Laser‐Induced Freestanding Graphene Papers: A New Route of Scalable Fabrication with Tunable Morphologies and Properties for Multifunctional Devices and Structures

The recently emergent laser‐induced graphene (LIG) technology has endowed the fabrication of smart devices with one‐step processing and scalable/designable features. Graphene paper (GP), an important architecture of 2D layered carbon, however, is never produced through LIG. Herein, a novel strategy is reported for production of freestanding GP through LIG technology. It is first determined that the unique spatial configuration of polyimide (PI) paper is critical for the preparation of GP without the appearance of intense shape distortion. Benefiting from the mechanism, the as‐produced laser‐induced graphene paper (LIGP) is foldable, trimmable, and integratable to customized shapes and structures with the largest dimension of 40 × 35 cm². Based on the processing–structure–property relationship study, one is capable of controlling and tuning various physical and chemical properties of LIGPs, rendering them unique for assembling flexible electronics and smart structures, e.g., human/robotic motion detectors, liquid sensors, water–oil separators, antibacterial media, and flame retardant/deicing/self‐sensing composites. With the key findings, the escalation of LIGP for commercialization, roll‐to‐roll manufacturing, and multidisciplinary applications are highly expected.     

Roll‐to‐Roll Production of Graphene Hybrid Electrodes for High‐Efficiency,Flexible Organic Photoelectronics

Despite nearly two decades of research, the absence of ideal, flexible, and transparent electrodes has been the biggest bottleneck for realizing flexible and printable electronics via roll‐to‐roll (R2R) method. A fabrication of poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate):graphene:ethyl cellulose (PEDOT:PSS:G:EC) hybrid electrodes by R2R process, which allows for the elimination of strong acid treatment. The high‐performance flexible printable electrode includes a transmittance (T) of 78% at 550 nm and a sheet resistance of 13 Ω sq⁻¹ with excellent mechanical stability. These features arise from the PSS interacting strongly with the ethyoxyl groups from EC promoting a favorable phase separation between PEDOT and PSS chains, and the highly uniform and conductive G:EC enable rearrangement of the PEDOT chains with more expanded conformation surrounded by G:EC via the π–π interaction between G:EC and PEDOT. The hybrid electrodes are fully functional as universal electrodes for outstanding flexible electronic applications. Organic solar cells based on the hybrid electrode exhibit a high power conversion efficiency of 9.4% with good universality for active layer. Moreover, the organic light‐emitting diodes and photodetector devices hold the same level to or outperform those based on indium tin oxide flexible transparent electrodes.     

Low‐Temperature Heteroepitaxy of 2D PbI2/Graphene for Large‐Area Flexible Photodetectors

Heterostructures based on graphene and other 2D atomic crystals exhibit fascinating properties and intriguing potential in flexible optoelectronics, where graphene films function as transparent electrodes and other building blocks are used as photoactive materials. However, large‐scale production of such heterostructures with superior performance is still in early stages. Herein, for the first time, the preparation of a submeter‐sized, vertically stacked heterojunction of lead iodide (PbI₂)/graphene on a flexible polyethylene terephthalate (PET) film by vapor deposition of PbI₂ on graphene/PET substrate at a temperature lower than 200 °C is demonstrated. This film is subsequently used to fabricate bendable graphene/PbI₂/graphene sandwiched photodetectors, which exhibit high responsivity (45 A W^?1 cm^?2), fast response (35 µs rise, 20 µs decay), and high‐resolution imaging capability (1 µm). This study may pave a facile pathway for scalable production of high‐performance flexible devices.     

