Suppressing the Photoinduced Halide Segregation in Wide-Bandgap Perovskite Solar Cells by Strain Relaxation

Efficient and stable wide bandgap (WBG) perovskite solar cells (PSCs) are imperative for fabricating superior tandem devices. However, small crystal grains and light-induced phase segregation of WBG perovskite result in large open-circuit voltage (V_OC) deficits, critically impeding the development of the related devices. Herein, the effective functional groups of Lewis-base trans-Ferulic acid (t-FA) are employed to release the residual microstrain in the perovskite lattice. Larger perovskite crystals are formed by strengthening the interaction between the perovskite solute and solution. The lattice structure is stabilized to suppress light-induced halide segregation. Finally, the power conversion efficiency (PCE) of the optimized device with a bandgap of ≈1.77 eV is increased from 17.33% to 19.31% with the enhancement of V_OC. Moreover, replacing a mixture of MeO-2PACZ and Me-4PACZ as the hole transporting layer (HTL), the PCE further lifts to 19.9% and V_OC is 1.32 V, one of the highest performances reported for WBG PSCs, especially for devices prepared entirely by solution spin-coating. Therefore, this study provides a practicable alternative for realizing efficient WBG PSCs, which can contribute to the growth of perovskite-based tandem devices.     

Low-Dimensional 2-thiopheneethylammonium Lead Halide Capping Layer Enables Efficient Single-Junction Methylamine-Free Wide-Bandgap and Tandem Perovskite Solar Cells

Wide-bandgap (WBG) perovskite solar cells (PSCs) have garnered significant attention for their potential applications in tandem solar cells. However, their large open-circuit voltage (V_OC) deficit and serious photo-induced halide segregation remain the main challenges that impede their applications. Herein, a post-treatment strategy without thermal annealing is presented to form a 2D top layer of 2-thiopheneethylammonium lead halide (n = 1) on WBG perovskites. This thermal annealing-free post-treatment method can more effectively passivate the defects of WBG methylamine (MA)-free formamidinium/cesium lead iodide/bromide perovskite films and suppress photo-induced perovskite phase segregation, as compared with the thermal annealing method that yields multi-2D phases. The resulting opaque and semi-transparent 1.66 eV-bandgap perovskite solar cells deliver maximum power conversion efficiencies of 21.47% (a small V_OC deficit of 0.43 V) and 19.11%, respectively, both of which are among the highest reports for inverted MA-free WBG PSCs. Consequently, four-terminal all-perovskite tandem cells realize a remarkable efficiency of 26.64%, showing great promise for their applications in efficient multi-junction tandem solar cells.     

24.64%-Efficiency MA-Free Perovskite Solar Cell with Voc of 1.19 V Enabled by a Hinge-Type Fluorine-Rich Complex

High density of defects at interface severely affects the performance of perovskite solar cells (PSCs). Herein, cobalt (II) hexafluoro-2,4-pentanedionat (CoFAc), a hinge-type fluorine-rich complex, is introduced onto the surface of formamidinium cesium lead iodide (FACsPbI₃) film to address the issues of perovskite/Spiro-OMeTAD interface. The existence of CoFAc passivates both organic cation and halide anion vacancies by establishing powerful hydrogen bonds with HC(NH₂)₂⁺ (FA⁺) and strong ionic bonds with Pb²⁺ in perovskite films. In addition, CoFAc serves as a connecting link to enhance interfacial hole-transport kinetics via interacting with Spiro-OMeTAD. Consequently, FACsPbI₃ PSCs with CoFAc modification display a champion power conversion efficiency (PCE) of 24.64% with a charming open-circuit voltage (V_OC) of 1.191 V, which is the record V_OC among all the reported organic-inorganic hybrid PSCs with TiO₂ as electron transport layer. Furthermore, CoFAc-modified devices exhibit an outstanding long-term stability, which can maintain 95% of their initial PCEs after exposure to ambient atmosphere for 1500 h without any encapsulation.     

