Ultraclean Surface Research Articles

Cyclododecane-based high-intactness and clean transfer method for fabricating suspended two-dimensional materials

The high-intactness and ultraclean fabrication of suspended 2D materials has always been a challenge due to their atomically thin nature. Here, we present a universal polymer-free transfer approach for fabricating suspended 2D materials by using volatile micro-molecule cyclododecane as the transfer medium, thus ensuring the ultraclean and intact surface of suspended 2D materials. For the fabricated monolayer suspended graphene, the intactness reaches 99% for size below 10 µm and suspended size reaches 36 µm. Owing to the advantages of ultra-cleanness and large size, the thermal conductivity reaches 4914 Wm−1K−1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm{W}}\\,{{\\rm{m}}}^{-1}{{\\rm{K}}}^{-1}$$\\end{document} at 338 K. Moreover, this strategy can also realize efficient batch transfer of suspended graphene and is applicable for fabricating other 2D suspended materials such as MoS2. Our research not only establishes foundation for potential applications and investigations of intrinsic properties of large-area suspended 2D materials, but also accelerates the wide applications of suspended graphene grid in ultrahigh-resolution TEM characterization.

Tunable Adhesion for All-Dry Transfer of 2D Materials Enabled by the Freezing of Transfer Medium.

The real applications of chemical vapor deposition (CVD)-grown graphene films require the reliable techniques for transferring graphene from growth substrates onto application-specific substrates. The transfer approaches that avoid the use of organic solvents, etchants, and strong bases are compatible with industrial batch processing, in which graphene transfer should be conducted by dry exfoliation and lamination. However, all-dry transfer of graphene remains unachievable owing to the difficulty in precisely controlling interfacial adhesion to enable the crack- and contamination-free transfer. Herein, through controllable crosslinking of transfer medium polymer, the adhesion is successfully tuned between the polymer and graphene for all-dry transfer of graphene wafers. Stronger adhesion enables crack-free peeling of the graphene from growth substrates, while reduced adhesion facilitates the exfoliation of polymer from graphene surface leaving an ultraclean surface. This work provides an industrially compatible approach for transferring 2D materials, key for their future applications, and offers a route for tuning the interfacial adhesion that would allow for the transfer-enabled fabrication of van der Waals heterostructures.

Ultraclean surface restoration and giant photoresponse enhancement of violet phosphorus

Violet phosphorus (VP), a recently developed kind of layered material, features exotic in-plane anisotropy, alluring thickness-dependent bandgap, and better thermal stability than its phosphorus allotropes. Such a broad variety of functionalities indicates VP is a promising candidate for advanced nanophotonics. However, its hydrophilic surface-induced air instability hinders further exploration and extensive device integration for photodetection and beyond. Herein, we report the successful restoration of the clean VP surfaces through nitrogen plasma combined with vacuum thermal annealing. Via manipulation of plasma excitation power, we can also achieve thickness etching and nondestructive p-doping to VP, paving the way for fabrication and engineering of VP photodetectors. As a proof-of-concept, plasma-treated VP photodetectors have been fabricated. Stemming from the plasma treatment-induced p-doping and hole trapping centers, the VP photodetectors exhibit giant photoresponse enhancement, reaching a high responsivity of 1.923 A/W, and is dramatically improved by 1300% compared with that before plasma treatments, which envisions high-sensitivity photodetection for next-generation more-than-Moore optoelectronics.

Atomic Level Chemical and Structural Properties of Silicon Surface and Initial Stages of Oxidation

This work aims to summarize previous results reported in literature on atomic level properties of the wet chemically treated hydrogen-terminated silicon surfaces and of the Si oxidation, in comparison to a model system of ultraclean Si surfaces prepared in ultrahigh vacuum (UHV) conditions. A literature review shows that a proper wet chemical treatment of Si(111) provides an atomically smooth, high-quality surface, similar to the model template obtained in UHV conditions after high temperature heating. However, it seems that Si(111) is an exception among semiconductor surfaces concerning the effects of wet chemistry. Although the insulator films grown by the atomic layer deposition (ALD) have replaced the thermal oxide of SiO2 in many applications, still an intermediate SiO2 layer is formed and often grown intentionally beneath the ALD film to improve the device performance. However, a detailed atomic structure of the SiO2/Si interface is still debatable, which might be due to differences in atomic level smoothness of the used Si(100) starting surfaces.

