Designing Contact Independent High-Performance Low-Cost Flexible Electronics.

Organic semiconductors enable low-cost solution processing of optoelectronic devices on flexible substrates. Their use in contemporary applications, however, is sparse due to persistent challenges in achieving the requisite performance levels in a reliable and reproducible manner. A critical bottleneck is the inefficiency associated with charge injection. Here, large-scale simulations are employed to identify operational windows where key device parameters that are difficult to control experimentally, such as the contact resistance, become less consequential to overall device functionality. This design methodology overcomes injection barrier limitations in organic field-effect transistors (OFETs), leading to high charge carrier mobility and significantly expanding the range of suitable electrode materials. Leveraging this new understanding, all-organic, solution-deposited OFETs are successfully fabricated on flexible substrates. These devices incorporate printed contacts and showcase mobilities exceeding 5 cm2 Vs-1. These results provide a route for accessing the fundamental limits of material properties even in the absence of ideal contacts - a critical step in establishing reliable structure/property relationships and optimal material design paradigms. While reducing the injection barrier and contact resistance remains critical for achieving high OFET performance, this work demonstrates a path toward consistently achieving high charge carrier mobility through device geometry design, ultimately reducing processing complexity and cost.

A Novel Crosslinked Hole Transport Layer with Enhanced Charge Injection Balance for Highly Efficient Inkjet-Printed Blue Quantum Dot-Based Light-Emitting Diodes.

In this work, an efficient and robust hole transport layer (HTL) based on blended poly((9,9-dioctylfluorenyl-2,7-diyl)-alt-(9-(2-ethylhexyl)-carbazole-3,6-diyl)) (PF8Cz) and crosslinkable 3,3'-(9,9-dimethyl-9H-fluorene-2,7-diyl)bis(9-(4-vinylphenyl)-9H-carbazole) (FLCZ-V) is introduced for high-performance and stable blue quantum dot-based light-emitting diodes (QLEDs), wherein FLCZ-V can in situ-crosslink to a continuous network polymer after thermal treatment and the linear polymer PF8CZ becomes intertwined and imprisoned. As a result, the blended HTL shows a high hole mobility (1.27 × 10-4 cm2 V-1 s-1) and gradient HOMO levels (-5.4 eV of PF8CZ and -5.7 eV of FLCZ-V) that can facilitate hole injecting so as to ameliorate the charge balance and, at the same time, achieve better electron-blocking capability that can effectively attenuate HTL decomposition. Meanwhile, the crosslinked blended HTL showed excellent solvent resistance and a high surface energy of 40.34 mN/m, which is favorable to enhance wettability for the deposition of a follow-up layer and attain better interfacial contact. Based on the blended HTL, blue QLEDs were fabricated by both spin-coating and inkjet printing. For the spin-coated blue QLED, a remarkable enhancement of external quantum efficiency (EQE) of 15.5% was achieved. Also, the EQE of the inkjet-printed blue QLED reached 9.2%, which is thus far the best result for the inkjet-printed blue QLED.

Robust Dipolar Layers between Organic Semiconductors and Silver for Energy-Level Alignment.

The interface between a metal electrode and an organic semiconductor (OS) layer has a defining role in the properties of the resulting device. To obtain the desired performance, interlayers are introduced to modify the adhesion and growth of OS and enhance the efficiency of charge transport through the interface. However, the employed interlayers face common challenges, including a lack of electric dipoles to tune the mutual position of energy levels, being too thick for efficient electronic transport, or being prone to intermixing with subsequently deposited OS layers. Here, we show that monolayers of 1,3,5-tris(4-carboxyphenyl)benzene (BTB) with fully deprotonated carboxyl groups on silver substrates form a compact layer resistant to intermixing while capable of mediating energy-level alignment and showing a large insensitivity to substrate termination. Employing a combination of surface-sensitive techniques, i.e., low-energy electron microscopy and diffraction, X-ray photoelectron spectroscopy, and scanning tunneling microscopy, we have comprehensively characterized the compact layer and proven its robustness against mixing with the subsequently deposited organic semiconductor layer. Density functional theory calculations show that the robustness arises from a strong interaction of carboxylate groups with the Ag surface, and thus, the BTB in the first layer is energetically favored. Synchrotron radiation photoelectron spectroscopy shows that this layer displays considerable electrical dipoles that can be utilized for work function engineering and electronic alignment of molecular frontier orbitals with respect to the substrate Fermi level. Our work thus provides a widely applicable molecular interlayer and general insights necessary for engineering of charge injection layers for efficient organic electronics.

