In Situ Growth of Graphene on Polyimide for High-Responsivity Flexible PbS-Graphene Photodetectors.

Graphene is an ideal material for flexible optoelectronic devices due to its excellent electrical and optical properties. However, the extremely high growth temperature of graphene has greatly limited the direct fabrication of graphene-based devices on flexible substrates. Here, we have realized in situ growth of graphene on a flexible polyimide substrate. Based on the multi-temperature-zone chemical vapor deposition cooperated with bonding a Cu-foil catalyst onto the substrate, the growth temperature of graphene was controlled at only 300 °C, enabling the structural stability of polyimide during growth. Thus, large-area high-quality monolayer graphene film was successfully in situ grown on polyimide. Furthermore, a PbS-graphene flexible photodetector was fabricated using the graphene. The responsivity of the device reached 105 A/W with 792 nm laser illumination. The in-situ growth ensures good contact between graphene and substrate; therefore, the device performance can remain stable after multiple bending. Our results provide a highly reliable and mass-producible path for graphene-based flexible devices.

Direct Growth of Patterned Vertical Graphene Using Thermal Stress Mismatch between Barrier Layer and Substrate.

Vertical graphene (VG) combines the excellent properties of conventional graphene with a unique vertical nanosheet structure, and has shown tremendous promise in the field of electronics and composites. However, its complex surface morphology brings great difficulties to micro-nano fabrication, especially regarding photolithography induced nanosheet collapse and remaining chemical residues. Here, we demonstrate an innovative method for directly growing patterned VG on a SiO2/Si substrate. A patterned Cr film was deposited on the substrate as a barrier layer. The VG was synthesized by PECVD on both the patterned Cr film and the exposed SiO2/Si substrate. During the cooling process, the patterned Cr film covered by VG naturally peeled off from the substrate due to the thermal stress mismatch, while the VG directly grown on the SiO2/Si substrate was remained. The temperature-dependent thermal stress distribution in each layer was analyzed using finite element simulations, and the separation mechanism of the Cr film from the substrate was explained. This method avoids the contamination and damage caused by the VG photolithography process. Our work is expected to provide a convenient and reliable solution for the manufacture of VG-based electronic devices.

In Situ Growth of Graphene Catalyzed by a Phase-Change Material at 400 °C for Wafer-Scale Optoelectronic Device Application.

The use of metal foil catalysts in the chemical vapor deposition of graphene films makes graphene transfer an ineluctable part of graphene device fabrication, which greatly limits industrialization. Here, an oxide phase-change material (V2 O5 ) is found to have the same catalytic effect on graphene growth as conventional metals. A uniform large-area graphene film can be obtained on a 10 nm V2 O5 film. Density functional theory is used to quantitatively analyze the catalytic effect of V2 O5 . Due to the high resistance property of V2 O5 at room temperature, the obtained graphene can be directly used in devices with V2 O5 as an intercalation layer. A wafer-scale graphene-V2 O5 -Si (GVS) Schottky photodetector array is successfully fabricated. When illuminated by a 792 nm laser, the responsivity of the photodetector can reach 266 mA W-1 at 0 V bias and 420 mA W-1 at 2 V. The transfer-free device fabrication process enables high feasibility for industrialization.

Transfer-Free CVD Growth of High-Quality Wafer-Scale Graphene at 300 °C for Device Mass Fabrication.

Direct chemical vapor deposition of graphene on semiconductors and insulators provides high feasibility for integration of graphene devices and semiconductor electronics. However, the current methods typically rely on high temperatures (>1000 °C), which can damage the substrates. Here, a growth method for high-quality large-area graphene at 300 °C is introduced. A multizone furnace with gradient temperature control was designed according to a computational fluid dynamics model. The crucial roles of the chamber pressure in the film continuity and hydrogen composition in the graphene defect density at low temperature were revealed. As a result, a uniform graphene film with the Raman ratio ID/IG = 0.08 was obtained. Furthermore, a technique of laminating single-crystal Cu foil as a sacrificial layer on the substrate was proposed to realize transfer-free growth, and a wafer-scale graphene transistor array was demonstrated with good performance consistency, which paves the way for mass fabrication of graphene devices.

Graphene-silicon-graphene Schottky junction photodetector with field effect structure.

