An electroconductive ink containing the reduced graphene oxide‒metal oxide‒carbon nanotube semiconductor applied to flexible electronic circuits

Abstract

We present an interesting low-cost, green, and scalable technique for direct ink writing for flexible electronic applications different from traditional fabrication techniques. In this work, a reduced graphene oxide (RGO)‒bismuth oxide (Bi₂O₃)/carbon nanotube (CNT) (RGBC) ternary conductive ink was prepared by an initial synthesis of RGO‒Bi₂O₃ (RGB) via a hydrothermal method. This was followed by the fabrication of conductive ink through homogenous mixing of the binary nanocomposite with CNTs in a mixture of ethanol, ethylene glycol, glycerol, and double-distilled water as the solvent. Electronic circuits were fabricated through directly writing the prepared ink on flexible nanocrystalline cellulose (NCC) thin film substrates. The nanocomposites consisted of rod-shaped nanoparticles that were grown on the surface of the nanographene sheet. The semiconductor nanocomposite exhibited excellent conductivity and further confirmed by applying it as an electrode in the electrical circuit to light a light-emitting diode (LED) bulb. The highest electrical conductivity achieved was 2.84 × 10³ S·m⁻¹ with a contact angle of 37°. The electronic circuit written using the conductive ink exhibited good homogeneity, uniformity, and adhesion. The LED experiment demonstrates the good conductivity of the electroconductive circuit and prepared ink. Hence, the NCC substrate and RGBC conductive ink showcase an excellent potential for flexible electronic applications.

Graphical abstract

Keywords

reduced graphene oxide / nanocrystalline cellulose / electroconductive ink / flexible electronic circuit / hydrothermal synthesis

References

[1] Xu L Q, Wei N, Zheng Y P . Mechanical properties of highly defective graphene: from brittle rupture to ductile fracture.Nanotechnology, 2013, 24(50): 505703

[2] Tai Y L, Yang Z G J . Fabrication of paper-based conductive patterns for flexible electronics by direct-writing.Journal of Materials Chemistry, 2011, 21(16): 5938–5943

[3] Russo A, Ahn B Y, Adams J J, . Pen-on-paper flexible electronics.Advanced Materials, 2011, 23(30): 3426–3430

[4] Hu L, Pasta M, Mantia F L, . Stretchable, porous, and conductive energy textiles.Nano Letters, 2010, 10(2): 708–714

[5] Jeong S, Song H C, Lee W W, . Stable aqueous-based Cu nanoparticle ink for printing well-defined highly conductive features on a plastic substrate.Langmuir, 2011, 27(6): 3144–3149

[6] Yang C, Gu H, Lin W, . Silver nanowires: from scalable synthesis to recyclable foldable electronics.Advanced Materials, 2011, 23(27): 3052–3056

[7] Siegel A C, Phillips S T, Dickey M D, . Foldable printed circuit boards on paper substrates.Advanced Functional Materials, 2010, 20(1): 28–35

[8] Lee J Y, Connor S T, Cui Y, . Solution-processed metal nanowire mesh transparent electrodes.Nano Letters, 2008, 8(2): 689–692

[9] Ellmer K . Past achievements and future challenges in the development of optically transparent electrodes.Nature Photonics, 2012, 6: 809–817

[10] Layani M, Kamyshny A, Magdassi S . Transparent conductors composed of nanomaterials.Nanoscale, 2014, 6(11): 5581–5591

[11] Ye S, Rathmell A R, Chen Z, . Metal nanowire networks: the next generation of transparent conductors.Advanced Materials, 2014, 26(39): 6670–6687

[12] Novoselov K S, Fal′ko V I, Colombo L, . A roadmap for graphene.Nature, 2012, 490(7419): 192–200

[13] Allen M J, Tung V C, Kaner R B . Honeycomb carbon: a review of graphene.Chemical Reviews, 2010, 110(1): 132–145

[14] Georgakilas V, Perman J A, Tucek J, . Broad family of carbon nanoallotropes: classification, chemistry, and applications of fullerenes, carbon dots, nanotubes, graphene, nanodiamonds, and combined superstructures.Chemical Reviews, 2015, 115(11): 4744–4822

[15] Georgakilas V, Otyepka M, Bourlinos A B, . Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications.Chemical Reviews, 2012, 112(11): 6156–6214