Material Design of Ultra-Thin InN/GaN Superlattices for a Long-Wavelength Light Emission.

GaN heterostructure is a promising material for next-generation optoelectronic devices, and Indium gallium nitride (InGaN) has been widely used in ultraviolet and blue light emission. However, its applied potential for longer wavelengths still requires exploration. In this work, the ultra-thin InN/GaN superlattices (SL) were designed for long-wavelength light emission and investigated by first-principles simulations. The crystallographic and electronic properties of SL were comprehensively studied, especially the strain state of InN well layers in SL. Different strain states of InN layers were applied to modulate the bandgap of the SL, and the designed InN/GaN heterostructure could theoretically achieve photon emission of at least 650 nm. Additionally, we found the SL had different quantum confinement effects on electrons and holes, but an efficient capture of electron-hole pairs could be realized. Meanwhile, external forces were also considered. The orbital compositions of the valence band maximum (VBM) were changed with the increase in tensile stress. The transverse electric (TE) mode was found to play a leading role in light emission in normal working conditions, and it was advantageous for light extraction. The capacity of ultra-thin InN/GaN SL on long-wavelength light emission was theoretically investigated.

Controllable Manipulation of Large-Volume Droplet on Non-Slippery Surfaces Based on Triboelectric Contactless Charge Injection.

Controllable droplet manipulation is crucial in diverse scientific and engineering fields. Traditional electric-based methods usually rely on commercial high-voltage (HV) power sources, which are typically bulky, expensive, and potentially hazardous. The triboelectric nanogenerator (TENG) is a highly studied device that can generate HV output with limited current, showing great potential in droplet manipulation applications. However, current TENG-based approaches usually utilize traditional free-standing TENGs that produce short-pulsed alternating-current signals. This limitation hinders continuous electrostatic forces necessary for precise droplet control, leading to complex circuitry and suboptimal droplet motion control in terms of volume, distance, direction, and momentum. Here, a triboelectric contactless charge injection (TCCI) method employing a novel dual-functional triboelectric nanogenerator (DF-TENG), is proposed. The DF-TENG can produce both high voltage and constant current during unidirectional motion, enabling continuous corona discharges for contactless charge injection into the droplets. Using this method, a large-volume droplet (3000 µL) can be controlled with momentum up to 115.2 g mm s-1, quintupling the highest value recorded by the traditional methods. Moreover, the TCCI method is adaptable for a variety of non-slippery substrates and droplets of different compositions and viscosities, which makes it an ideal manipulation strategy for droplet transport, chemical reactions, and even driving solids.

Changes in Hole and Electron Injection under Electrical Stress and the Rapid Electroluminescence Loss in Blue Quantum-Dot Light-Emitting Devices.

Blue quantum dot light-emitting devices (QLEDs) suffer from fast electroluminescence (EL) loss when under electrical bias. Here, it is identified that the fast EL loss in blue QLEDs is not due to a deterioration in the photoluminescence quantum yield of the quantum dots (QDs), contrary to what is commonly believed, but rather arises primarily from changes in charge injection overtime under the bias that leads to a deterioration in charge balance. Measurements on hole-only and electron-only devices show that hole injection into blue QDs increases over time whereas electron injection decreases. Results also show that the changes are associated with changes in hole and electron trap densities. The results are further verified using QLEDs with blue and red QDs combinations, capacitance versus voltage, and versus time characteristics of the blue QLEDs. The changes in charge injection are also observed to be partially reversible, and therefore using pulsed current instead of constant current bias for driving the blue QLEDs leads to an almost 2.5× longer lifetime at the same initial luminance. This work systematically investigates the origin of blue QLEDs EL loss and provides insights for designing improved blue QDs paving the way for QLEDs technology commercialization.

The Stark Effect: A Tool for the Design of High-Performance Molecular Rectifiers.