Graphene‐Based Linear Tandem Micro‐Supercapacitors with Metal‐Free Current Collectors and High‐Voltage Output

Printable supercapacitors are regarded as a promising class of microscale power source, but are facing challenges derived from conventional sandwich‐like geometry. Herein, the printable fabrication of new‐type planar graphene‐based linear tandem micro‐supercapacitors (LTMSs) on diverse substrates with symmetric and asymmetric configuration, high‐voltage output, tailored capacitance, and outstanding flexibility is demonstrated. The resulting graphene‐based LTMSs consisting of 10 micro‐supercapacitors (MSs) present efficient high‐voltage output of 8.0 V, suggestive of superior uniformity of the entire integrated device. Meanwhile, LTMSs possess remarkable flexibility without obvious capacitance degradation under different bending states. Moreover, areal capacitance of LTMSs can be sufficiently modulated by incorporating polyaniline‐based pseudocapacitive nanosheets into graphene electrodes, showing enhanced capacitance of 7.6 mF cm^?2. To further improve the voltage output and energy density, asymmetric LTMSs are fabricated through controlled printing of linear‐patterned graphene as negative electrodes and MnO₂ nanosheets as positive electrodes. Notably, the asymmetric LTMSs from three serially connected MSs are easily extended to 5.4 V, triple voltage output of the single cell (1.8 V), suggestive of the versatile applicability of this technique. Therefore, this work offers numerous opportunities of graphene and analogous nanosheets for one‐step scalable fabrication of flexible tandem energy storage devices integrating with printed electronics on same substrate.     

Laser Fabrication of Graphene-Based Flexible Electronics

Recent years have witnessed the rise of graphene and its applications in various electronic devices. Specifically, featuring excellent flexibility, transparency, conductivity, and mechanical robustness, graphene has emerged as a versatile material for flexible electronics. In the past decade, facilitated by various laser processing technologies, including the laser-treatment-induced photoreduction of graphene oxides, flexible patterning, hierarchical structuring, heteroatom doping, controllable thinning, etching, and shock of graphene, along with laser-induced graphene on polyimide, graphene has found broad applications in a wide range of electronic devices, such as power generators, supercapacitors, optoelectronic devices, sensors, and actuators. Here, the recent advancements in the laser fabrication of graphene-based flexible electronic devices are comprehensively summarized. The various laser fabrication technologies that have been employed for the preparation, processing, and modification of graphene and its derivatives are reviewed. A thorough overview of typical laser-enabled flexible electronic devices that are based on various graphene sources is presented. With the rapid progress that has been made in the research on graphene preparation methodologies and laser micronanofabrication technologies, graphene-based electronics may soon undergo fast development.     

Heterogeneous Integration of Carbon‐Nanotube–Graphene for High‐Performance,Flexible, and Transparent Photodetectors

Low‐dimensional carbon materials, such as semiconducting carbon nanotubes (CNTs), conducting graphene, and their hybrids, are of great interest as promising candidates for flexible, foldable, and transparent electronics. However, the development of highly photoresponsive, flexible, and transparent optoelectronics still remains limited due to their low absorbance and fast recombination rate of photoexcited charges, despite the considerable potential of photodetectors for future wearable and foldable devices. This work demonstrates a heterogeneous, all‐carbon photodetector composed of graphene electrodes and porphyrin‐interfaced single‐walled CNTs (SWNTs) channel, exhibiting high photoresponse, flexibility, and full transparency across the device. The porphyrin molecules generate and transfer photoexcited holes to the SWNTs even under weak white light, resulting in significant improvement of photoresponsivity from negligible to 1.6 × 10^?2 A W^?1. Simultaneously, the photodetector exhibits high flexibility allowing stable light detection under ≈50% strain (i.e., a bending radius of ≈350 µm), and retaining a sufficient transparency of ≈80% at 550 nm. Experimental demonstrations as a wearable sunlight sensor highlight the utility of the photodetector that can be conformally mounted on human skin and other curved surfaces without any mechanical and optical constraints. The heterogeneous integration of porphyrin–SWNT–graphene may provide a viable route to produce invisible, high‐performance optoelectronic systems.     