A Polymer Defect Passivator for Efficient Hole-Conductor-Free Printable Mesoscopic Perovskite Solar Cells

Due to the low cost and excellent potential for mass production, printable mesoscopic perovskite solar cells (p-MPSCs) have drawn a lot of attention among other device structures. However, the low open-circuit voltage (V_OC) of such devices restricts their power conversion efficiency (PCE). This limitation is brought by the high defect density at perovskite grain boundaries in the mesoporous scaffold, which results in severe nonradiative recombination and is detrimental to the V_OC. To improve the perovskite crystallization process, passivate the perovskite defects, and enhance the PCE, additive engineering is an effective way. Herein, a polymeric Lewis base polysuccinimide (PSI) is added to the perovskite precursor solution as an additive. It improves the perovskite crystallinity and its carbonyl groups strongly coordinate with Pb²⁺, which can effectively passivate defects. Additionally, compared with its monomer, succinimide (SI), PSI serves as a better defect passivator because the long-chained macromolecule can be firmly anchored on those defect sites and form a stronger interaction with perovskite grains. As a result, the champion device has a PCE of 18.84%, and the V_OC rises from 973 to 1030 mV. This study offers a new strategy for fabricating efficient p-MPSCs.     

Illumination Enhanced Crystallization and Defect Passivation for High Performance CsPbI3 Perovskite Solar Cells by Sacrificing Dye

All-inorganic perovskite solar cells (PSCs) have been the research focus due to their high thermal stability and proper band gap for tandem solar cells. However, their power conversion efficiency (PCE) is still lower than that of organic-inorganic hybrid PSCs. Herein, a sacrificing dye (Rhodamine B isothiocyanate, RBITC) is developed to regulate the growth of perovskite film by in situ release of ethylammonium cations, isothiocyanate anions and benzoic acid molecules upon annealing and illumination. The ethylammonium cations can efficiently passivate surface defects. The isothiocyanate anions incorporate with uncoordinated Pb to regulate the crystallization process. The benzoic acid molecules facilitate the nucleation of the perovskite crystals. Especially, the illumination can accelerate the release of these beneficial ions/molecules to improve the quality of perovskite films further. After optimization with RBITC, a high open circuit voltage (V_OC) of 1.24 V and a champion PCE of 20.95% are obtained, which are among the highest Voc and PCE values of CsPbI₃ PSCs. Accordingly, the operational stability of the PSC devices is significantly improved. The results provide an efficient chemical strategy to regulate the formation of perovskite films in whole crystallization process for high performance all-inorganic PSCs.     

Rubidium Fluoride Modified SnO2 for Planar n-i-p Perovskite Solar Cells

Regulating the electron transport layer (ETL) has been an effective way to promote the power conversion efficiency (PCE) of perovskite solar cells (PSCs) as well as suppress their hysteresis. Herein, the SnO₂ ETL using a cost-effective modification material rubidium fluoride (RbF) is modified in two methods: 1) adding RbF into SnO₂ colloidal dispersion, F and Sn have a strong interaction, confirmed via X-ray photoelectron spectra and density functional theory results, contributing to the improved electron mobility of SnO₂; 2) depositing RbF at the SnO₂/perovskite interface, Rb⁺ cations actively escape into the interstitial sites of the perovskite lattice to inhibit ions migration and reduce non-radiative recombination, which dedicates to the improved open-circuit voltage (V_oc) for the PSCs with suppressed hysteresis. In addition, double-sided passivated PSCs, RbF on the SnO₂ surface, and p-methoxyphenethylammonium iodide on the perovskite surface, produces an outstanding PCE of 23.38% with a V_oc of 1.213 V, corresponding to an extremely small V_oc deficit of 0.347 V.     

Fully Printed High-Performance Quasi-Two-Dimensional Perovskite Solar Cells via Multifunctional Interfacial Engineering

Planar n–i–p carbon perovskite solar cells (PSCs) with a hole transport layer that can be fabricated at low temperatures at low-cost exhibit great potential for large-scale manufacturing. Moreover, 2D perovskites have attracted considerable attention owing to their higher stability. In this work, scalable and highly efficient fully printed large-area carbon electrode-based 2D perovskite modules are reported through the insertion of a thin naphthaleneimide derivative (CATNI)-based interfacial layer between tin (IV) oxide and the perovskite layer. The results show that this facilitates the formation of the interfacial contact, suppresses energy losses, and substantially improves the performance parameters of the PSCs, especially their V_OC value. A significantly enhanced V_OC of 1.13 V is achieved resulting in the device PCE value reaching over 18%, which is one of the highest reported for fully printed PSCs so far. It is found that with the deployment of this CATNI-based interfacial layer, a more efficient carrier extraction is achieved. This ultimately contributed to enhanced spectral response as well as improved V_OC for these carbon electrodes based on fully printed devices. Finally, the carbon-perovskite solar modules (carbon-PSMs) are fabricated on ITO glass substrates with dimensions of 5.0 × 5.0 cm. These prepared modules exhibited outstanding photovoltaic performance with the highest PCE value of over 14.6%.     