Molecular electronic devices offer a path to the miniaturization of electronic circuits and could potentially facilitate novel functionalities that can be embedded into the molecular structure. Given their nanoscale dimensions, device properties are strongly influenced by quantum effects, yet many of these phenomena have been largely overlooked. We investigated the mechanism responsible for current rectification in molecular diodes and found that efficient rectification is achieved by enhancing the Stark effect strength and enabling a large number of molecules to participate in transport. These findings provided insights into the operation of molecular rectifiers and guided the development of high-performance devices via the design of molecules containing polarizable aromatic rings. Our results are consistent for different molecular structures and are expected to have broad applicability to all molecular devices by answering key questions related to charge transport mechanisms in such systems.

Efficient Perovskite Light-Emitting Diodes with Chemically Bonded Contact and Regulated Charge Behavior.

Efficient charge injection and radiative recombination are essential to achieving high-performance perovskite light-emitting diodes (Pero-LEDs). However, the perovskite emission layer (EML) and the electron transport layer (ETL) form a poor physically interfacial contact and non-negligible charge injection barrier, limiting the device performance. Herein, we utilize a phosphine oxide, 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T), to treat the perovskite/ETL interface and form a chemically bonded contact. Specifically, PO-T2T firmly bonds on the perovskite's surface and grain boundaries through a dative bond, effectively passivating the uncoordinated lead defects. Additionally, PO-T2T has high electron mobility and establishes an electron transport highway to bridge the ETL and EML. As a result, a maximum external quantum efficiency (EQEmax) of 22.06% (average EQEmax of 20.02 ± 1.00%) and maximum luminance (Lmax) of 103286 cd m-2 have been achieved for the champion device. Our results indicate that EML/ETL interface modifications are crucial for the fabrication of highly efficient Pero-LEDs.

Fabrication of a photo-crosslinkable fluoropolymer-passivated flexible neural probe and acute recording and stimulation performances in vivo.

Herein, we fabricated fluorine-containing, polymer-based, flexible neural probes with fluorinated ethylene propylene (FEP) films as the substrates and photo-crosslinkable fluoropolymers as the passivation material. For fabrication, metal-free Au layer formation on the FEP film, the simultaneous photo-adhesion and photo-patterning technique, and the pulsed-laser scanning probe shaping technique were combined, followed by Au electrode surface modification. The resultant probes achieved a charge injection limit equal to 5.18 mC cm-2 by implementing iridium oxide-modified nanoporous Au (IrOx/NPG) structures. We performed simultaneous in vivo micro-stimulations of the Schaffer collateral fibres and recorded the evoked field excitatory postsynaptic potentials (fEPSPs) in the stratum radiatum layer of the hippocampal Cornu Ammonis 1 region using a single probe. Inducing the fEPSP at very low charge per pulse settings (3.2-3.6 nC/pulse) indicates the efficient charge injection capability of the IrOx/NPG electrode, thereby enabling safe, prolonged, and thrifty micro-stimulations. Furthermore, the single probe-induced and recorded long-term potentiation persisted for periods longer than 60 min following theta-burst stimulation. The materials used in this study are all biocompatible and chemically robust. The fabricated neural probes can be applied in chronic clinical trials in vivo.

Functional Enhancement and Characterization of an Electrophysiological Mapping Electrode Probe with Carbonic, Directional Macrocontacts.

Electrophysiological mapping (EM) using acute electrode probes is a common procedure performed during functional neurosurgery. Due to their constructive specificities, the EM probes are lagging in innovative enhancements. This work addressed complementing a clinically employed EM probe with carbonic and circumferentially segmented macrocontacts that are operable both for neurophysiological sensing ("recording") of local field potentials (LFP) and for test stimulation. This paper illustrates in-depth the development that is based on the direct writing of functional materials. The unconventional fabrication processes were optimized on planar geometry and then transferred to the cylindrically thin probe body. We report and discuss the constructive concept and architecture of the probe, characteristics of the electrochemical interface deduced from voltammetry and chronopotentiometry, and the results of in vitro and in vivo recording and pulse stimulation tests. Two- and three-directional macrocontacts were added on probes having shanks of 550 and 770 µm diameters and 10-23 cm lengths. The graphitic material presents a ~2.7 V wide, almost symmetric water electrolysis window, and an ultra-capacitive charge transfer. When tested with clinically relevant 150 µs biphasic current pulses, the interfacial polarization stayed safely away from the water window for pulse amplitudes up to 9 mA (135 µC/cm2). The in vivo experiments on adult rat models confirmed the high-quality sensing of LFPs. Additionally, the in vivo-prevailing increase in the electrode impedance and overpotential are discussed and modeled by an ionic mobility-reducing spongiform structure; this restricted diffusion model gives new applicative insight into the in vivo-uprisen stimulation overpotential.