[16] Kuilla T, Bhadra S, Yao D, . Recent advances in graphene based polymer composites.Progress in Polymer Science, 2010, 35(11): 1350–1375

[17] Potts J R, Dreyer D R, Bielawski C W, . Graphene-based polymer nanocomposites.Polymer, 2011, 52(1): 5–25

[18] Eigler S . Graphite sulphate — a precursor to graphene.Chemical Communications, 2015, 51(15): 3162–3165

[19] Gao H, Duan H . 2D and 3D graphene materials: preparation and bioelectrochemical applications.Biosensors & Bioelectronics, 2015, 65(55): 404–419

[20] Kamat P V . Graphene-based nanoassemblies for energy conversion.The Journal of Physical Chemistry Letters, 2011, 2(3): 242–251

[21] Roy-Mayhew J D, Aksay I A . Graphene materials and their use in dye-sensitized solar cells.Chemical Reviews, 2014, 114(12): 6323–6348

[22] Sahoo N G, Pan Y, Li L, . Graphene-based materials for energy conversion.Advanced Materials, 2012, 24(30): 4203–4210

[23] Huang X J, Leng T, Zhu M J, . Highly flexible and conductive printed graphene for wireless wearable communications applications.Scientific Reports, 2015, 5: 18298

[24] Secor E B, Hersam M C . Emerging carbon and post-carbon nanomaterial inks for printed electronics.The Journal of Physical Chemistry Letters, 2015, 6(4): 620–626

[25] Bae S, Kim H, Lee Y, . Roll-to-roll production of 30-inch graphene films for transparent electrodes.Nature Nanotechnoloby, 2010, 5: 574–578

[26] Aleeva Y, Pignataro B . Recent advances in upscalable wet methods and ink formulations for printed electronics.Journal of Materials Chemistry C: Materials for Optical, Magnetic and Electronic Devices, 2014, 2(32): 6436–6453

[27] Mates J E, Bayer I S, Salerno M, . Durable and flexible graphene composites based on artists’ paint for conductive paper applications.Carbon, 2015, 87(2): 163–174

[28] Nirmalraj P N, Lyons P E, De S, . Electrical connectivity in single-walled carbon nanotube networks.Nano Letters, 2009, 9(11): 3890–3895

[29] Wu C, Huang X, Wang G, . Highly conductive nanocomposites with three-dimensional, compactly interconnected graphene networks via a self-assembly process.Advanced Functional Materials, 2013, 23(4): 506–513

[30] Xia L, Li X, Wu X, . Fe₃O₄ nanoparticles embedded in cellulose nanofibre/graphite carbon hybrid aerogels as advanced negative electrodes for flexible asymmetric supercapacitor.Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2018, 6(36): 17378–17388

[31] Yu D S, Kuila T, Kim N H, . Enhanced properties of aryl diazonium salt-functionalized graphene/poly(vinyl alcohol) composites.Chemical Engineering Journal, 2014, 245(6): 311–322

[32] Bourlinos A B, Georgakilas V, Zboril R, . Liquid-phase exfoliation of graphite towards solubilized graphenes.Small, 2009, 5(16): 1841–1845

[33] Ciesielski A, Samorì P . Graphene via sonication assisted liquid-phase exfoliation.Chemical Society Reviews, 2014, 43(1): 381–398

[34] Torrisi F, Hasan T, Wu W, . Inkjet-printed graphene electronics.ACS Nano, 2012, 6(4): 2992–3006

[35] Finn D J, Lotya M, Cunningham G, . Inkjet deposition of liquid-exfoliated graphene and MoS₂ nanosheets for printed device applications.Journal of Materials Chemistry C: Materials with Applications in Optical, Magnetic & Electronic Devices, 2014, 2(5): 925–932

[36] Secor E B, Prabhumirashi P L, Puntambekar K, . Inkjet printing of high conductivity, flexible graphene patterns.The Journal of Physical Chemistry Letters, 2013, 4(8): 1347–1351

[37] Secor E B, Lim S, Zhang H, . Gravure printing of graphene for large-area flexible electronics.Advanced Materials, 2014, 26(26): 4533–4538

