Electrochemically Exfoliated High-Quality 2H-MoS2 for Multiflake Thin Film Flexible Biosensors.

2D molybdenum disulfide (MoS2 ) gives a new inspiration for the field of nanoelectronics, photovoltaics, and sensorics. However, the most common processing technology, e.g., liquid-phase based scalable exfoliation used for device fabrication, leads to the number of shortcomings that impede their large area production and integration. Major challenges are associated with the small size and low concentration of MoS2 flakes, as well as insufficient control over their physical properties, e.g., internal heterogeneity of the metallic and semiconducting phases. Here it is demonstrated that large semiconducting MoS2 sheets (with dimensions up to 50 µm) can be obtained by a facile cathodic exfoliation approach in nonaqueous electrolyte. The synthetic process avoids surface oxidation thus preserving the MoS2 sheets with intact crystalline structure. It is further demonstrated at the proof-of-concept level, a solution-processed large area (60 × 60 µm) flexible Ebola biosensor, based on a MoS2 thin film (6 µm thickness) fabricated via restacking of the multiple flakes on the polyimide substrate. The experimental results reveal a low detection limit (in femtomolar-picomolar range) of the fabricated sensor devices. The presented exfoliation method opens up new opportunities for fabrication of large arrays of multifunctional biomedical devices based on novel 2D materials.

[1]  Yang Li,et al.  Coral‐Like MoS2/Cu2O Porous Nanohybrid with Dual‐Electrocatalyst Performances , 2016 .

[2]  Haitao Liu,et al.  Understanding the Intrinsic Water Wettability of Molybdenum Disulfide (MoS2). , 2015, Langmuir : the ACS journal of surfaces and colloids.

[3]  S. Prasad,et al.  Ultrasensitive and low-volume point-of-care diagnostics on flexible strips – a study with cardiac troponin biomarkers , 2016, Scientific Reports.

[4]  Shalini Prasad,et al.  Portable biosensor for monitoring cortisol in low-volume perspired human sweat , 2017, Scientific Reports.

[5]  R. Prins,et al.  Electron diffraction study of intercalation compounds derived from 1T-MoS2 , 1999 .

[6]  Daniil Karnaushenko,et al.  Light Weight and Flexible High‐Performance Diagnostic Platform , 2015, Advanced healthcare materials.

[7]  Gerhard Tröster,et al.  Fabrication and transfer of flexible few-layers MoS2 thin film transistors to any arbitrary substrate. , 2013, ACS nano.

[8]  Ronald Tetzlaff,et al.  Ultrasensitive detection of Ebola matrix protein in a memristor mode , 2018, Nano Research.

[9]  Hua Zhang,et al.  Single-layer MoS2 phototransistors. , 2012, ACS nano.

[10]  Hua Zhang,et al.  Solution-Processed Two-Dimensional MoS2 Nanosheets: Preparation, Hybridization, and Applications. , 2016, Angewandte Chemie.

[11]  J. Coleman,et al.  Liquid Exfoliation of Layered Materials , 2013, Science.

[12]  T. Mikolajick,et al.  Compact Nanowire Sensors Probe Microdroplets. , 2016, Nano letters.

[13]  S. Morrison,et al.  Thin oriented films of molybdenum disulphide , 1990 .

[14]  Na Liu,et al.  Large-area atomically thin MoS2 nanosheets prepared using electrochemical exfoliation. , 2014, ACS nano.

[15]  Mustafa Lotya,et al.  Solvent Exfoliation of Transition Metal Dichalcogenides: Dispersability of Exfoliated Nanosheets Varies Only Weakly between Compounds /v Sol (mol/ml) Characterisation of Dispersions , 2022 .

[16]  Zhiqiang Su,et al.  Synthesis and sensor applications of MoS2-based nanocomposites. , 2015, Nanoscale.

[17]  H. Erickson Size and Shape of Protein Molecules at the Nanometer Level Determined by Sedimentation, Gel Filtration, and Electron Microscopy , 2009, Biological Procedures Online.

[18]  John A Rogers,et al.  Erratum: Capacitively coupled arrays of multiplexed flexible silicon transistors for long-term cardiac electrophysiology , 2017, Nature Biomedical Engineering.

[19]  Heekyeong Park,et al.  Real-time electrical detection of epidermal skin MoS2 biosensor for point-of-care diagnostics , 2017, Nano Research.

[20]  O. Schmidt,et al.  MoS2 nanosheets decorated with gold nanoparticles for rechargeable Li–O2 batteries , 2015 .

[21]  G. Cuniberti,et al.  Negative Photoconductance in Heavily Doped Si Nanowire Field-Effect Transistors. , 2017, Nano letters.

[22]  Stefan Meister,et al.  Ultrathin topological insulator Bi2Se3 nanoribbons exfoliated by atomic force microscopy. , 2010, Nano letters.

[23]  Benjamin C. K. Tee,et al.  Flexible polymer transistors with high pressure sensitivity for application in electronic skin and health monitoring , 2013, Nature Communications.

[24]  M. Durrieu,et al.  RGD peptides grafting onto poly(ethylene terephthalate) with well controlled densities. , 2007, Biomolecular engineering.