In situ polymerized ionic liquids in polyester fiber composite membranes for detection of trace oil

In situ trace detection on ultra-clean surfaces is an important technology. The polyester fiber (PF) was introduced to serve as the template, to which the ionic liquids were bonded by hydrogen bonding. Polymerized ionic liquids (PIL) in PF were formed by in situ polymerization with the azodiisobutyronitrile (AIBN) and IL. The trace oil on metal surfaces was enriched by the composite membrane based on similar compatibility principle. The absolute recovery of the trace oil ranged from 91%-99% using this composite membrane. In the extraction samples, desirable linear correlations were obtained for trace oil in the range of 1.25-20mg/mL. It has been proven that a 1cm2 PIL-PF composite membrane can effectively extract as little as 1mg of lubricating oil on an ultra-clean metal surface of 0.1m2 with the LOD of 0.9mg/mL, making it a promising material for in situ detection of trace oil on metal surfaces.

Hydrodynamic Investigation of Ultraclean Wafer Drying Combining Marangoni Effect and Centrifugal Force

The Marangoni effect induced by organic vapor has drawn considerable attention in integrated circuit manufacturing for eliminating watermark defects encountered in the wafer drying process. Accordingly, a vertical rotational Marangoni (VRM) dryer based on the combination of the Marangoni effect and centrifugal force is proposed and developed. In particular, the hydrodynamic behavior of the VRM dryer is investigated to reveal the mechanism of ultraclean drying. A three-dimensional model of the VRM dryer is proposed, and the flow field of the water film and distribution of organic species are adequately analyzed. The results show that the rotational velocity and wettability significantly affect the coverage uniformity of the water film, and the exposure region at the three-contact line leads to the watermark. Furthermore, the coupling behavior of the Marangoni effect and centrifugal force is revealed. A higher rotational velocity leads to worse integrity of the water film covering, and thus, fainter Marangoni effect. Polishing and cleaning experiments are conducted to verify the effectiveness of theoretical analysis. The results indicate that the optimized rotational velocity for the hydrophilic surface is higher than that of the hydrophobic surface. The mechanism analysis of wafer drying based on the VRM drying technology provides effective guidance for ultraclean surface manufacturing during the cleaning process.

Controlled Adhesion of Ice-Toward Ultraclean 2D Materials.

The scalable 2Ddevice fabrication and integration demand either the large-area synthesis or the post-synthesis transfer of 2D layers. While the direct synthesis of 2D materials on most targeted surfaces remains challenging, the transfer approach from the growth substrate onto the targeted surfaces offers an alternative pathway for applications and integrations. However, the current transfer techniques for 2D materials predominantly involve polymers and organic solvents, which are liable to contaminate or deform the ultrasensitive atomic layers. Here, novel ice-aided transfer and ice-stamp transfer methods are developed, in which water (ice) is the only medium in the entire process. In practice, the adhesion between various 2D materials and ice can be well controlled by temperature. Through such controlled adhesion of ice, it is shown that the new transfer methods can yield ultrahigh quality and exceptional cleanliness in transferred 2D flakes and continuous 2D films, and are applicable for a wide range of substrates. Furthermore, beyond transfer, ice can also be used for cleaning the surfaces of 2D materials at higher temperatures. These novel techniques can enable unprecedented ultraclean 2D materials surfaces and performances, and will contribute to the upcoming technological revolutions associated with 2D materials.

Ultraclean and Facile Patterning of CVD Graphene by a UV-Light-Assisted Dry Transfer Method

The synthesis of large-area graphene by the chemical vapor deposition (CVD) method is a mature technology; however, a transfer procedure is required to integrate CVD-grown graphene into a functional device. The reported methods for transferring graphene films cause different degrees of defects (cracking, rupture) and ion/polymer residues, which deteriorate or alter the electrical properties of as-grown graphene. Developing a reliable and fast transfer method that can maintain high-quality graphene remains a challenge. In this work, we employed UV light release tape (UV-RT) as the support layer to replace the frequently used thermal release tape (TRT) in a typical roll-to-roll dry transfer process. In this process, we used an easier-to-remove polymer as an adhesion layer to greatly reduce the strain and defects that occur during the transfer process. The cleanliness of graphene transferred by this method is above 99%, and the carrier mobility is 1.6 and 1.1 times higher than that obtained with conventional wet transfer and TRT transfer methods, respectively. UV illumination leads to facile and uniform release of the graphene film onto the target substrate, achieving one-step and selective patterning of graphene (feature size of <100 μm). The UV-assisted decomposition of the polymer molecular structure into small molecules enables a residue-free and ultraclean graphene surface. This proposed transfer method enables facile patterning of graphene and 2D films while maintaining high quality, which paves the way for versatile functional graphene applications.