Excitation-Wavelength-Dependent Charge Injection and Hole Localization in Diblock Oligomers Anchored to TiO2.

A series of diblock oligomers containing oligothiophene (Tn, n = 4, 5) and 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadizole (TBT) segments, functionalized with carboxylic acid anchoring groups, were prepared and anchored to mesoporous TiO2 films to study wavelength-dependent interfacial electron transfer mechanisms. Thin films of the surface-anchored diblock oligomers contained two absorption bands centered at 400 and 500 nm, corresponding to the Tn and TBT blocks, respectively. Pulsed-laser excitation of the oligomer-sensitized films yielded local excited-states that promoted electron injection into TiO2. The injection pathway was dependent on the excitation wavelength, as electron injection occurred from the oligomer block that was locally excited. Recombination between the injected electron and the oxidized oligomer was sensitive to the bridging unit that separates the oligomer conjugated segments (-C≡C- vs trans-Pt(PBu3)2-). When the bridge facilitated strong coupling between the two blocks (-C≡C- bridge), the excitation wavelength had no effect on the recombination pathway, as the hole was delocalized over the entire oligomer. However, in the weak coupling case (Pt(PBu3)2- bridge), selective excitation resulted in wavelength-dependent hole localization that persisted to the µs time scale, providing control over the recombination pathway by varying the excitation wavelength. Dye-sensitized solar cells (DSSCs) were fabricated by using the diblock oligomers as sensitizers. The photocurrent action spectra were measured, and the absorbed photon-to-current efficiency (APCE) provided further insight into the electron-transfer mechanisms that are operative under continuous illumination.

Edge-Functionalized Graphene/Polydimethylsiloxane Composite Films for Flexible Neural Cuff Electrodes.

The design of neural electrodes has changed in the past decade, driven mainly by the development of new materials that open the possibility of manufacturing electrodes with adaptable mechanical properties and promising electrical properties. In this paper, we report on the mechanical and electrochemical properties of a polydimethylsiloxane (PDMS) composite with edge-functionalized graphene (EFG) and demonstrate its potential for use in neural implants with the fabrication of a novel neural cuff electrode. We have shown that a 200 µm thick 1:1 EFG/PDMS composite film has a stretchability of up to 20%, a Young's modulus of 2.52 MPa, and a lifetime of more than 10000 mechanical cycles, making it highly suitable for interfacing with soft tissue. Electrochemical characterization of the EFG/PDMS composite film showed that the capacitance of the composite increased up to 35 times after electrochemical reduction, widening the electrochemical water window and remaining stable after soaking for 5 weeks in phosphate buffered saline. The electrochemically activated EFG/PDMS electrode had a 3 times increase in the charge injection capacity, which is more than double that of a commercial platinum-based neural cuff. Electrochemical and spectrochemical investigations supported the conclusion that this effect originated from the stable chemisorption of hydrogen on the graphene surface. The biocompatibility of the composite was confirmed with an in vitro cell culture study using mouse spinal cord cells. Finally, the potential of the EFG/PDMS composite was demonstrated with the fabrication of a novel neural cuff electrode, whose double-layered and open structured design increased the cuff stretchability up to 140%, well beyond that required for an operational neural cuff. In addition, the cuff design offers better integration with neural tissue and simpler nerve fiber installation and locking.

Combining PEDOT:PSS Polymer Coating with Metallic 3D Nanowires Electrodes to Achieve High Electrochemical Performances for Neuronal Interfacing Applications.

This study presents a novel approach to improve the performance of microelectrode arrays (MEAs) used for electrophysiological studies of neuronal networks. The integration of 3D nanowires (NWs) with MEAs increases the surface-to-volume ratio, which enables subcellular interactions and high-resolution neuronal signal recording. However, these devices suffer from high initial interface impedance and limited charge transfer capacity due to their small effective area. To overcome these limitations, the integration of conductive polymer coatings, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) is investigated as a mean of improving the charge transfer capacity and biocompatibility of MEAs. The study combines platinum silicide-based metallic 3D nanowires electrodes with electrodeposited PEDOT:PSS coatings to deposit ultra-thin (<50 nm) layers of conductive polymer onto metallic electrodes with very high selectivity. The polymer-coated electrodes were fully characterized electrochemically and morphologically to establish a direct relationship between synthesis conditions, morphology, and conductive features. Results show that PEDOT-coated electrodes exhibit thickness-dependent improved stimulation and recording performances, offering new perspectives for neuronal interfacing with optimal cell engulfment to enable the study of neuronal activity with acute spatial and signal resolution at the sub-cellular level.