[38] Majee S, Song M, Zhang S L, . Scalable inkjet printing of shear-exfoliated graphene transparent conductive films.Carbon, 2016, 102(12): 51–57

[39] Eda G, Chhowalla M J . Chemically derived graphene oxide: towards large-area thin-film electronics and optoelectronics.Advanced Materials, 2010, 22(22): 2392–2415

[40] Luo Z, Lu Y, Somers L A, . High yield preparation of macroscopic graphene oxide membranes.Journal of the American Chemical Society, 2009, 131(3): 898–899

[41] Li W, Li F, Li H, . Flexible circuits and soft actuators by printing assembly of graphene.ACS Applied Materials & Interfaces, 2016, 8(19): 12369–12376

[42] Capasso A, Castillo A E D R, Sun H, . Ink-jet printing of graphene for flexible electronics: an environmentally-friendly approach.Solid State Communications, 2015, 224: 53–63

[43] Cummins G, Desmulliez M P . Inkjet printing of conductive materials: a review.Circuit World, 2012, 38(4): 193–213

[44] Giardi R, Porro S, Chiolerio A, . Inkjet printed acrylic formulations based on UV-reduced graphene oxide nanocomposites.Journal of Materials Science, 2013, 48(3): 1249–1255

[45] Snow E, Novak J, Campbell P, . Random networks of carbon nanotubes as an electronic material.Applied Physics Letters, 2003, 82(13): 2145–2147

[46] Kamyshny A, Steinke J, Magdassi S . Metal-based inkjet inks for printed electronics.The Open Applied Physics Journal, 2011, 4: 19–36

[47] Prakash S, Chakrabarty T, Singh A K, . Polymer thin films embedded with metal nanoparticles for electrochemical biosensors applications.Biosensors & Bioelectronics, 2013, 41(23): 43–53

[48] Pawar S G, Patil S L, Chougule M A, . Synthesis and characterization of polyaniline:TiO₂ nanocomposites.International Journal of Polymeric Materials and Polymeric Biomaterials, 2010, 59(10): 777–785

[49] Rao C P K , Vijayan M . Ruthenium(II)-mediated synthesis of conducting polyaniline (PAni): a novel route for PAni‒RuO₂ composite.Synthetic Metals, 2008, 158(12): 516–519

[50] Zidan M, Tan W T, Zainal Z, . Electrocatalytic oxidation of ascorbic acid mediated by lithium doped microparticles Bi₂O₃/MWCNT modified glassy carbon electrode.International Journal of Electrochemical Science, 2010, 5(4): 501–508

[51] Li L, Yan B . BiVO₄/Bi₂O₃ submicrometer sphere composite: microstructure and photocatalytic activity under visible-light irradiation.Journal of Alloys and Compounds, 2009, 476(1‒2): 624–628

[52] Jain R, Tiwari D C, Shrivastava S . Polyaniline‒bismuth oxide nanocomposite sensor for quantification of anti-parkinson drug pramipexole in solubilized system.Materials Science & Engineering B: Advanced Functional Solid-State Materials, 2014, 185(41): 53–59

[53] Takenobu T, Miura N, Lu S Y, . Ink-jet printing of carbon nanotube thin-film transistors on flexible plastic substrates.Applied Physics Express, 2009, 2(10): 025005–025010

[54] Ha M, Xia Y, Green A A, . Printed, sub-3V digital circuits on plastic from aqueous carbon nanotube inks.ACS Nano, 2010, 4(8): 4388–4395

[55] Singh V, Joung D, Zhai L, . Graphene-based materials: past, present, and future.Progress in Materials Science, 2011, 56(8): 1178–1271

[56] Avouris P, Chen Z, Perebeinos V, . Carbon-based electronics.Nanoscience and Technology, 2010, 2(7): 174–184

[57] Choi J K, Hwang I S, Kim S J, . Design of selective gas sensors using electrospun Pd-doped SnO₂ hollow nanofibers.Sensors and Actuators B: Chemical, 2010, 150(1): 191–199

[58] Li J, Ye F, Vaziri S, . Efficient inkjet printing of graphene.Advanced Materials, 2013, 25(29): 3985–3992

[59] Siegel A C, Tang S K, Nijhuis C A, . Cofabrication: a strategy for building multicomponent microsystems.Accounts of Chemical Research, 2010, 43(4): 518–528