Mechanism Analysis of Megasonic and Brush Cleaning Processes for Silicon Substrate after Chemical Mechanical Polishing

Cleaning processes draw considerable attention in integrated circuit manufacturing because of the rapid development of technology nodes. Bare silicon wafer cleaning after chemical mechanical polishing (CMP) is one of the most difficult processes used to meet the extremely strict industrial requirements. Herein, the silicon wafer cleaning mechanism is studied in detail. The effects of megasonic and brush cleaning on nanoparticle removal are both analysed through experiments and simulations. The experimental results show that chemical concentration, megasonic vibration power, and brush clamp gap all significantly affect the cleaning performance, and that excessive megasonic power reduces the cleaning performance because more defects are introduced. A model of megasonic nozzle trajectory is also proposed, and optimized parameters, especially the relative velocity between the wafer rotation and nozzle movement, are critical to removing nanoparticles effectively. Furthermore, analysis of combining megasonic and brush cleaning shows that including megasonic cleaning improves the wafer cleaning performance by several orders of magnitude. Based on the optimized cleaning conditions, an ultraclean wafer surface is achieved after CMP.

Large-area transfer of two-dimensional materials free of cracks, contamination and wrinkles via controllable conformal contact

The availability of graphene and other two-dimensional (2D) materials on a wide range of substrates forms the basis for large-area applications, such as graphene integration with silicon-based technologies, which requires graphene on silicon with outperforming carrier mobilities. However, 2D materials were only produced on limited archetypal substrates by chemical vapor deposition approaches. Reliable after-growth transfer techniques, that do not produce cracks, contamination, and wrinkles, are critical for layering 2D materials onto arbitrary substrates. Here we show that, by incorporating oxhydryl groups-containing volatile molecules, the supporting films can be deformed under heat to achieve a controllable conformal contact, enabling the large-area transfer of 2D films without cracks, contamination, and wrinkles. The resulting conformity with enhanced adhesion facilitates the direct delamination of supporting films from graphene, providing ultraclean surfaces and carrier mobilities up to 1,420,000 cm2 V−1 s−1 at 4 K.

Emergent Multifunctional Magnetic Proximity in van der Waals Layered Heterostructures.

Proximity effect, which is the coupling between distinct order parameters across interfaces of heterostructures, has attracted immense interest owing to the customizable multifunctionalities of diverse 3D materials. This facilitates various physical phenomena, such as spin order, charge transfer, spin torque, spin density wave, spin current, skyrmions, and Majorana fermions. These exotic physics play important roles for future spintronic applications. Nevertheless, several fundamental challenges remain for effective applications: unavoidable disorder and lattice mismatch limits in the growth process, short characteristic length of proximity, magnetic fluctuation in ultrathin films, and relatively weak spin–orbit coupling (SOC). Meanwhile, the extensive library of atomically thin, 2D van der Waals (vdW) layered materials, with unique characteristics such as strong SOC, magnetic anisotropy, and ultraclean surfaces, offers many opportunities to tailor versatile and more effective functionalities through proximity effects. Here, this paper focuses on magnetic proximity, i.e., proximitized magnetism and reviews the engineering of magnetism‐related functionalities in 2D vdW layered heterostructures for next‐generation electronic and spintronic devices. The essential factors of magnetism and interfacial engineering induced by magnetic layers are studied. The current limitations and future challenges associated with magnetic proximity‐related physics phenomena in 2D heterostructures are further discussed.

Single electrons on solid neon as a solid-state qubit platform.

Progress towards the realization of quantum computers requires persistent advances in their constituent building blocks-qubits. Novel qubit platforms that simultaneously embody long coherence, fast operation and large scalability offer compelling advantages in the construction of quantum computers and many other quantum information systems1-3. Electrons, ubiquitous elementary particles of non-zero charge, spin and mass, have commonly been perceived as paradigmatic local quantum information carriers. Despite superior controllability and configurability, their practical performance as qubits through either motional or spin states depends critically on their material environment3-5. Here we report our experimental realization of a qubit platform based on isolated single electrons trapped on an ultraclean solid neon surface in vacuum6-13. By integrating an electron trap in a circuit quantum electrodynamics architecture14-20, we achieve strong coupling between the motional states of a single electron and a single microwave photon in an on-chip superconducting resonator. Qubit gate operations and dispersive readout are implemented to measure the energy relaxation time T1 of 15 μs and phase coherence time T2 over 200 ns. These results indicate that the electron-on-solid-neon qubit already performs near the state of the art for a charge qubit21.

Revealing the Phase Segregation and Evolution Dynamics in Binary Nanoalloys via Electron Beam-Assisted Ultrafast Heating and Cooling.