Surface Regulation through Dipolar Molecule Boosting the Efficiency of Mixed 2D/3D Perovskite Solar Cell to 24%

Mixed 2D/3D perovskite solar cells (PSCs) show promising performances in efficiency and long-term stability. The functional groups terminated on a large organic molecule used to construct 2D capping layer play a key role in the chemical interaction mechanism and thus influence the device performance. In this study, 4-(trifluoromethyl) benzamidine hydrochloride (TFPhFACl) is adopted to construct 2D capping layer atop 3D perovskite. It is found that there are two mechanisms synergistically contributing to the increase of efficiency: 1) The TFPhFA⁺ cations form a dipole layer promoting the interfacial charge transport. 2) The suppressed nonradiative recombination of perovskite through the coordination of TFPhFA⁺ cations with Pb–I octahedron, as well as the recrystallization of 3D perovskite induced by Cl^- ions. As a result, the PSC delivers an efficiency of 24.0% with improved open-circuit voltage (V_OC) of 1.16 V, short-circuit current density (J_SC) of 25.42 mA cm^-2, and fill factor of 81.26%. The device shows no decrease in efficiency after 1500 h stored in the air indicating the good stability. The utilization of TFPhFACl not only provides a facile way to optimize the interfacial problems, but also gives a new perspective for rational design of large spacer molecule for constructing efficient 2D/3D PSCs.     

The Impact of Sequential Fluorination of π‐Conjugated Polymers on Charge Generation in All‐Polymer Solar Cells

The performance of all‐polymer solar cells (all‐PSCs) is often limited by the poor exciton dissociation process. Here, the design of a series of polymer donors ( P1 – P3 ) with different numbers of fluorine atoms on their backbone is presented and the influence of fluorination on charge generation in all‐PSCs is investigated. Sequential fluorination of the polymer backbones increases the dipole moment difference between the ground and excited states (Δµ_ge) from P1 (18.40 D) to P2 (25.11 D) and to P3 (28.47 D). The large Δµ_ge of P3 leads to efficient exciton dissociation with greatly suppressed charge recombination in P3 ‐based all‐PSCs. Additionally, the fluorination lowers the highest occupied molecular orbital energy level of P3 and P2 , leading to higher open‐circuit voltage (V_OC). The power conversion efficiency of the P3 ‐based all‐PSCs (6.42%) outperforms those of the P2 and P1 (5.00% and 2.65%)‐based devices. The reduced charge recombination and the enhanced polymer exciton lifetime in P3 ‐based all‐PSCs are confirmed by the measurements of light‐intensity dependent short‐circuit current density (J_SC) and V_OC, and time‐resolved photoluminescence. The results provide reciprocal understanding of the charge generation process associated with Δµ_ge in all‐PSCs and suggest an effective strategy for designing π‐conjugated polymers for high performance all‐PSCs.     

Highly-Stable CsPbI3 Perovskite Solar Cells with an Efficiency of 21.11% via Fluorinated 4-Amino-Benzoate Cesium Bifacial Passivation

The poor interface quality between cesium lead triiodide (CsPbI₃) perovskite and the electron transport layer limits the stability and efficiency of CsPbI₃ perovskite solar cells (PSCs). Herein, a 4-amino-2,3,5,6-tetrafluorobenzoate cesium (ATFC) is designed as a bifacial defect passivator to tailor the perovskite/TiO₂ interface. The comprehensive experiments demonstrate that ATFC can not only optimize the conductivity, electron mobility, and energy band structure of the TiO₂ layer by passivation of the undercoordinated Ti⁴⁺, oxygen vacancy (V_O), and free  OH defects but also promote the yield of high-quality CsPbI₃ film by synergistic passivation of undercoordinated Pb²⁺ defects with the  CO group and F atom, and limiting I⁻ migration via F···I interaction. Benefiting from the above interactions, the ATFC-modified CsPbI₃ device yields a champion power conversion efficiency (PCE) of 21.11% and an excellent open-circuit voltage (V_OC) of 1.24 V. Meanwhile, the optimized CsPbI₃ PSC maintains 92.74% of its initial efficiency after aging 800 h in air atmosphere, and has almost no efficiency attenuation after tracking at maximum power point for 350 h.     