Graphene has unique advantages in ultrabroadband detection. However, nowadays graphene-based photodetectors cannot meet the requirements for practical applications due to their poor performance. Here, we report a graphene-silicon-graphene Schottky junction photodetector assisted by field effect. Two separate graphene sheets are located on both sides of the n-doped silicon to form two opposite lateral series heterojunctions with silicon, and a transparent top gate is designed to modulate the Schottky barrier. Low doping concentration of silicon and negative gate bias can significantly raise the barrier height. Under the combined action of these two measures, the barrier height increases from 0.39 eV to 0.77 eV. Accordingly, the performance of the photodetector has been greatly improved. The photoresponsivity of the optimized device is 2.6 A/W at 792 nm, 1.8 A/W at 1064 nm, and 0.42 A/W at 1550 nm, and the on/off photo-switching ratio reaches 104. Our work provides a feasible solution for the development of graphene-based optoelectronic devices.

Efficiency improvement of GaN-based micro-light-emitting diodes embedded with Ag NPs into a periodic arrangement of nano-hole channel structure by ultra close range localized surface plasmon coupling.

NH-µLED, namely a micro light-emitting diode structure with nano-holes dug all the way through the active region, is designed to make silver nanoparticles in extremely close contact with the quantum wells for improving the coupling between the localized surface plasmon and the quantum wells (LSP-QWs coupling) and thus enhancing the optical properties of theµLED. The experimental results show that, thanks to this deep nanohole structure, the LSP-QWs coupling can be realized effectively, which ultimately increases the optical performance of theµLED. The internal quantum efficiency of the NH-µLED filled with silver nanoparticles is increased by 12%, and the final optical output power is also enhanced. We have further carried out a comparison study which measures the transient lifetime of two different types ofµLEDs, and the results provide convincing evidence for the existence of the ultra close range LSP-QWs coupling effect.

High responsivity graphene-InGaAs near-infrared photodetector realized by hole trapping and its response saturation mechanism.

Graphene is an ideal material for wide spectrum detector owing to its special band structure, but its low light absorption and fast composite of photogenerated carriers lead to a weak response performance. In this paper, we designed a unique photoconductive graphene-InGaAs photodetector. The built-in electric field was formed between graphene and InGaAs, which can prolong the lifetime of photogenerated carriers and improve the response of devices by confining the holes. Compared with graphene-Si structure, a higher built-in electric field and reach to 0.54 eV is formed. It enables the device to achieve a responsivity of 60 AW-1 and a photoconductive gain of 79.4 at 792 nm. In the 1550 nm communication band, the responsivity of the device is also greater than 10 AW-1 and response speed is less than 2 ms. Meanwhile, the saturation phenomenon of light response was also found in this photoconductive graphene heterojunction detector during the experiment, we have explained the phenomenon by the capacitance theory of the built-in electric field, and the maximum optical responsivity of the detector is calculated theoretically, which is in good agreement with the measurement result.

Graphene-assisted preparation of large-scale single-crystal Ag(111) nanoparticle arrays for surface-enhanced Raman scattering.

Surface plasmon resonance (SPR) of metal nanostructures has broad application prospects in the fields of sensing, energy, catalysis and optics. This paper reports a graphene-assisted method for preparing large-scale single-crystal Ag(111) nanoparticle (NP) arrays based on the ion implantation technique. By surface periodic patterning treatment and annealing of the implanted sample, regularly arranged Ag NPs can be prepared on the sample surface. A new application for graphene is proposed, that is, as a perfect barrier layer to prevent metal atoms from evaporating or diffusing. All the Ag NPs show (111) crystal orientation. Besides, the Ag atoms are covered by graphene immediately when they precipitate from the substrate, which can prevent them from being oxidized. On the basis of this structure, as one of the applications of the metal SPR, we have measured the surface-enhanced Raman scattering effect and found that the G peak of the Raman spectrum of the graphene achieved about 20 times enhancement.

Transfer-free, lithography-free and fast growth of patterned CVD graphene directly on insulators by using sacrificial metal catalyst.

Chemical vapor deposited graphene suffers from two problems: transfer from metal catalysts to insulators, and photoresist induced degradation during patterning. Both result in macroscopic and microscopic damages such as holes, tears, doping, and contamination, translated into property and yield dropping. We attempt to solve the problems simultaneously. A nickel thin film is evaporated on SiO2 as a sacrificial catalyst, on which surface graphene is grown. A polymer (PMMA) support is spin-coated on the graphene. During the Ni wet etching process, the etchant can permeate the polymer, making the etching efficient. The PMMA/graphene layer is fixed on the substrate by controlling the surface morphology of Ni film during the graphene growth. After etching, the graphene naturally adheres to the insulating substrate. By using this method, transfer-free, lithography-free and fast growth of graphene realized. The whole experiment has good repeatability and controllability. Compared with graphene transfer between substrates, here, no mechanical manipulation is required, leading to minimal damage. Due to the presence of Ni, the graphene quality is intrinsically better than catalyst-free growth. The Ni thickness and growth temperature are controlled to limit the number of layers of graphene. The technology can be extended to grow other two-dimensional materials with other catalysts.