[60] Chen X D, Chen L, Sun Q Q, . Hybrid density functional theory study of Cu(In_1−xGa_x)Se₂ band structure for solar cell application.AIP Advances, 2014, 4(8): 087118

[61] Krebs F C . Fabrication and processing of polymer solar cells: a review of printing and coating techniques.Solar Energy Materials and Solar Cells, 2009, 93(4): 394–412

[62] Wang J C, Weng W T, Tsai M Y, . Highly efficient flexible inverted organic solar cells using atomic layer deposited ZnO as electron selective layer.Journal of Materials Chemistry, 2010, 20(5): 862–866

[63] Zhou Y H, Khan T M, Liu J C, . Efficient recyclable organic solar cells on cellulose nanocrystal substrates with a conducting polymer top electrode deposited by film-transfer lamination.Organic Electronics, 2014, 15(3): 661–666

[64] Zhu W W, Wang S W, Lu Y, . High-toughness multifunctional conductive hydrogel fibers via microfluidic spinning for flexible strain sensor.Industrial Crops and Products, 2024, 222(Part 1): 119598

[65] Yang X, Biswas S K, Han J, . Surface and interface engineering for nanocellulosic advanced materials.Advanced Materials, 2021, 33(28): 2002264–2002287

[66] Lu Y, Sun H, Deng F, . Green fabrication of all-nanocellulose-based flexible electroluminescent devices with biodegradability, recyclability, and extreme environment tolerance.ACS Sustainable Chemistry & Engineering, 2024, 12(20): 7976–7986

[67] Cheng X, Wang H, Wang S, . Hierarchically core–shell structured nanocellulose/carbon nanotube hybrid aerogels for patternable, self-healing and flexible supercapacitors.Journal of Colloid and Interface Science, 2024, 660(5): 923–933

[68] Gu Y, Wang D, Gao Y, . Solar-powered high-performance lignin-wood evaporator for solar steam generation.Advanced Functional Materials, 2023, 33(43): 2306947

[69] Vartiainen J, Pöhler T, Sirola K, . Health and environmental safety aspects of friction grinding and spray drying of microfibrillated cellulose.Cellulose, 2011, 18(3): 775–786

[70] Lin N, Huang J, Dufresne A . Preparation, properties and applications of polysaccharide nanocrystals in advanced functional nanomaterials: a review.Nanoscale, 2012, 4(24): 3274–3294

[71] Habibi Y, Lucia L A, Rojas O J . Cellulose nanocrystals: chemistry, self-assembly, and applications.Chemical Reviews, 2010, 110(6): 3479–3500

[72] Klemm D, Kramer F, Moritz S, . Nanocelluloses: a new family of nature-based materials.Angewandte Chemie International Edition, 2011, 50(11): 5438–5466

[73] Siró I, Plackett D . Microfibrillated cellulose and new nanocomposite materials: a review.Cellulose, 2010, 17(3): 459–494

[74] Thomas B, Raj M C, Athira K B, . Nanocellulose, a versatile green platform: from biosources to materials and their applications.Chemical Reviews, 2018, 118(24): 11575–11625

[75] Pammo A, Christophliemk H, Keskinen J. Nanocellulose films as substrates for printed electronics. 2019 International Conference on Manipulation, Automation and Robotics at Small Scales (MARSS). IEEE, 2019

[76] Yu H, Fang D J, Dirican M, . Binding conductive ink initiatively and strongly: transparent and thermally stable cellulose nanopaper as a promising substrate for flexible electronics.ACS Applied Materials & Interfaces, 2019, 11(22): 20281–20290

[77] Shukla S, Domican K, Karan K, . Analysis of low platinum loading thin polymer electrolyte fuel cell electrodes prepared by inkjet printing.Electrochimica Acta, 2015, 156(30): 289–300

[78] Ji A, Chen Y M, Wang X Y, . Inkjet printed flexible electronics on paper substrate with reduced graphene oxide/carbon black ink.Journal of Materials Science: Materials in Electronics, 2018, 29(15): 13032–13042

[79] Labulo A H, Omondi B, Nyamori V O . Graphene/pyrrolic-structured nitrogen-doped CNT nanocomposite supports for Pd-catalysed Heck coupling and chemoselective hydrogenation of nitroarenes.SN: Applied Sciences, 2019, 1(2): 142

