Average Hole Mobility Research Articles

Thienothiophene and benzothiadiazole based conjugated donor-acceptor polymers; synthesis, photophysical properties and organic field effect transistor applications

Novel conjugated donor-acceptor (D-A) type polymers (P1-P3) possessing thieno[3,2-b]thiophenes (TT) as donors having different functional groups and 2,1,3-benzothiadiazole (BT) as an acceptor were designed and synthesized via palladium-catalyzed Sonogashira coupling reaction. Their electronic and optical properties were investigated by UV–Vis and fluorescence spectroscopies and cylic voltammetry analysis. Organic field-effect transistor (OFET) of the polymers were fabricated using biodegradable and environmental-friendly khaya gum as a high dielectric layer to investigate their charge transport characteristics were at low voltage. All the polymers displayed a p-type field-effect behaviour, among which alkyl chain (C9H19) substituted P2 exhibited the highest average saturated hole mobility, μsat, 0.086 cm2 V−1 s−1, on/off current ratio, Ion/Ioff = 1.0 × 103, and subthreshold swing, SS, 425 mV dec−1. The results presented in this work corroborate that the three novel TT-BT polymers have promising potential for electronic and optoelectronic applications, in particular, where tunability of the field-effect behaviour is essential for performance.

High-performance tin perovskite transistors through formate pseudohalide engineering

The lack of high-performance p-type semiconducting materials hinders the integration of complementary metal-oxide semiconductors with well-established n-type metal-oxide counterparts. Although tin halide perovskites are promising p-type material candidates, their practical implementation is hindered by excessive hole concentrations and difficulties in precisely controlling crystallization, which leads to poor device performance and yield. In this paper, we propose a formate pseudohalide engineering method to overcome these issues and demonstrate high-performance tin perovskite thin-film transistors (TFTs). The incorporation of formate anion greatly suppresses the vacancy defects at the surfaces of the perovskite films with an increase in crystallinity and grain size. This reduces the hole concentration and eliminates the dependence on the addition of excessive tin fluoride for hole suppression. Hence, high-performance TFTs with a high average field-effect hole mobility of 57.34 cm2 V−1 s−1 and on/off current ratios surpassing 108 can be achieved, approaching p-channel low-temperature polysilicon devices.

Selenium-alloyed tellurium oxide for amorphous p-channel transistors.

Compared to polycrystalline semiconductors, amorphous semiconductors offer inherent cost-effective, simple and uniform manufacturing. Traditional amorphous hydrogenated Si falls short in electrical properties, necessitating the exploration of new materials. The creation of high-mobility amorphous n-type metal oxides, such as a-InGaZnO (ref. 1), and their integration into thin-film transistors (TFTs) have propelled advancements in modern large-area electronics and new-generation displays2-8. However, finding comparable p-type counterparts poses notable challenges, impeding the progress of complementary metal-oxide-semiconductor technology and integrated circuits9-11. Here we introduce a pioneering design strategy for amorphous p-type semiconductors, incorporating high-mobility tellurium within an amorphous tellurium suboxide matrix, and demonstrate its use in high-performance, stable p-channel TFTs and complementary circuits. Theoretical analysis unveils a delocalized valence band from tellurium 5p bands with shallow acceptor states, enabling excess hole doping and transport. Selenium alloying suppresses hole concentrations and facilitates the p-orbital connectivity, realizing high-performance p-channel TFTs with an average field-effect hole mobility of around 15 cm2 V-1 s-1 and on/off current ratios of 106-107, along with wafer-scale uniformity and long-term stabilities under bias stress and ambient ageing. This study represents a crucial stride towards establishing commercially viable amorphous p-channel TFT technology and complementary electronics in a low-cost and industry-compatible manner.