High‐Responsivity Graphene/InAs Nanowire Heterojunction Near‐Infrared Photodetectors with Distinct Photocurrent On/Off Ratios

Graphene is a promising candidate material for high‐speed and ultra‐broadband photodetectors. However, graphene‐based photodetectors suffer from low photoreponsivity and I_light/I_dark ratios due to their negligible‐gap nature and small optical absorption. Here, a new type of graphene/InAs nanowire (NW) vertically stacked heterojunction infrared photodetector is reported, with a large photoresponsivity of 0.5 AW^?1 and I_light/I_dark ratio of 5 × 10², while the photoresponsivity and I_light/I_dark ratio of graphene infrared photodetectors are 0.1 mAW^?1 and 1, respectively. The Fermi level (E_F ) of graphene can be widely tuned by the gate voltage owing to its 2D nature. As a result, the back‐gated bias can modulate the Schottky barrier (SB) height at the interface between graphene and InAs NWs. Simulations further demonstrate the rectification behavior of graphene/InAs NW heterojunctions and the tunable SB controls charge transport across the vertically stacked heterostructure. The results address key challenges for graphene‐based infrared detectors, and are promising for the development of graphene electronic and optoelectronic applications.     

Graphene‐Contacted Ultrashort Channel Monolayer MoS2 Transistors

2D semiconductors are promising channel materials for field‐effect transistors (FETs) with potentially strong immunity to short‐channel effects (SCEs). In this paper, a grain boundary widening technique is developed to fabricate graphene electrodes for contacting monolayer MoS₂. FETs with channel lengths scaling down to ≈4 nm can be realized reliably. These graphene‐contacted ultrashort channel MoS₂ FETs exhibit superior performances including the nearly Ohmic contacts and excellent immunity to SCEs. This work provides a facile route toward the fabrication of various 2D material‐based devices for ultrascaled electronics.     

Highly Efficient and Ultrasensitive Large‐Area Flexible Photodetector Based on Perovskite Nanowires

Hybrid organic–inorganic perovskites have shown exceptional semiconducting properties and microstructural versatility for inexpensive, solution‐processable photovoltaic and optoelectronic devices. In this work, an all‐solution‐based technique in ambient environment for highly sensitive and high‐speed flexible photodetectors using high crystal quality perovskite nanowires grown on Kapton substrate is presented. At 10 V, the optimized photodetector exhibits a responsivity as high as 0.62 A W^?1, a maximum specific detectivity of 7.3 × 10¹² cm Hz^1/2 W^?1, and a rise time of 227.2 µs. It also shows remarkable photocurrent stability even beyond 5000 bending cycles. Moreover, a deposition of poly(methyl methacrylate) (PMMA) as a protective layer on the perovskite yields significantly better stability under ambient air operation: the PMMA‐protected devices are stable for over 30 days. This work demonstrates a cost‐effective fabrication technique for high‐performance flexible photodetectors and opens opportunities for research advancements in broadband and large‐scale flexible perovskite‐based optoelectronic devices.     

Direct Laser‐Patterned Micro‐Supercapacitors from Paintable MoS2 Films

Micrometer‐sized electrochemical capacitors have recently attracted attention due to their possible applications in micro‐electronic devices. Here, a new approach to large‐scale fabrication of high‐capacitance, two‐dimensional MoS₂ film‐based micro‐supercapacitors is demonstrated via simple and low‐cost spray painting of MoS₂ nanosheets on Si/SiO₂ chip and subsequent laser patterning. The obtained micro‐supercapacitors are well defined by ten interdigitated electrodes (five electrodes per polarity) with 4.5 mm length, 820 μm wide for each electrode, 200 μm spacing between two electrodes and the thickness of electrode is ～0.45 μm. The optimum MoS₂‐based micro‐supercapacitor exhibits excellent electrochemical performance for energy storage with aqueous electrolytes, with a high area capacitance of 8 mF cm^?2 (volumetric capacitance of 178 F cm^?3) and excellent cyclic performance, superior to reported graphene‐based micro‐supercapacitors. This strategy could provide a good opportunity to develop various micro‐/nanosized energy storage devices to satisfy the requirements of portable, flexible, and transparent micro‐electronic devices.     