An Ultrathin Ferroelectric Perovskite Oxide Layer for High‐Performance Hole Transport Material Free Carbon Based Halide Perovskite Solar Cells

The hole transport material (HTM) free carbon based perovskite solar cells (C‐PSCs) are promising for its manufactural simplicity, but they currently suffer from low power conversion efficiencies (PCE) largely because of the voltage loss. Here, a new strategy to increase the PCE by incorporating an ultrathin ferroelectric oxide PbTiO₃ layer between the electron transport material and the halide perovskite is reported. The resulting C‐PSCs have achieved PCEs up to 16.37%, which is the highest record for HTM‐free C‐PSCs to date, mainly ascribable to the ferroelectric layer enhanced open circuit voltage. Detail measurements and analysis show an enhanced built‐in potential in the C‐PSCs as well as suppression of the non‐radiative recombination due to the ferroelectric PbTiO₃ layer incorporation, accounting for the boosted V_OC and photovoltaic performance.     

Molecularly Tailored Surface Defect Modifier for Efficient and Stable Perovskite Solar Cells

Surface defects cause non-radiative charge recombination and reduce the photovoltaic performance of perovskite solar cells (PSCs), thus effective passivation of defects has become a crucial method for achieving efficient and stable devices. Organic ammonium halides have been widely used for perovskite surface passivation, due to their simple preparation, lattice matching with perovskite, and high defects passivation ability. Herein, a surface passivator 2,4,6-trimethylbenzenaminium iodide (TMBAI) is employed as the interfacial layer between the spiro-OMeTAD and perovskite layer to modify the surface defect states. It is found that TMBAI treatment suppresses the nonradiative charge carrier recombination, resulting in a 60 mV increase of the open-circuit voltage (V_oc) (from 1.11 to 1.17 V) and raises the fill factor from 76.3% to 80.3%. As a result, the TMBAI-based PSCs device demonstrates a power conversion efficiency (PCE) of 23.7%. Remarkably, PSCs with an aperture area of 1 square centimeter produce a PCE of 21.7% under standard AM1.5 G sunlight. The unencapsulated TMBAI-modified device retains 92.6% and 90.1% of the initial values after 1000 and 550 h under ambient conditions (humidity 55%–65%) and one-sun continuous illumination, respectively.     

Synergistic effect of MACl and DMF towards efficient perovskite solar cells

The performance of perovskite solar cells (PSCs) is extremely dependent on morphology and crystallinity of perovskite film. One of the most effective methods to achieve high performance perovskite solar cells has been to introduce additives that serve as dopants, crystallization or passivation agents. Herein a facile strategy by introducing methylammonium chloride (MACl) and polar solvent N,N-Dimethylformamide (DMF) as co-additives in two-step sequential method is proposed to realize high quality perovskite film. It is demonstrated that DMF facilitates methylammonium iodide (MAI) penetrating easily into PbI₂ layer to form highly crystalized perovskite film with uniform morphology which is essential to achieve high V_OC. While MACl induces MAPbI₃ to crystallize in a pure α-phase and suppress non-photovoltaic phase, which guarantees high FF. Pure α-phase perovskite film with uniform morphology can be achieved by adopting MACl and DMF together and the corresponding solar cell illustrates a power conversion efficiency (PCE) of 19.02% with substantially promoted durability. Moreover, A V_OC as high as 1.181 V is succeeded for MAPbI₃ based solar cell benefiting from the synergistic effect.     

Anti-Dissociation Passivation via Bidentate Anchoring for Efficient Carbon-Based CsPbI2.6Br0.4 Solar Cells

Molecular passivation on perovskite surface is an effective strategy to inhibit surface defect-assisted recombination and reduce nonradiative recombination loss in perovskite solar cells (PSCs). However, the majority of passivating molecules bind to perovskite surface through weak interactions, resulting in weak passivation effects and susceptible to interference from various factors. Especially in carbon-based perovskite solar cells (C-PSCs), the molecular passivation effect is more susceptible to disturbance in subsequent harsh preparation of carbon electrodes via blade-coating route. Herein, bidentate ligand 2,2′-Bipyridine (2Bipy) is explored to passivate surface defects of CsPbI_2.6Br_0.4 perovskite films. The results indicate that compared with monodentate pyridine (Py), bidentate 2Bipy shows a stronger chelation with uncoordinated Pb(II) defects and exhibits a greater passivation effect on perovskite surface. As a result, 2Bipy-modified perovskite films display a significantly boosted photoluminescence lifetime, accompanied by excellent anchoring stability and anti-dissociation of passivating molecules. Meanwhile, the moisture resistance of the 2Bipy-modified perovskite films is also significantly enhanced. Consequently, the efficiency of C-PSCs is improved to 16.57% (J_sc = 17.16 mA cm⁻², V_oc = 1.198 V, FF = 80.63%). As far as it is known, this value represents a new record efficiency for hole transport material-free inorganic C-PSCs.     