α‐TeO2 Oxide as Transparent p‐Type Semiconductor for Low Temperature Processed Thin Film Transistor Devices

AbstractIn comparison to reports on n‐type semiconducting oxides, p‐type oxide semiconducting materials are still rare. Scarcely reported p‐type oxide transistors demonstrated unsatisfactory environmental stability which still hinders their implementation for all oxide transistors and circuit applications. In this study, for the first time on α‐TeO2 as an active channel material with p‐type characteristics accessible by direct evaporation technique. Notably, the fabricated 5 nm α‐TeO2 thin film in connection with an equally thin passivation layer exhibits a remarkable low processing temperature of 50 °C generating a hole mobility of 3.8 cm2 V−1 s−1, an on‐state current of 966 µA, and an on/off ratio of 3.8 × 103. Additionally, the reproducibility of these devices confirmed a narrow variation in the TFT metrics, yielding an average hole mobility, on‐current, and on/off ratio of 3.59 cm2 V−1 s−1, 914 µA, and 3.3 × 103, respectively. Furthermore, the devices are subjected to extensive stability testing under ambient atmospheric conditions that exhibits a marginal mobility reduction while maintaining a stable on/off ratio over 125‐day period, highlighting their robust environmental stability. Notably, the low processing temperatures with both exceptional transistor performance and environmental endurance makes them suitable for the integration onto flexible substrates, particularly bendable/stretchable displays.

Well-Balanced Ambipolar Charge Transport of Diketopyrrolepyrrole-Based Copolymers: Organic Field-Effect Transistors and High-Voltage Logic Applications.

A poly (3,6-bis(thiophen-2-yl)-2,5-bis(2-decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione-co-(2,3-bis(phenyl)acrylonitrile)) (PDPADPP) copolymer, composed of diketopyrrolopyrrole (DPP) and a cyano (nitrile) group with a vinylene spacer linking two benzene rings, is synthesized via a palladium-catalyzed Suzuki coupling reaction. The electrical performance of PDPADPP in organic field-effect transistors (OFETs) and circuits is investigated. The OFETs based on PDPADPP exhibit typical ambipolar transport characteristics, with the as-cast OFETs demonstrating low field-effect hole and electron mobility values of 0.016 and 0.004cm2 V-1 s-1 , respectively. However, after thermal annealing at 240°C, the OFETs exhibit improved transport characteristics with highly balanced ambipolar transport, showing average hole and electron mobility values of 0.065 and 0.116cm2 V-1 s-1 , respectively. To verify the application of the PDPADPP OFETs in high-voltage logic circuits, compact modeling using the industry-standard small-signal Berkeley short-channel IGFET model (BSIM) is performed, and the logic application characteristics are evaluated. The circuit simulation results demonstrate excellent logic application performance of the PDPADPP-based ambipolar transistor and illustrate that the device annealed at 240°C exhibits ideal circuit characteristics.

Enhanced Mobility in Suspended Chemical Vapor-Deposited Graphene Field-Effect Devices in Ambient Conditions.

High-field-effect mobility and the two-dimensional nature of graphene films make it an interesting material for developing sensing applications with high sensitivity and low power consumption. The chemical vapor deposition process allows for producing high-quality graphene films in a scalable manner. Considering the significant impact of the underlying substrate on the graphene device performance, methods to enhance the field-effect mobility are highly desired. This work demonstrates a simplified fabrication process to develop suspended, two-terminal chemical vapor deposition (CVD) graphene devices with enhanced field-effect mobility operating at room temperature. Enhanced hole field-effect mobility of up to ∼4.8 × 104 cm2/Vs and average hole mobility >1 × 104 cm2/Vs across all of the devices is demonstrated. A gradual increase in the width of the graphene device resulted in the increase of the full width at half-maximum (FWHM) of field-effect characteristics and a decrease in the field-effect mobility. Our work presents a simplified fabrication approach to realize high-mobility suspended CVD graphene devices, beneficial for developing CVD graphene-related applications.