Gas-phase synthesized binary nanoparticles (NPs) possess ultraclean surfaces, which benefit versatile uses in sensors and catalysts. However, precise control of their configuration and properties is still a big challenge because the growth mechanism and phase evolution dynamics in these NPs are very hard to unveil. Here, we report a strategy to investigate the phase evolution dynamics in binary NPs by using e-beam assisted ultrafast local heating and cooling inside a transmission electron microscope. With this strategy, the phase segregation and corresponding shape evolution of PbBi NPs are in situ revealed. It is found that the as-prepared PbBi alloy NPs will transform into heterostructures under e-beam stimulated structural relaxation, leading to the formation of featured Janus configurations with faceted Bi polyhedron parts and intermetallic hemisphere parts. During phase segregation, Pb1Bi1 and Pb7Bi3 phases are captured and identified, and a model of phase and shape evolution of PbBi nanoalloys is developed and contrasted with that of their bulk counterparts. These findings benefit the understanding of the phase dynamics of binary NPs and can provide in-depth information for engineering their structures for practical applications.

Instant Preparation of Ultraclean Gold Nanothorns under Ambient Conditions for SERS Kit-Enabled Mobile Diagnosis.

Availability of surface-enhanced Raman scattering (SERS) substrates with good stability, high sensitivity, and a clean surface is crucial for the practical usefulness of the SERS technology in biochemical sensing, especially for point-of-care testing (POCT). Hereby, we develop a "ready-to-use" SERS kit, which requires only 20 s to fabricate ultraclean gold nanothorn (AuNT)-based SERS chips under ambient conditions with simple solution processing steps. By varying the thickness of the pre-coated platinum (Pt) nanolayer, we can control the size and number density of the grown AuNT. Taking advantage of the ultraclean surface of the instantly obtained fresh AuNT, Raman reporter molecules can also be immediately modified, by means of which specific detection of three analytes including H2O2, NO2-, and ClO- is realized. Furthermore, we propose the concept of an SERS kit and apply it to smartphone-based Raman analysis for POCT applications. This on-site preparation method solves the long-standing challenges hindering the practical use of SERS substrates, such as complicated fabrication processes, interference of residual surfactants, poor surface stability, and easy contamination. Besides performing SERS analysis conveniently and quickly, this SERS kit-enabled POCT technology can integrate remote data terminals and medical resources, which shows great potential for environmental protection or online-healthcare systems.

Strong localization in suspended monolayer graphene by intervalley scattering

A gate induced insulating behavior at zero magnetic field is observed in a high mobility suspended monolayer graphene near the charge neutrality point. The graphene device initially cleaned by a current annealing technique was undergone a thermo-pressure cycle to allow short range impurities to be adsorbed directly on the ultra clean graphene surface. The adsorption process generated a strong temperature and electric field dependent behavior on the conductance of the graphene device. The conductance around the neutrality point is observed to be reduced from around $e^2/h$ at 30 K to $\sim0.01~e^2/h$ at 20 mK. A direct transition from insulator to quantum Hall conductor within $\approx0.4~T$ accompanied by broken-symmetry-induced $\nu=0,\pm1$ plateaux confirms the presence of intervalley scatterers.

A low noise cryogen-free scanning tunneling microscope-superconducting magnet system with vacuum sample transfer.

Imaging atomically resolved surfaces and performing spectroscopy of exotic surfaces at cryogenic temperature in the presence of the magnetic field is an engineering challenge. Additionally, performing these measurements in an all-cryogen-free environment compounds the above complexity due to the associated vibration and acoustic noise generated by the running of cryogenic cold heads. We here report successful integration of a cryogen-free scanning tunneling microscope (STM) with a cryogen-free superconducting vector-magnet, connected to an ultra-high vacuum cluster assembly for in situ sample transfer. We present details of the integration involving vibration and electrical noise isolation procedures allowing for operation of the STM at extremely low noise levels below 30 fA/Hz during normal operations of the complete vacuum-line assembly with multiple turbomolecular pumps. We demonstrate the above STM capability at cryogenic temperature and in the presence of the magnetic field through atomic resolution imaging of graphite and thin films of gold on the mica substrate transferred in situ to the STM chamber. We also demonstrate spectroscopy signatures of the superconducting gap in MgB2 thin films. The design of our in-house customized cluster-vacuum-line assembly provides unsought opportunities in continuous uninterrupted imaging of ultra-clean in-vacuum grown surfaces without the need for cryogenic refills in either the STM or the magnet.