In situ synthesis of SnO2/graphene nanocomposite and their application as anode material for lithium ion battery

SnO₂/graphene nanocomposite was prepared via an in situ chemical synthesis method. The nanocomposite was characterized by X-ray diffraction, filed emission scanning electron microscope and transmission electron microscope, which revealed that tiny SnO₂ nanoparticles could be homogeneously distributed on the graphene matrix. The electrochemical performance of the SnO₂/graphene nanocomposite as anode material was measured by galvanostatic charge/discharge cycling. The SnO₂/graphene nanocomposite showed a reversible capacity of 665 mAh/g after 50 cycles and an excellent cycling performance for lithium ion battery, which was ascribed to the three-dimensional architecture of SnO₂/graphene nanocomposite. These results suggest that SnO₂/graphene nanocomposite would be a promising anode material for lithium ion battery.     

SnO<Subscript>2</Subscript>/graphene composite with high lithium storage capability for lithium rechargeable batteries

SnO₂/graphene nanocomposites have been fabricated by a simple chemical method. In the fabrication process, the control of surface charge causes echinoid-like SnO₂ nanoparticles to be formed and uniformly decorated on the graphene. The electrostatic attraction between a graphene nanosheet (GNS) and the echinoid-like SnO₂ particles under controlled pH creates a unique nanostructure in which extremely small SnO₂ particles are uniformly dispersed on the GNS. The SnO₂/graphene nanocomposite has been shown to perform as a high capacity anode with good cycling behavior in lithium rechargeable batteries. The anode retained a reversible capacity of 634 mA·h·g⁻¹ with a coulombic efficiency of 98% after 50 cycles. The high reversibility can be attributed to the mechanical buffering by the GNS against the large volume change of SnO₂ during delithiation/lithiation reactions. Furthermore, the power capability is significantly enhanced due to the nanostructure, which enables facile electron transport through the GNS and fast delithiation/lithiation reactions within the echinoid-like nano-SnO₂. The route suggested here for the fabrication of SnO₂/graphene hybrid materials is a simple economical route for the preparation of other graphene-based hybrid materials which can be employed in many different fields.     

2D In2S3 Nanoflake Coupled with Graphene toward High‐Sensitivity and Fast‐Response Bulk‐Silicon Schottky Photodetector

Silicon‐based electronic devices, especially graphene/Si photodetectors (Gr/Si PDs), have triggered tremendous attention due to their simple structure and flexible integration of the Schottky junction. However, due to the relatively poor light–matter interaction and mobility of silicon, these Gr/Si PDs typically suffer an inevitable compromise between photoresponsivity and response speed. Herein, a novel strategy for coupling 2D In₂S₃ with Gr/Si PDs is demonstrated. The introduction of the double‐heterojunction design not only strengthens the light absorption of graphene/Si but also combines the advantages of the photogating effect and photovoltaic effect, which suppresses the dark current, accelerates the separation of photogenerated carriers, and brings photoconductive gain. As a result, In₂S₃/graphene/Si devices present an ultrahigh photoresponsivity of 4.53 × 10⁴ A W^?1 and fast response speed less than 40 µs, simultaneously. These parameters are an order of magnitude higher than pristine Gr/Si PDs and among the best values compared with reported 2D materials/Si heterojunction PDs. Furthermore, the In₂S₃/graphene/Si PD expresses outstanding long‐term stability, with negligible performance degradation even after 1 month in air or 1000 cycles of operation. These findings highlight a simple and novel strategy for constructing high‐sensitivity and ultrafast Gr/Si PDs for further optoelectronic applications.     