Investigating the Device Performance Variation of a Buried Locally Gated Al/Al2O3 Graphene Field-Effect Transistor Process

In this study, a process is developed for the fabrication of buried top-gated graphene transistors with Al2O3 as a gate dielectric, yielding devices that can be suitable for not only flexible electronics but also laser-induced graphene (LIG)-based technology implementations. A new processing option is presented with the use of tetraethyl-orthosilicate (TEOS) as an etch stop for contact via etching of Al2O3. Buried locally gated Al/Al2O3 graphene field-effect transistors (GFETs) are fabricated with Dirac points as low as 4 V, with a metal-to-graphene contact resistance as low as ∼1.7 kΩ·µm, and an average hole mobility of 457.97 cm2/V·s with a non-uniformity of 93%. Large device variation and non-uniformity in electrical performance are not uncommon for graphene-based devices, as process-induced defects play a major role in such variation. AFM, SEM, Raman spectroscopy, and model fitting indicated that the rough Al/Al2O3 surface was the main factor for the observed device variation. AFM analysis indicated a graphene surface roughness Ra of 16.19 nm on top of the buried Al/Al2O3 gate in contrast to a Ra of 4.06 nm over Al2O3/SiO2. The results presented indicate the need to reduce device variability and non-uniformity by improving transfer methods, as well as the use of smoother surfaces and compatible materials. The presented analyses provide a framework with which other researchers can analyze and correlate device variation and non-uniformities while methods to reduce variability are investigated.

High-performance flexible organic field effect transistors with print-based nanowires

Polymer nanowire (NW) organic field-effect transistors (OFETs) integrated on highly aligned large-area flexible substrates are candidate structures for the development of high-performance flexible electronics. This work presents a universal technique, coaxial focused electrohydrodynamic jet (CFEJ) printing technology, to fabricate highly aligned 90-nm-diameter polymer arrays. This method allows for the preparation of uniformly shaped and precisely positioned nanowires directly on flexible substrates without transfer, thus ensuring their electrical properties. Using indacenodithiophene-co-benzothiadiazole (IDT-BT) and poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8-BT) as example materials, 5 cm2 arrays were prepared with only minute size variations, which is extremely difficult to do using previously reported methods. According to 2D-GIXRD analysis, the molecules inside the nanowires mainly adopted face-on π-stacking crystallite arrangements. This is quite different from the mixed arrangement of thin films. Nanowire-based OFETs exhibited a high average hole mobility of 1.1 cm2 V−1 s−1 and good device uniformity, indicating the applicability of CFEJ printing as a potential batch manufacturing and integration process for high-performance, scalable polymer nanowire-based OFET circuits. This technique can be used to fabricate various polymer arrays, enabling the use of organic polymer semiconductors in large-area, high-performance electronic devices and providing a new path for the fabrication of flexible displays and wearable electronics in the future.

Corona Poling Induced Phase Transition to Highly Polar Phase in P(VDF-TrFE-CFE) Dielectric and Charge Transport of Organic Field-Effect Transistors.

Increasing the number of charge carriers flowing through the charge transport channel to improve the electrical performance of organic field-effect transistors (OFETs) is important because it leads to a low driving voltage and a high drain current value. This paper proposes a new strategy, the corona poling process, to enhance the electrical performance of OFETs using an external electric field when forming a dielectric film using a PVDF-based high-k dielectric terpolymer, P(VDF-TrFE-CFE). A corona poling process was applied to align the dipoles with high-k dielectric molecules and improve the capacitance, thereby increasing the number of charge carriers. Through this process, by observing the phase transition of a PVDF dielectric through a corona poling process in the GIWAXS data, the phase transition through an external electric field was thoroughly revealed for the first time. As a result, the capacitance of high-k dielectric films can be improved, and the amount of charge carriers can be increased by a simple corona poling process. In addition, to reduce the effect of deep trap sites caused by the dipole alignment, a thin low-k dielectric, polystyrene (PS), was introduced between the active and high-k dielectric layers to provide trap site passivation, thereby increasing the electrical performance of the OFET. Therefore, through this strategy, using a diketopyrrolopyrrole (DPP)-based donor-acceptor (D-A) copolymer as an active material of OFET, the average saturation region hole mobility was improved from 0.34 to 0.60 cm2/Vs. Thus, the electrical performances of the OFETs were improved by enhancing the capacitance through the corona poling process and reducing the charge carrier trap sites introduced by the high-k and low-k bi-layer dielectric layer. Importantly, this work offers a new strategy for the post-treatment to improve electrical performance of organic devices.

