9.4% power conversion efficiency enhancement. Moreover, ternary devices are also fabricated, considering good compatibility between ABP6T‐4F and CH1007, to deliver a power conversion efficiency over 17%.

Tin oxide (SnO2) has recently attracted significant research interest for its role functioning as an efficient electron-transporting layer (ETL) due to its higher charge mobility than the commonly used titanium oxide (TiO2) for realizing high-performance perovskite solar cells (PVSCs). However, it is still challenging to develop a facile, low-temperature solution-based (

Although organic-inorganic hybrid perovskite solar cells (PVSCs) have achieved dramatic improvement in device efficiency, their long-term stability remains a major concern prior to commercialization. To address this issue, extensive research efforts are dedicated to exploiting all-inorganic PVSCs by using cesium (Cs)-based perovskite materials, such as α-CsPbI3 . However, the black-phase CsPbI3 (cubic α-CsPbI3 and orthorhombic γ-CsPbI3 phases) is not stable at room temperature, and it tends to convert to the nonperovskite δ-CsPbI3 phase. Here, a simple yet effective approach is described to prepare stable black-phase CsPbI3 by forming a heterostructure comprising 0D Cs4 PbI6 and γ-CsPbI3 through tuning the stoichiometry of the precursors between CsI and PbI. Such heterostructure is manifested to enable the realization of a stable all-inorganic PVSC with a high power conversion efficiency of 16.39%. This work provides a new perspective for developing high-performance and stable all-inorganic PVSCs.

The rational design and development of the low-cost and effective electrocatalysts toward oxygen evolution reaction (OER) are essential in the storage and conversion of clean and renewable energy sources. Herein, a ternary copper-cobalt sulfide nanosheets electrocatalysts (denoted as CuCoS/CC) for electrochemical water oxidation has been synthesized on carbon cloth (CC) via the sulfuration of CuCo-based precursors. The obtained CuCoS/CC reveals excellent electrocatalytic performance toward OER in 1.0 M KOH. It exhibits a particularly low overpotential of 276 mV at current density of 10 mA cm&minus, 2, and a small Tafel slope (58 mV decade&minus, 1), which is superior to the current commercialized noble-metal electrocatalysts, such as IrO2. Benefiting from the synergistic effect of Cu and Co atoms and sulfidation, electrons transport and ions diffusion are significantly enhanced with the increase of active sites, thus the kinetic process of OER reaction is boosted. Our studies will serve as guidelines in the innovative design of non-noble metal electrocatalysts and their application in electrochemical water splitting

We report an exploratory study on the crystal formation behavior of CsPbI

Low cost, highly efficient dopant-free hole transporting materials (HTMs) are highly desirable for the commercialization of perovskite solar cells (PVSCs). Herein, a facile synthetic route is designed to prepare two new D-A- D -type HTMs (BTF5 and BTF6) with low lab synthetic costs by making dicyanofluoranthene as the key intermediate. The rational structure modifications of donor subunits enable a significant optimization of photophysical, charge transporting properties and final device performance for resulting HTMs. BTF6 with meta-methoxyl substitutions exhibits more matched energy levels with perovskites and much enhanced hole mobility in comparison to BTF5 with para-methoxyl substitutions, thereby leading to significantly distinct device efficiencies as dopant-free HTMs in inverted PVSCs, 20.34% for BTF6 vs. 11.42% for BTF5. In addition, the unsatisfactory crystallinity of perovskite films atop BTF5 is found to be another major reason for its significantly poor device efficiency. More encouragingly, it is further demonstrated that BTF6 can be suitable for fabricating dopant-free flexible PVSCs towards a promising PCE over 18% with a low hysteresis, which is the highest value for flexible devices based on small molecule HTMs, and even can be comparable to the best PCEs reported from self-doped PEDOT:PSS.

Fe–Co bimetallic electrocatalysts show tremendous promise for both oxygen reduction reaction (ORR) and oxygen evolution reaction in the alkaline medium to replace precious metal catalysts. Here, we report a successful size modulation strategy for FeCo binary alloys in situ growth on the carbon matrix. Analogous to Pt nanoparticles, the size modulation could give rise to increased active sites in FeCo-based catalysts without altering their chemical properties. The compositionally optimized template with abundant carbon nanotubes and uniform distribution of FeCo alloy nanoparticles, exhibits superior electrocatalytic activity by achieving a high-performance half-wave potential of 0.88 V toward ORR as well as robust stability after 10 000 cycles. The open-circuit potential (Voc) of the liquid Zn–air battery is close to 1.40 V which is comparable with that of the Zn–air battery equipped with Pt/C+IrO2. Our findings offer new prospects for understanding metal particle sizes and electrocatalytic performance of pyrolyzed transition metal–carbon materials.

Wide-bandgap perovskite solar cells (PVSCs) possess significant potential in providing reliable power sources for applications in the Internet of Things (IoT) ecosystem under indoor light illumination. However, the wide-bandgap PVSCs usually suffer from photo-induced phase segregation and non-radiative energy loss caused by the Shockley-Read-Hall (SRH) type trap-assisted recombination at the interfaces in the devices. To address these issues, a simple strategy by applying phenethylammonium halides to reduce the energy loss and suppress the phase segregation of wide-bandgap PVSCs is developed. The devices incorporated with phenethylammonium chloride (PEACl) is revealed to achieve a high open-circuit voltage (VOC) of 1.26 V, leading to a merit power conversion efficiency (PCE) of 18.3%, which is the best performance among the inverted wide-bandgap PVSCs (~1.75 eV) under one sun illumination. Meanwhile, the photovoltaic performance of the device is also significantly enhanced, especially under a white light-emitting diode (LED) with an illumination of 1000 lux, showing a PCE of 35.6% with a high VOC of 1.08 V. Impressively, the device delivers a minimum energy loss of 670 meV, which is among the smallest value reported for perovskite-based indoor photovoltaics.