Low‐Voltage Photodetectors with High Responsivity Based on Solution‐Processed Micrometer‐Scale All‐Inorganic Perovskite Nanoplatelets

All‐inorganic photodetectors based on scattered CsPbBr₃ nanoplatelets with lateral dimension as large as 10 µm are fabricated, and the CsPbBr₃ nanoplatelets are solution processed governed by a newly developed ion‐exchange soldering mechanism. Under illumination of a 442 nm laser, the photoresponsivity of photodetectors based on these scattered CsPbBr₃ nanoplatelets is as high as 34 A W^?1, which is the largest value reported from all‐inorganic perovskite photodetectors with an external driven voltage as small as 1.5 V. Moreover, the rise and fall times are 0.6 and 0.9 ms, respectively, which are comparable to most of the state‐of‐the‐art all‐inorganic perovskite‐based photodetectors. All the material synthesis and device characterization are conducted at room temperature in ambient air. This work demonstrates that the solution‐processed large CsPbBr₃ nanoplatelets are attractive candidates to be applied in low‐voltage, low‐cost, ultra highly integrated optoelectronic devices.     

Flexible Visible‐Light Photodetectors with Broad Photoresponse Based on ZrS3 Nanobelt Films

Two new flexible visible‐light photodetectors based on ZrS₃ nanobelts films are fabricated on a polypropylene (PP) film and printing paper, respectively, by an adhesive‐tape transfer method, and their light‐induced electric properties are investigated in detail. The devices demonstrate a remarkable response to 405 to 780 nm light, a photocurrent that depends on the optical power and light wavelength, and an excellent photoswitching effect and stability. This implies that ZrS₃ nanobelts are prospective candidates for high‐performance nanoscale optoelectronic devices that may be practically applied in photodetection of visible to near infrared light. The facile fabrication method is extendable to flexible nanodevices with different nanostructures.     

Printable Transparent Conductive Films for Flexible Electronics

Printed electronics are an important enabling technology for the development of low‐cost, large‐area, and flexible optoelectronic devices. Transparent conductive films (TCFs) made from solution‐processable transparent conductive materials, such as metal nanoparticles/nanowires, carbon nanotubes, graphene, and conductive polymers, can simultaneously exhibit high mechanical flexibility, low cost, and better photoelectric properties compared to the commonly used sputtered indium‐tin‐oxide‐based TCFs, and are thus receiving great attention. This Review summarizes recent advances of large‐area flexible TCFs enabled by several roll‐to‐roll‐compatible printed techniques including inkjet printing, screen printing, offset printing, and gravure printing using the emerging transparent conductive materials. The preparation of TCFs including ink formulation, substrate treatment, patterning, and postprocessing, and their potential applications in solar cells, organic light‐emitting diodes, and touch panels are discussed in detail. The rational combination of a variety of printed techniques with emerging transparent conductive materials is believed to extend the opportunities for the development of printed electronics within the realm of flexible electronics and beyond.     

Lowering the Schottky Barrier Height by Graphene/Ag Electrodes for High‐Mobility MoS2 Field‐Effect Transistors

2D transition metal dichalcogenides (TMDCs) have emerged as promising candidates for post‐silicon nanoelectronics owing to their unique and outstanding semiconducting properties. However, contact engineering for these materials to create high‐performance devices while adapting for large‐area fabrication is still in its nascent stages. In this study, graphene/Ag contacts are introduced into MoS₂ devices, for which a graphene film synthesized by chemical vapor deposition (CVD) is inserted between a CVD‐grown MoS₂ film and a Ag electrode as an interfacial layer. The MoS₂ field‐effect transistors with graphene/Ag contacts show improved electrical and photoelectrical properties, achieving a field‐effect mobility of 35 cm² V^?1 s^?1, an on/off current ratio of 4 × 10⁸, and a photoresponsivity of 2160 A W^?1, compared to those of devices with conventional Ti/Au contacts. These improvements are attributed to the low work function of Ag and the tunability of graphene Fermi level; the n‐doping of Ag in graphene decreases its Fermi level, thereby reducing the Schottky barrier height and contact resistance between the MoS₂ and electrodes. This demonstration of contact interface engineering with CVD‐grown MoS₂ and graphene is a key step toward the practical application of atomically thin TMDC‐based devices with low‐resistance contacts for high‐performance large‐area electronics and optoelectronics.     