Synthesis, Photophysical properties and OFET application of thienothiophene and benzothiadiazole based Donor-π-Acceptor-π (D-π -A-π) type conjugated polymers

Novel conjugated donor- π -acceptor- π (D- π -A- π) type polymers (P1-P3), possessing thieno[3,2-b]thiophene (TT) with different aromatic substituents as donors, benzo[1–3]thiadiazole (BT) as an acceptor and thiophene as a π -linker, were designed and synthesized via palladium-catalyzed Stille coupling reaction. Their electronic, optical and thermal properties were investigated using UV–vis and fluorescence spectroscopies, cylic voltammetry, and thermal gravimetric analysis. Photophysical characterizations of these novel polymers showed a remarkable mega Stokes shift, reaching up to 130 nm and optic/electronic band gaps between 1.70 and 2.00 eV, as well as good thermal stability of degradation temperature at around 260 °C. To study the effect of electron donating and withdrawing groups on the electronic properties of the π -extended polymers, their organic field-effect transistors (OFETs) were fabricated and charge transport characteristics were investigated. While all three polymers showed a p-type field-effect behaviour, dimethylamine substituted P3 exhibited the highest average saturated hole mobility, μsat, 0.04 cm2 V−1 s−1, on/off current ratio, Ion/Ioff = 3.0 × 103, and the smallest subthreshold swing, SS, 250 mV dec-1, outperforming similar p-type D- π -A- π semiconducting polymers reported in the literature. The results presented in this work corroborate that the three novel TT-BT polymers have promising potential for electronic and optoelectronic applications, in particular where the tunability of field-effect behaviour is essential for performance.

Tetramethylammonium Iodide Additive for Enhancing the Charge Carrier Mobilities of Diketopyrrolopyrrole‐Based Conjugated Polymer in Ambipolar Organic Field‐Effect Transistors†

Comprehensive SummaryDiketopyrrolopyrrole (DPP) is one of the most promising building blocks for constructing polymer semiconductors with high charge‐carrier mobilities in organic field‐effect transistors (OFETs). In this study, a novel DPP‐based conjugated polymer, PDPPy‐BDD, was designed and synthesized. The ambipolar field‐effect transistor characteristics were realized with the average hole and electron mobilities of 3.5 × 10–3 and 3.07 × 10–2 cm2 V−1 s−1, respectively. Both the hole and electron mobilities could be successfully enhanced by using a tetramethylammonium iodide (NMe4I) additive. Such an enhancement was attributed to the formation of stronger interchain π–π stackings, the weakening of the face‐on packing orientation in the thin film state, and the higher channel conductivities in the OFETs.

Highly Efficient, Low‐Dose, and Ultrafast Carbazole X‐Ray Scintillators

AbstractOrganic fluorescence scintillators, owing to the ultrafast response time, versatile chemical structures, low processing temperature, and low cost, are considered as one of the promising materials for medical diagnostics, radiation detection, and X‐ray astronomy. However, the low radioluminescence (RL) intensity and low sensitivity hinder their practical applications. In this work, a highly efficient organic fluorescent scintillator, 4,4′‐bis(9‐carbazolyl)biphenyl (CBP), is presented, exhibiting a high X‐ray RL intensity, narrow full width at half‐maximum of 49 nm, and ultrafast decay time of 1.15 ns. More importantly, it has a low detection limit of 25.5 nGy s−1, which is only 1/215 dose rate compared with the commercial X‐ray diagnostics. Such an excellent scintillation performance is mainly attributed to its high photoluminescence quantum yield (PLQY = 61.92%) and good carrier transport (average hole mobility of 0.094 cm2 V−1 s−1). By mixing the CBP into polydimethylsiloxane, the fabricated large area flexible film can be applied in X‐ray radiography, which exhibits a high spatial resolution of 14.3 lp mm−1 at MTF > 0.2. This work paves a way for the implementation of organic fluorescence dyes with high PLQY, high carrier mobility in efficient X‐ray scintillation and imaging.