Erasable Domain Wall Current-Dominated Resistive Switching in BiFeO3 Devices with an Oxide-Metal Interface.

Electric transport in the charged domain wall (CDW) region has emerged as a promising phenomenon for the development of next-generation ferro-resistive memory with ultrahigh data storage density. However, accurately measuring the conductivity of CDWs induced by polarization reversal remains challenging due to the polarization modulation of the Schottky barrier at the thin film-electrode interface, which could partially contribute to the collected "on" current of the device. Here, we propose carefully selecting an electrode that can suppress the effect of interfacial barrier modulation induced by polarization reversal, allowing the collected current mainly from the conductive CDWs. The experiment was conducted on epitaxial BiFeO3(001) thin-film devices with vertical and horizontal geometries. Piezo-response force microscopy scanning showed the local polarization experienced 180° rotation to form CDWs under the vertical electric field. However, devices with SrRuO3 epitaxial top electrodes still exhibit an interfacial barrier-dominated diode behavior, with the "on" current proportional to the electrode area. To identify the CDW current, more interfacial defects were introduced by the deposition of Pt top electrodes, which significantly enhanced charge injection for the compensation of the reversed polarization driven by the electric field, leading to the suppressed polarization modulation of the Schottky barrier height. It was observed that the current flow through Pt electrodes is significantly lower compared to that of SRO electrodes and appears to be primarily influenced by the electrode perimeter instead of the electrode area, indicating CDW-dominated conduction behavior in these devices. Planar nanodevices were further fabricated to support the quantitative investigation of the Pt electrode size-dependent "on" current with a linear fit of the current magnitude versus the CDW cross-sectional area. This work constitutes an essential part of understanding the role of the CDW current in ferro-resistive memory devices.

Direct Measurement of Negative Capacitance in Ferroelectric/Semiconductor Heterostructures.

Negative capacitance (NC) is now an attractive research topic owing to its potential applications. For better integration, investigation about the phenomenon and mechanism of NC in ferroelectric materials on semiconductor substrates is important. In this work, ferroelectric BaTiO3 (BTO) films are deposited on the low-resistance Si(100) substrates to constitute Pt/BTO/p-Si/Pt samples with the metal/ferroelectric/semiconductor/metal (MFSM) structure, on which NC are directly measured at low frequencies with a large DC bias. Because of the unique asymmetric interface, the NC value is tunable by the polarity and magnitude of the DC bias. Analysis based on the impedance and ferroelectric characteristics reveals that, in addition to the displacement current related to the electric polarization, there is also relaxation current caused by interface charge injection and oxygen vacancy migration. This work provides another idea for studying miniaturized and low-energy devices utilizing NC, which is of great significance for the development of silicon-based ferroelectric devices.

High-Performance Organic Source-Gated Transistors Enabled by the Indium-Tin Oxide-Diketopyrrolopyrrole Polymer Interface.

Source-gated transistors are a new driver of low-power high-gain thin-film electronics. However, source-gated transistors based on organic semiconductors are not widely investigated yet despite their potential for future display and sensor technologies. We report on the fabrication and modeling of high-performance organic source-gated transistors utilizing a critical junction formed between indium-tin oxide and diketopyrrolopyrrole polymer. This partially blocked hole-injection interface is shown to offer both a sufficient level of drain currents and a strong depletion effect necessary for source pinch-off. As a result, our transistors exhibit a set of outstanding metrics, including an intrinsic gain of 160 V/V, an output resistance of 4.6 GΩ, and a saturation coefficient of 0.2 at an operating voltage of 5 V. Drift-diffusion simulation is employed to reproduce and rationalize the experimental data. The modeling reveals that the effective contact length is significantly reduced in an interdigitated electrode geometry, eventually contributing to the realization of low-voltage saturation.

Graphene/Ge Photoconductive Position-Sensitive Detectors Based on the Charge Injection Effect.