Ultraclean Graphene Transfer Using a Sacrificial Fluoropolymer Nanolayer: Implications for Sensor and Electronic Applications

The transfer of chemical vapor deposited (CVD) monolayer graphene by using poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole-co-tetrafluoroethylene] (Teflon AF1600) fluoropolymer (FP) as a sacrificial nanolayer is demonstrated. Owing to the chemical inertness of FPs, the AF1600-assisted transfer produces an ultraclean surface with excellent transfer integrity. Compared with the widely used poly(methyl methacrylate)-assisted transfer, AF1600-assisted transfer produces better overall transfer quality as measured by root-mean-square (RMS) roughness. Adding a noncovalent surface monolayer between the graphene and the FP facilitates the FP removal after graphene transfer, resulting in a surface with RMS roughness of 0.4–0.5 nm due to a better reduction of the surface residue after transfer. The remaining residue is found to be primarily associated with thermal-expansion ripples in the graphene that act as trapping sites for the low-molecular-weight FP particles. This work provides a scalable solution to clean CVD graphene transfer for many applications, particularly in sensors where surface cleanliness is paramount. The use of prefunctionalized graphene via self-assembled monolayers as molecular scale passivation layer could further enhance its utility as an integration scheme for graphene sensors.

Flexible Organic Solar Cells Over 15% Efficiency with Polyimide-Integrated Graphene Electrodes

Summary The performance of organic solar cells (OSCs) has been steadily increasing, surpassing 16% power conversion efficiency (PCE) with advances in photoactive and charge transport materials. Nonetheless, the performance of flexible OSCs still falls behind that of their rigid counterparts. Furthermore, commonly used plastic substrates are vulnerable to high-temperature annealing processes. Herein, a highly flexible and durable electrode with thermal stability achieved through direct integration of polyimide (PI) on graphene is introduced. The PI-assisted graphene electrode exhibits an ultra-clean surface together with an optical transmittance exceeding 92%, a sheet resistance of 83 Ω/sq, and thermal stability. Moreover, direct integration of PI improved the durability of the graphene electrode by inhibiting delamination of the graphene under mechanical stress. Using the PI-assisted graphene electrode, flexible OSC with a PCE of 15.2% was obtained with outstanding mechanical robustness. The proposed electrode is promising for use in various optoelectronic devices requiring high efficiency and flexibility.

Mechanism Analysis of Nanoparticle Removal Induced by the Marangoni-driven Flow in Post-CMP Cleaning

Wafer drying induced by Marangoni effect is crucial to achieving an ultraclean surface in integrated circuit manufacturing. According to the previous opinions, the entrained water film on wafer surface was stripped by Marangoni effect, and thus the watermark defect induced by evaporation was inhibited. However, the influence of particle removal induced by Marangoni effect on the ultraclean surface preparation is lack of adequate understanding. The present work implements an experimental and numerical investigation of wafer cleaning behavior engendered by Marangoni effect during the wafer withdrawn process. The impacts of critical process parameters and substrate properties on the particle removal efficiency are systematically studied. The results show that Marangoni effect has better cleaning performance on the glass substrate compared with that of silicon and copper. The numerical simulation indicates that the Marangoni effect is more dramatic on glass substrate owing to the better wettability. Furthermore, the stress analysis reveals the adsorption force of fluorescent particle on the copper surface is stronger than that of silicon and glass. Therefore, particle cleaning on the copper surface is much more difficult. The investigation of cleaning performance driven by the Marangoni effect will contribute to a comprehensive understanding of the mechanism of ultraclean surface preparation.

A novel method for in situ visualization of the growth kinetics, structures and behaviours of gas-phase fabricated metallic alloy nanoparticles.

Modulation of gas-phase nanoparticles is unmethodical as there is a lack of information on the growth kinetics and its determinants. Here, we developed a novel in situ evaporation-and-deposition (EAD) method inside a transmission electron microscope which enables direct visualization of the nucleation, growth, coalescence and shape/phase evolution of gas-phase fabricated nanoparticles. Using a Bi49Pb18Sn12In21 alloy as a sample, the critical factors that determine the feasibility of this EAD method are revealed. By direct observation, it is unambiguously evidenced that pristine nanoparticles with ultra-clean surfaces are extremely energetic during growth. Coalescence between EAD-fabricated nanoparticles takes place in a manner beyond conventional understanding acquired by postmortem analyses. Moreover, the EAD-fabricated diverse nanoparticles show distinct size distributions and sandwich-type or Janus-type phase segregations. These features offer an effective tool to identify atomic surface steps of thin films and can provide an ideal case for exploring the phase diagrams of nanoalloys in the future.