[25]  Hao Wu,et al.  Few-layer molybdenum disulfide transistors and circuits for high-speed flexible electronics , 2014, Nature Communications.

[26]  Quan-hong Yang,et al.  Graphene-DNA hybrids: self-assembly and electrochemical detection performance , 2010 .

[27]  Yee-Hsien Ho,et al.  Directly deposited MoS2 thin film electrodes for high performance supercapacitors , 2015 .

[28]  Giuseppe Iannaccone,et al.  Electronics based on two-dimensional materials. , 2014, Nature nanotechnology.

[29]  A. Ferrari,et al.  High Responsivity, Large-Area Graphene/MoS2 Flexible Photodetectors , 2015, ACS nano.

[30]  Xiaoyun He,et al.  Liquid Phase Exfoliated MoS2 Nanosheets Percolated with Carbon Nanotubes for High Volumetric/Areal Capacity Sodium-Ion Batteries. , 2016, ACS nano.

[31]  Haixin Chang,et al.  Graphene and graphene-like two-dimensional materials in photodetection: mechanisms and methodology. , 2014, ACS nano.

[32]  Zhiyuan Zeng,et al.  Single-layer semiconducting nanosheets: high-yield preparation and device fabrication. , 2011, Angewandte Chemie.

[33]  Tri-Rung Yew,et al.  Flexible direct-growth CNT biosensors. , 2013, Biosensors & bioelectronics.

[34]  Andras Kis,et al.  Ultrasensitive photodetectors based on monolayer MoS2. , 2013, Nature nanotechnology.

[35]  V. G. Makotchenko,et al.  Chemically modified graphene sheets by functionalization of highly exfoliated graphite , 2011 .

[36]  A. Radenović,et al.  Single-layer MoS2 transistors. , 2011, Nature nanotechnology.

[37]  Kangho Lee,et al.  High‐Performance Sensors Based on Molybdenum Disulfide Thin Films , 2013, Advanced materials.

[38]  Nae-Eung Lee,et al.  Field-effect transistor with a chemically synthesized MoS2 sensing channel for label-free and highly sensitive electrical detection of DNA hybridization , 2015, Nano Research.

[39]  M. Pumera,et al.  Exfoliation of Layered Topological Insulators Bi2Se3 and Bi2Te3 via Electrochemistry. , 2016, ACS nano.

[40]  W. Sirisaksoontorn,et al.  Preparation and characterization of a tetrabutylammonium graphite intercalation compound. , 2011, Journal of the American Chemical Society.

[41]  Taesung Kim,et al.  Low‐Temperature Synthesis of Large‐Scale Molybdenum Disulfide Thin Films Directly on a Plastic Substrate Using Plasma‐Enhanced Chemical Vapor Deposition , 2015, Advanced materials.

[42]  D. Neumaier,et al.  Flexible Hall sensors based on graphene. , 2016, Nanoscale.

[43]  Ajeet Kaushik,et al.  Towards detection and diagnosis of Ebola virus disease at point-of-care , 2015, Biosensors and Bioelectronics.

[44]  Qing Hua Wang,et al.  Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. , 2012, Nature nanotechnology.

[45]  J. Coleman,et al.  Preparation of High Concentration Dispersions of Exfoliated MoS2 with Increased Flake Size , 2012 .

[46]  D. Williams,et al.  Kinetic analysis of antibody-antigen interactions at a supported lipid monolayer. , 1999, Analytical biochemistry.

[47]  Martin Pumera,et al.  Covalent functionalization of MoS2 , 2016 .

[48]  Lufeng Che,et al.  A novel fabrication process of MEMS devices on polyimide flexible substrates , 2008 .

[49]  K. Banerjee,et al.  MoS₂ field-effect transistor for next-generation label-free biosensors. , 2014, ACS nano.

[50]  A. Haes,et al.  Anionic functionalized gold nanoparticle continuous full filling separations: importance of sample concentration. , 2012, Analytical chemistry.

[51]  I. Kinloch,et al.  On the controlled electrochemical preparation of R4N+ graphite intercalation compounds and their host structural deformation effects , 2014 .

[52]  Heung Cho Ko,et al.  Highly flexible and transparent multilayer MoS2 transistors with graphene electrodes. , 2013, Small.

[53]  J. D. de Visser,et al.  Nanowire sensors monitor bacterial growth kinetics and response to antibiotics. , 2017, Lab on a chip.

[54]  Joonhyung Lee,et al.  Two-dimensional Layered MoS2 Biosensors Enable Highly Sensitive Detection of Biomolecules , 2014, Scientific Reports.

[55]  Chong-Yun Park,et al.  Fabrication of flexible optoelectronic devices based on MoS2/graphene hybrid patterns by a soft lithographic patterning method , 2017 .

[56]  Y. Jeong,et al.  Nanowire Field Effect Transistors: Principles and Applications , 2014 .

[57]  Xu Cui,et al.  Flexible and transparent MoS2 field-effect transistors on hexagonal boron nitride-graphene heterostructures. , 2013, ACS nano.

[58]  D. Peters,et al.  Electrochemical reduction of tetraalkylammonium tetrafluoroborates at carbon cathodes in dimethylformamide , 1996 .

[59]  J. Coleman,et al.  Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials , 2011, Science.