Position-sensitive detectors (PSDs) are of great significance to optical communication, automatic alignment, and dislocation detection domains, by precisely obtaining the position information of infrared light spots which are invisible to human eyes. Herein, a kind of PSD based on graphene/germanium (Ge) heterojunction architecture is proposed and demonstrated, which exhibits amplified signals by unitizing the charge injection effect. Driven by the graphene/Ge heterojunction, a large number of photogenerated carriers diffuse from the incident position of the light spot and subsequently inject into graphene, which ultimately generates a photoresponse with high efficiency. The experimental results show that the device can exhibit a fast response speed of 3 µs, a high responsivity of ~40 A/W, and a detection distance of 3000 µm at the 1550 nm band, which hints that the graphene/Ge heterojunction can be used as an efficient platform for near-infrared light spot position sensing.

Polarization Switching Kinetics in Thin Ferroelectric HZO Films.

Ferroelectric polycrystalline HfO2 thin films are the most promising material for the implementation of novel non-volatile ferroelectric memories because of their attractive properties, such as compatibility with modern Si technology, perfect scalability, low power consumption and high endurance. However, for the commercialization of ferroelectric memory, some crucial aspects of its operation should be addressed, including the polarization switching mechanism that determines the switching speed. Although several reports on polarization switching kinetics in HfO2-based layers already exist, the physical origin of retardation behavior of polarization switching at the low and medium switching fields remains unclear. In this work, we examine several models of switching kinetics that can potentially explain or describe retardation behavior observed in experimental switching kinetics for Hf0.5Zr0.5O2 (HZO)-based capacitors and propose a new model. The proposed model is based on a statistical model of switching kinetics, which has been significantly extended to take into account the specific properties of HZO. The model includes contributions of the depolarization field and the built-in internal field originating from the charge injection into the functional HZO layer during the read procedure as well as in-plane inhomogeneity of the total electric field in ferroelectric. The general model of switching kinetics shows excellent agreement with the experimental results.

A portable neurostimulator circuit with anodic bias enhances stimulation injection capacity.

Objective.Electrochemically safe and efficient charge injection for neural stimulation necessitates monitoring of polarization and enhanced charge injection capacity of the stimulating electrodes. In this work, we present improved microstimulation capability by developing a custom-designed multichannel portable neurostimulator with a fully programmable anodic bias circuitry and voltage transient monitoring feature.Approach.We developed a 16-channel multichannel neurostimulator system, compared charge injection capacities as a function of anodic bias potentials, and demonstrated convenient control of the system by a custom-designed user interface allowing bidirectional wireless data transmission of stimulation parameters and recorded voltage transients. Charge injections were conducted in phosphate-buffered saline with silicon-based iridium oxide microelectrodes.Main results.Under charge-balanced 200µs cathodic first pulsing, the charge injection capacities increased proportionally to the level of anodic bias applied, reaching a maximum of ten-fold increase in current intensity from 10µA (100µC cm-2) to 100µA (1000µC cm-2) with a 600 mV anodic bias. Our custom-designed and completely portable 16-channel neurostimulator enabled a significant increase in charge injection capacityin vitro. Significance.Limited charge injection capacity has been a bottleneck in neural stimulation applications, and our system may enable efficacious behavioral animal study involving chronic microstimulation while ensuring electrochemical safety.

Surface Modification-Dominated Space-Charge Behaviors of LDPE Films: A Role of Charge Injection Barriers.

Gradually increasing power transmission voltage requires an improved high-voltage capability of polymeric insulating materials. Surface modification emerges as an easily accessible approach in enhancing breakdown and flashover performances due to the widely acknowledged modification of space-charge behaviors. However, as oxidation and fluorination essentially react within a limited depth of 2 µm underneath polymer surfaces, the nature of such bulk space-charge modulation remains a controversial issue, and further investigation is needed to realize enhancement of insulating performance. In this work, the surface oxidation-dependent space-charge accumulation in LDPE film was found to be dominated by an electrode/polymer interfacial barrier, but not by the generation of bulk charge traps. Through quantitative investigation of space-charge distributions along with induced electric field distortion, the functions of surface oxidation on the interfacial barrier of a typical dielectric polymer, LDPE, is discussed and linked to space-charge behaviors. As the mechanism of surface modification on space-charge behaviors is herein proposed, space-charge accumulation can be effectively modified by selecting an appropriate surface modification method, which consequentially benefits breakdown and flashover performances of polymeric insulating films for high-voltage applications.