Low-Operating-Voltage Two-Dimensional Tin Perovskite Field-Effect Transistors with Multilayer Gate Dielectrics Based on a Fluorinated Copolymer.

The fabrication of organic-inorganic perovskite field-effect transistors (FETs) with polymer gate dielectrics is challenging because of the solvent corrosion and wettability issues at interfaces. A few polymers have been integrated into perovskite transistors; however, these devices have high operating voltages due to low dielectric constants. Herein, poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE) with a high dielectric constant is introduced into bottom-gate phenylethylammonium tin iodide perovskite [(PEA)2SnI4] FETs. Polytetrafluoroethylene (PTFE) and cross-linked poly(4-vinylphenol) (PVP) (CL-PVP) are used to address the issues of solvent corrosion and wettability. We design the PVDF-TrFE/PTFE and PVDF-TrFE/PTFE/CL-PVP dielectric layers, where the ferroelectric properties of PVDF-TrFE are reduced by PTFE. The (PEA)2SnI4 FETs operate at relatively low gate voltages, exhibiting good overall performance with average hole mobilities of 0.42 and 0.36 cm2 V-1 s-1. Our findings provide a feasible strategy for constructing low-operating-voltage perovskite FETs with large-dielectric-constant ferroelectric polymers as gate dielectrics by a solution processing technique.

Surface tension traction transfer method for wafer-scale device grade graphene film

The integrity and cleanliness of graphene film is the core of graphene devices. However, the cleanliness and integrity of the graphene film can only be ensured when the transferred film area is small (less than 2╳2 cm2), which leads to the extremely low preparation efficiency of graphene devices and limits its industrialization applications. But, the integrity and cleanliness of the graphene film will decrease with the increase of the transfer film area. Therefore, the clean and intact transfer of large area graphene films is extremely difficult, which limits the performance and development of graphene electronic devices. Hence, a wafer-scale(6-inch), intact and clean transfer method (Surface tension traction method) of chemical vapor deposition (CVD) copper-based monolayer, multilayer graphene and single crystals graphene are proposed, which is suitable for various target substrate (rigid substrate, such as:SiO2/Si, GaN, glass etc. or flexible substrate, such as PI, PET, PEN, etc.). The use of the watch glass ensures that the graphene film is not directly contacted with the transfer medium (slides, glass or silicon wafers) when the film is transferred between various solutions. And the surface tension of the water can ensure that the graphene is spread on the water surface, which minimizing the probability of graphene breakage, wrinkles and contamination. This also directly greatly reduces the residue of the PMMA layer. The average of 62500 spots of Raman spectrum peak intensity ratios (ID/IG) is only 0.02318, The average hole mobility of GFETs prepared from graphene transferred can reach 3438 ± 84 cm2/Vs, which reveals the outstanding quality and uniformity of graphene transferred. The graphene transferred is expected to be applied in the fields of transparent, conductive electrodes, flexible films, electronic devices, heat dissipation and anti-corrosion, etc, to promote the industrial production of CVD graphene films.