Perovskite Solar Cells Consisting of PTAA Modified with Monomolecular Layer and Application to All-Perovskite Tandem Solar Cells with Efficiency over 25%

This study is on the enhancement of the efficiency of wide bandgap (FA_0.8Cs_0.2PbI_1.8Br_1.2) perovskite solar cells (PSCs) used as the top layer of the perovskite/perovskite tandem solar cell. Poly[bis(4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA) and the monomolecular layer called SAM layer are effective hole collection layers for APbI₃ PSCs. However, these hole transport layers (HTL) do not give high efficiencies for the wide bandgap FA_0.8Cs_0.2PbI_1.8Br_1.2 PSCs. It is found that the surface-modified PTAA by monomolecular layer (MNL) improves the efficiency of PSCs. The improved efficiency is explained by the improved FA_0.8Cs_0.2PbI_1.8Br_1.2 film quality, decreased film distortion (low lattice disordering) and low density of the charge recombination site, and improves carrier collection by the surface modified PTAA layer. In addition, the relationship between the length of the alkyl group linking the anchor group and the carbazole group is also discussed. Finally, the wide bandgap lead PSCs (E_g = 1.77 eV) fabricated on the PTAA/monomolecular bilayer give a higher power conversion efficiency of 16.57%. Meanwhile, all-perovskite tandem solar cells with over 25% efficiency are reported by using the PTAA/monomolecular substrate.     

Synergetic Excess PbI2 and Reduced Pb Leakage Management Strategy for 24.28% Efficient,Stable and Eco-Friendly Perovskite Solar Cells

Introducing excess PbI₂ has proven to be an effective in situ passivation strategy for enhancing efficiency of perovskite solar cells (PSCs). Nevertheless, the photoinstability and hysteresis are still tough issues owing to the photolysis nature of PbI₂. Moreover, the humidity-related degradation of perovskite films is also a difficult territory to cover in such an in situ passivation strategy. Herein, a synergistic strategy is reported via initiatively inducing vertical graded PbI₂ distribution (GPD) in the whole perovskite film and capping a cis-Ru(H₂dcbpy)(dnbpy)(NCS)₂ (Z907) internal encapsulation (IE) layer on the surface to ameliorate the above issues. The GPD design can enhance luminescence, prolong carrier lifetimes, ascertaining the improvement of efficiency and elimination of photoinstability in the PSCs. Besides, the introduced IE layer not only can promote the moisture and thermal resistance, but also inhibit Pb leakage and ion migration in the PSCs. Through the synergetic regulations, the resultant PSCs exhibit an impressive open circuit voltage (V_OC) of 1.253 V, fill factor of 81.25%, and power conversion efficiency (PCE) of 24.28%. Moreover, the PSCs maintain 91% of its initial PCE at relative humidity of 85% after 500 h aging and 94% under continuous heating at 85 °C after 750 h aging.     

Chemical Reduction of Iodine Impurities and Defects with Potassium Formate for Efficient and Stable Perovskite Solar Cells

The performance of perovskite solar cells (PSCs) is negatively affected by iodine (I₂) impurities generated from the oxidation of iodide ions in the perovskite precursor powder, solution, and perovskite films. In this study, the use of potassium formate (HCOOK) as a reductant to minimize the presence of detrimental I₂ impurities is presented. It is demonstrated that HCOOK can effectively reduce I₂ back to I⁻ in the precursor solution as well as in the devices under external conditions. Furthermore, the introduced formate anion (HCOO⁻) and alkali metal cation (K⁺) can reduce the defect density within the perovskite film by modulating perovskite growth and passivating electronic defects, significantly prolonging the carrier lifetime and reducing the J–V hysteresis. Consequently, the maximum efficiency of the HCOOK-doped planar n–i–p PSCs reaches 23.8%. After 1000 h of operation at maximum power point tracking under continuous 1 sun illumination, the corresponding encapsulated devices retain 94% of their initial efficiency.     