Solution‐Processed 3D RGO–MoS2/Pyramid Si Heterojunction for Ultrahigh Detectivity and Ultra‐Broadband Photodetection

Molybdenum disulfide (MoS₂), a typical 2D metal dichalcogenide (2DMD), has exhibited tremendous potential in optoelectronic device applications, especially in photodetection. However, due to the weak light absorption of planar mono‐/multilayers, limited cutoff wavelength edge, and lack of high‐quality junctions, most reported MoS₂‐based photodetectors show undesirable performance. Here, a structurized 3D heterojunction of RGO–MoS₂/pyramid Si is demonstrated via a simple solution‐processing method. Owing to the improved light absorption by the pyramid structure, the narrowed bandgap of the MoS₂ by the imperfect crystallinity, and the enhanced charge separation/transportation by the inserted reduced graphene oxide (RGO), the assembled photodetector exhibits excellent performance in terms of a large responsivity of 21.8 A W^?1, extremely high detectivity up to 3.8 × 10¹⁵ Jones (Jones = cm Hz^1/2 W^?1) and ultrabroad spectrum response ranging from 350 nm (ultraviolet) to 4.3 µm (midwave infrared). These device parameters represent the best results for MoS₂‐based self‐driven photodetectors, and the detectivity value sets a new record for the 2DMD‐based photodetectors reported thus far. Prospectively, the design of novel 3D heterojunction can be extended to other 2DMDs, opening up the opportunities for a host of high‐performance optoelectronic devices.     

A General Method for the Chemical Synthesis of Large‐Scale,Seamless Transition Metal Dichalcogenide Electronics

The capability to directly build atomically thin transition metal dichalcogenide (TMD) devices by chemical synthesis offers important opportunities to achieve large‐scale electronics and optoelectronics with seamless interfaces. Here, a general approach for the chemical synthesis of a variety of TMD (e.g., MoS₂, WS₂, and MoSe₂) device arrays over large areas is reported. During chemical vapor deposition, semiconducting TMD channels and metallic TMD/carbon nanotube (CNT) hybrid electrodes are simultaneously formed on CNT‐patterned substrate, and then coalesce into seamless devices. Chemically synthesized TMD devices exhibit attractive electrical and mechanical properties. It is demonstrated that chemically synthesized MoS₂–MoS₂/CNT devices have Ohmic contacts between MoS₂/CNT hybrid electrodes and MoS₂ channels. In addition, MoS₂–MoS₂/CNT devices show greatly enhanced mechanical stability and photoresponsivity compared with conventional gold‐contacted devices, which makes them suitable for flexible optoelectronics. Accordingly, a highly flexible pixel array based on chemically synthesized MoS₂–MoS₂/CNT photodetectors is applied for image sensing.     

A 2D Titanium Carbide MXene Flexible Electrode for High-Efficiency Light-Emitting Diodes

Although several transparent conducting materials such as carbon nanotubes, graphene, and conducting polymers have been intensively explored as flexible electrodes in optoelectronic devices, their insufficient electrical conductivity, low work function, and complicated electrode fabrication processes have limited their practical use. Herein, a 2D titanium carbide (Ti₃C₂) MXene film with transparent conducting electrode (TCE) properties, including high electrical conductivity (≈11 670 S cm⁻¹) and high work function (≈5.1 eV), which are achieved by combining a simple solution processing with modulation of surface composition, is described. A chemical neutralization strategy of a conducting-polymer hole-injection layer is used to prevent detrimental surface oxidation and resulting degradation of the electrode film. Use of the MXene electrode in an organic light-emitting diode leads to a current efficiency of ≈102.0 cd A⁻¹ and an external quantum efficiency of ≈28.5% ph/el, which agree well with the theoretical maximum values from optical simulations. The results demonstrate the strong potential of MXene as a solution-processable electrode in optoelectronic devices and provide a guideline for use of MXenes as TCEs in low-cost flexible optoelectronic devices.