Electrochemically exfoliated phosphorene nanosheet thin films for wafer-scale near-infrared phototransistor array

Two-dimensional (2D) black phosphorus (BP), or phosphorene, has recently emerged as a promising 2D semiconductor because of its p-type charge transport behavior and near-infrared photoresponsivity. However, the application of BP in practical electronic and optoelectronic devices is hindered by challenges in producing high-quality BP films over large areas. In this manuscript, we present a facile solution-based process to create wafer-scale BP films for fabrication of p-channel field-effect transistors that are responsive to near infrared light. Few-layer BP nanosheets are first exfoliated from the bulk crystal via electrochemical intercalation of cationic molecules and then vacuum-filtered through an anodic aluminum oxide membrane. The resulting BP film can be transferred onto an SiO2-coated silicon substrate, thereby allowing for realization of field-effect transistors after electrode deposition and thermal annealing. The transistor array exhibits spatial uniformity in electrical performance with an average hole mobility of ~0.002 cm2 V−1 s−1 and on/off ratio of 130. Furthermore, gate-induced modulation of the BP channel allows for enhancement in the photoresponsivity for 1550-nm light illumination up to 24 mA W−1, which benefits the application of the phototransistor array for near infrared imaging.

Effect of Ni toward the optical and transport properties of the spinel solid solution NixCu1−xFe2O4 nanoparticles

The solid solution NixCu1−xFe2O4 (x = 0, x = 0. 2,….x = 1) crystallizing in the spinel structure were prepared by the Sol-Gel method at 800 °C. The novelty of the work is also devoted to the synthesis of the spinel ferrites NixCu1−xFe2O4 (0 < x < 1) using the sol gel technique and the measurement of their structural and magnetic properties by X-ray diffraction and magnetic measurements. The structural, magnetic, optical and electrical properties were investigated. The formation of the tetragonal phase with a good crystallization and stoichiometric contents were confirmed by X-ray diffraction (x = 0 and 0.2) while a transition to cubic symmetry is observed for the other compositions. NixCu1−xFe2O4 exhibits n-type conduction with an increased band gap (Eg) as Ni is introduced in the crystal lattice while it decreases with augmenting the Ni-content in the cubic phase. The transport properties are characteristic of n-type behavior where the electrical conductivity decreases up to x = 0.4. Then, it increases and the conduction is mainly governed by the thermal emission over the inter-crystallites. An average hole mobility of ∼ 10−5 cm2 V−1 s−1 was determined for both symmetries. Magnetic measurements revealed that the saturation magnetization (Ms) increases with the Ni-content whereas the coercivity decreases. NiFe2O4 has the largest saturation magnetization (38.16 emu/g). The optical properties namely the energy gap (Eg), reflection index (n), extinction coefficient (k), dielectric complex (ɛ), optical conductivity (σopt), dissipation factor (tan δ) and relaxation time (τ) were determined.

Employing aldol condensation to prepare benzodifurandione based small molecules for application in thin-film transistors

A family of benzodifurandione-based small molecules is reported by employing aldol condensation reactions with aldehydes of selected heterocycles, ring-fused functional groups, and fluorinated phenyl substituents. The influence of the peripheral moieties on the resulting optical and electrochemical properties were analyzed, revealing that the absolute energy levels within this series of benzodifurandione-based small molecules are significantly impacted, whereas the difference in HOMO/LUMO energy gap is moderate. Upon incorporation of these materials into organic thin-film transistors through physical vapor deposition, the thiophene-capped benzodifurandione derivative exhibited average hole mobilities of 10−4 cm2·V−1·s−1 both in air and vacuum. Although device performance was less than ideal for this series of compounds, this may be attributed to poor thin film morphology as determined by atomic force microscopy.

Air processed Cs2AgBiBr6 lead-free double perovskite high-mobility thin-film field-effect transistors