In this work, an efficient inverted perovskite solar cell with decent ambient stability is successfully demonstrated by employing an n-type polymer, poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalene diimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (N2200), as the electron-transporting layer (ETL). The device performance can be further enhanced from a power conversion efficiency (PCE) of 15 to 16.8 % by tailoring the electronic properties of N2200 with a polymeric additive, poly[9,9-bis(6'-(N,N-diethylamino)propyl)-fluorene-alt-9,9-bis(3-ethyl(oxetane-3-ethyloxy)-hexyl) fluorene] (PFN-Ox). More importantly, the device derived from this hybrid ETL can maintain good ambient stability inherent from the pristine N2200 ETL, for which 60-70 % of initial PCE can be retained after being stored in air with 10-20 % humidity for 45 days.

NiO is a promising hole transporting material for perovskite solar cells due to its high hole mobility, good stability, easy processibility, and suitable Fermi level for hole extraction. However, the efficiency of NiO-based cells is still limited by the slow hole extraction due to the poor perovskite/NiO interface and the inadequate quality of the two solution-processed material phases. Here, large influences of a monolayer surface modification of NiO nanocrystal layers with ethanolamine molecules are demonstrated on the enhancement of hole extraction/transport and thus the photovoltaic performance. The underlying causes have been revealed by a series of studies, pointing to a favorable dipole layer formed by the molecular adsorption along with the enhanced perovskite crystallization and the improved interface contact. Comparatively, the solar cells based on a diethanolamine-modified NiO layer have achieved a rather high fill factor, indeed one of the highest among NiO-based perovskite solar cells, and high short-circuit photocurrent density (Jsc), resulting in a power conversion efficiency of ≈16%, most importantly, without hysteresis.

In this work, we have successfully utilized a facile hydrothermal method to prepare crystalline Zn2SnO4 nanoparticles (ZSO NPs) and applied them as an efficient electron-transporting layer (ETL) via a simple room-temperature solution process for perovskite solar cells (PVSCs). The superior semiconducting properties of this ZSO-based ETL enable an efficient (PCE: 17.7%) inverted p–i–n PVSC to be fabricated with respectable ambient stability. It can retain over 90% of its original PCE after being stored under ambient conditions for 14 days under 30 ± 5% relative humidity. Moreover, it also facilitates the fabrication of efficient conventional n–i–p PVSCs with a PCE of ∼14.5% and ∼11.4% achieved on a glass/ITO rigid substrate and PEG/ITO flexible substrate, respectively.

Cesium-based inorganic perovskites have recently attracted great research focus due to their excellent optoelectronic properties and thermal stability. However, the operational instability of all-inorganic perovskites is still a main hindrance for the commercialization. Herein, a facile approach is reported to simultaneously enhance both the efficiency and long-term stability for all-inorganic CsPbI2.5Br0.5 perovskite solar cells via inducing excess lead iodide (PbI2) into the precursors. Comprehensive film and device characterizations are conducted to study the influences of excess PbI2 on the crystal quality, passivation effect, charge dynamics, and photovoltaic performance. It is found that excess PbI2 improves the crystallization process, producing high-quality CsPbI2.5Br0.5 films with enlarged grain sizes, enhanced crystal orientation, and unchanged phase composition. The residual PbI2 at the grain boundaries also provides a passivation effect, which improves the optoelectronic properties and charge collection property in optimized devices, leading to a power conversion efficiency up to 17.1% with a high open-circuit voltage of 1.25 V. More importantly, a remarkable long-term operational stability is also achieved for the optimized CsPbI2.5Br0.5 solar cells, with less than 24% degradation drop at the maximum power point under continuous illumination for 420 h.

Currently, there are only very few dopant‐free polymer hole‐transporting materials (HTMs) that can enable perovskite solar cells (PVSCs) to demonstrate a high power conversion efficiency (PCE) of greater than 20%. To address this need, a simple and efficient way is developed to synthesize novel crossconjugated polymers as high performance dopant‐free HTMs to endow PVSCs with a high PCE of 21.3%, which is among the highest values reported for single‐junction inverted PVSCs. More importantly, rational understanding of the reasons why two isomeric polymer HTMs (PPE1 and PPE2) with almost identical photophysical properties, hole‐transporting ability, and surface wettability deliver so distinctly different device performance under similar device fabrication conditions is manifested. PPE2 is found to improve the quality of perovskite films cast on top with larger grain sizes and more oriented crystallization. These results help unveil the new HTM design rules to influence the perovskite growth/crystallization for improving the performance of inverted PVSCs., Two isomeric crossconjugated polymer hole‐transporting materials (HTMs) are developed to demonstrate significantly distinct device power conversion efficiencies (PCEs) under the same device fabrication conditions, 11.1% PPE1 and 19.3% for PPE2, which is found to be due to the improved quality of perovskite films made on top of PPE2. More excitingly, the PPE2‐based perovskite solar cells (PVSCs) can further achieve a more impressive PCE of 21.3% through suitable surface passivation.