Wide bandgap Cu(In,Ga)Se2 solar cells with improved energy conversion efficiency

We report on improvements to the energy conversion efficiency of wide bandgap (E_g > 1.2 eV) solar cells on the basis of CuIn_1−xGa_xSe₂. Historically, attaining high efficiency (>16%) from these types of compound semiconductor thin films has been difficult. Nevertheless, by using (a) the alkaline‐containing high‐temperature EtaMax glass substrates from Schott AG, (b) elevated substrate temperatures of 600–650 °C, and (c) high vacuum evaporation from elemental sources following National Renewable Energy Laboratory's three‐stage process, we have been able to improve the performance of wider bandgap solar cells with 1.2 < E_g < 1.45 eV. The current density–voltage (J–V) data we present includes efficiencies >18% for absorber bandgaps of ~1.30 eV and efficiencies of ~16% for bandgaps up to ~1.45 eV. In comparing J–V parameters in similar materials, we establish gains in the open‐circuit voltage and, to a lesser degree, the fill factor value, as the reason for the improved performance. The higher voltages seen in these wide gap materials grown at high substrate temperatures are due to reduced recombination. We establish the existence of random and discrete grains within the CIGS absorbers that yield limited or no generation/collection of minority carriers. We also show that interfacial recombination is the main mechanism limiting additional enhancements to open‐circuit voltage and therefore performance. Solar cell results, absorber materials characterization, and experimental details and discussion are presented. Copyright © 2012 John Wiley & Sons, Ltd.     

Vertical Phase Separated Cesium Fluoride Doping Organic Electron Transport Layer: A Facile and Efficient “Bridge” Linked Heterojunction for Perovskite Solar Cells

In perovskite solar cells (PSCs), the interfaces of the halide perovskite/electron transport layer (ETL) and ETL/metal oxide electrode (MOE) always attract and trap free carriers via the surface electrostatic force, altering quasi‐Fermi level (E_Fq) splitting of contact interfaces, and significantly limit the charge extraction efficiency and intrinsic stability of devices. Herein, a graded “bridge” is first reported to link the MOE and perovskite interfaces by self vertical phase separation doping (PSD), diminishing the side effect of notorious ionic defects via both reinforced interface E_bi and the vacancies filling. Experimental and theoretical results prove that the inhomogeneous distribution of CsF in the bulk or surface of PC₆₁BM would not only form metal–oxygen (M–O) dipole on MOE, reinforcing the interface E_bi, but also create a graded energy bridge to alleviate the disadvantage of band offset raised by the enhanced interface E_bi, which significantly avoid the carrier accumulation and recombination at defective interfaces. Employing PSD, the power conversion efficiency of the devices approaches 21% with a high open‐circuit voltage (1.148 V) and delivers a high stability of 89% after aging 60 days in atmosphere without encapsulation, which is the highest efficiency of organic electron transport layers for n–i–p PSCs.     

Near‐Infrared Small Molecule Acceptor Enabled High‐Performance Nonfullerene Polymer Solar Cells with Over 13% Efficiency

One of the most promising approaches to achieve high‐performance polymer solar cells (PSCs) is to develop nonfullerene small molecule acceptors (SMAs) with an absorption extending to the near‐infrared (NIR) region. In this work, two novel SMAs, namely, BTTIC and BTOIC, are designed and synthesized, with optical bandgaps (E_g^opt) of 1.47 and 1.39 eV, respectively. Desipte the narrow E_g^opt, the PBDB‐T:BTTIC‐ and PBDB‐T:BTOIC‐based PSCs can maintain high V_OCs of over 0.90 and 0.86 V, respectively, with low energy losses (E_loss) < 0.6 eV. Meanwhile, due to the favorable morphology of the PBDB‐T:BTTIC blend, balanced carrier mobilities are achieved. The high external quantum efficiencies enable a high power conversion efficiency (PCE) up to 13.18% for the PBDB‐T:BTTIC‐based PSCs. In comparison, BTOIC shows an excessive crystallization propensity owing to its oxyalkyl side groups, which eventually leads to a relatively low PCE for the PBDB‐T:BTOIC‐based PSCs. Overall, this work provides insights into the design of novel NIR‐absorbing SMAs for nonfullerene PSCs.