This study focuses on the fabrication and characterization of Cs2AgBiBr6 double perovskite thin film for field-effect transistor (FET) applications. The Cs2AgBiBr6 thin films were fabricated using a solution process technique and the observed XRD patterns demonstrate no diffraction peaks of secondary phases, which confirm the phase-pure crystalline nature. The average grain sizes of the spin-deposited film were also calculated by analysing the statistics of grain size in the SEM image and was found to be around 412 (± 44) nm, and larger grain size was also confirmed by the XRD measurements. FETs with different channel lengths of Cs2AgBiBr6 thin films were fabricated, under ambient conditions, on heavily doped p-type Si substrate with a 300 nm thermally grown SiO2 dielectric. The fabricated Cs2AgBiBr6 FETs showed a p-type nature with a positive threshold voltage. The on-current, threshold voltage and hole-mobility of the FETs decreased with increasing channel length. A high average hole mobility of 0.29 cm2 s−1 V−1 was obtained for the FETs with a channel length of 30 µm, and the hole-mobility was reduced by an order of magnitude (0.012 cm2 s−1 V−1) when the channel length was doubled. The on-current and hole-mobility of Cs2AgBiBr6 FETs followed a power fit, which confirmed the dominance of channel length in electrostatic gating in Cs2AgBiBr6 FETs. A very high-hole mobility observed in FET could be attributed to the much larger grain size of the Cs2AgBiBr6 film made in this work.

Tellurium Single-Crystal Arrays by Low-Temperature Evaporation and Crystallization.

Thermally evaporated tellurium possesses an intriguing crystallization behavior, where an amorphous to crystalline phase transition happens at near-ambient temperature. However, a comprehensive understanding and delicate control of the crystallization process for the evaporated Te films is lacking. Here, the kinetics and dynamics of the crystallization of thermally evaporated Te films is visualized and modeled. Low-temperature processing of highly crystalline tellurium films with large grain size and preferred out-of-plane orientation ((100) plane parallel to the surface) is demonstrated by controlling the crystallization process. Tellurium single crystals with a lateral dimension of up to 6µm are realized on various substrates including glass and plastic. Field-effect transistors based on 5°C crystallized Te single grains (6-nm-thick) exhibit an average effective hole mobility of ≈100 cm2 V-1 s-1 , and on/off current ratio of ≈3 × 104 .

Crystallography, Morphology, Electronic Structure, and Transport in Non-Fullerene/Non-Indacenodithienothiophene Polymer:Y6 Solar Cells.

Emerging nonfullerene acceptors (NFAs) with crystalline domains enable high-performance bulk heterojunction (BHJ) solar cells. Thermal annealing is known to enhance the BHJ photoactive layer morphology and performance. However, the microscopic mechanism of annealing-induced performance enhancement is poorly understood in emerging NFAs, especially regarding competing factors. Here, optimized thermal annealing of model system PBDB-TF:Y6 (Y6 = 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]-thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) decreases the open circuit voltage (VOC) but increases the short circuit current (JSC) and fill factor (FF) such that the resulting power conversion efficiency (PCE) increases from 14 to 15% in the ambient environment. Here we systematically investigate these thermal annealing effects through in-depth characterizations of carrier mobility, film morphology, charge photogeneration, and recombination using SCLC, GIXRD, AFM, XPS, NEXAFS, R-SoXS, TEM, STEM, fs/ns TA spectroscopy, 2DES, and impedance spectroscopy. Surprisingly, thermal annealing does not alter the film crystallinity, R-SoXS characteristic size scale, relative average phase purity, or TEM-imaged phase separation but rather facilitates Y6 migration to the BHJ film top surface, changes the PBDB-TF/Y6 vertical phase separation and intermixing, and reduces the bottom surface roughness. While these morphology changes increase bimolecular recombination (BR) and lower the free charge (FC) yield, they also increase the average electron and hole mobility by at least 2-fold. Importantly, the increased μh dominates and underlies the increased FF and PCE. Single-crystal X-ray diffraction reveals that Y6 molecules cofacially pack via their end groups/cores, with the shortest π-π distance as close as 3.34 Å, clarifying out-of-plane π-face-on molecular orientation in the nanocrystalline BHJ domains. DFT analysis of Y6 crystals reveals hole/electron reorganization energies of as low as 160/150 meV, large intermolecular electronic coupling integrals of 12.1-37.9 meV rationalizing the 3D electron transport, and relatively high μe of 10-4 cm2 V-1 s-1. Taken together, this work clarifies the richness of thermal annealing effects in high-efficiency NFA solar cells and tasks for future materials design.