[80] Hummers W S, Offeman R E . Preparation of graphitic oxide.Journal of the American Chemical Society, 1958, 80(6): 1339

[81] Li K X, Xiong J J, Chen T, , . Preparation of graphene/TiO₂ composites by nonionic surfactant strategy and their simulated sunlight and visible light photocatalytic activity towards representative aqueous POPs degradation. Journal of Hazardous Materials, 2013, 250–251: 19–28

[82] Ghasemi S, Esfandiar A, Setayesh S R, , . Synthesis and characterization of TiO₂–graphene nanocomposites modified with noble metals as a photocatalyst for degradation of pollutants. Applied Catalysis A: General, 2013, 462–463: 82–90

[83] Wang J, Zhang H, Hunt M R, . Synthesis and characterisation of reduced graphene oxide/bismuth composite for electrodes in electrochemical energy storage devices.ChemSusChem, 2017, 10(2): 363–371

[84] Das T R, Patra S, Madhuri R, . Bismuth oxide decorated graphene oxide nanocomposites synthesized via sonochemical assisted hydrothermal method for adsorption of cationic organic dyes.Journal of Colloid and Interface Science, 2018, 509(14): 82–93

[85] Chen X X, Chen B L . Macroscopic and spectroscopic investigations of the adsorption of nitroaromatic compounds on graphene oxide, reduced graphene oxide, and graphene nanosheets.Environmental Science & Technology, 2015, 49(10): 6181–6189

[86] Liu J, Liu Z, Barrow C J, . Molecularly engineered graphene surfaces for sensing applications: a review.Analytica Chimica Acta, 2015, 859(16): 1–19

[87] Astuti Y, Fauziyah A, Nurhayati S, . Synthesis of α-bismuth oxide using solution combustion method and its photocatalytic properties.IOP Conference Series: Materials Science and Engineering, 2016, 107: 012006

[88] Madhusudan P, Yu J, Wang W, . Facile synthesis of novel hierarchical graphene‒Bi₂O₂CO₃ composites with enhanced photocatalytic performance under visible light.Dalton Transactions, 2012, 41(47): 14345–14353

[89] Pramanik N, De J, Basu R K, . Fabrication of magnetite nanoparticle doped reduced graphene oxide grafted polyhydroxyalkanoate nanocomposites for tissue engineering application.RSC Advances, 2016, 6(52): 46116–46133

[90] Pumera M . Graphene-based nanomaterials and their electrochemistry.Chemical Society Reviews, 2010, 39(11): 4146–4159

[91] Polat Y, Akalan H, Arı M . Thermo-electrical and structural properties of Gd₂O₃ and Lu₂O₃ double-doped Bi₂O₃.International Journal of Hydrogen Energy, 2017, 42(1): 614–622

[92] Yu H X, Lan H, Yan L, . TiNb₂O₇ hollow nanofiber anode with superior electrochemical performance in rechargeable lithium ion batteries.Nano Energy, 2017, 38: 109–117

[93] Yang J, Gunasekaran S . Electrochemically reduced graphene oxide sheets for use in high-performance supercapacitors.Carbon, 2013, 51(9): 36–44

[94] Li Z, Wang J, Liu S, . Synthesis of hydrothermally reduced graphene/MnO₂ composites and their electrochemical properties as supercapacitors.Journal of Power Sources, 2011, 196(19): 8160–8165

[95] Bae W K, Joo J, Padilha L A, . Highly effective surface passivation of PbSe quantum dots through reaction with molecular chlorine.Journal of the American Chemical Society, 2012, 134(49): 20160–20168

[96] Doncea S M, Ion R M, Fierascui R C, . Spectral methods for historical paper analysis: composition and age approximation.Instrumentation Science & Technology, 2009, 38(1): 96–106

[97] Choi E Y, Han T H, Hong J . Non-covalent functionalization of graphene with end-functional polymers.Journal of Materials Chemistry, 2010, 20(10): 1907–1912

[98] Fan H L, Wang L L, Zhao K K, . Fabrication, mechanical properties, and biocompatibility of graphene-reinforced chitosan composites.Biomacromolecules, 2010, 11(9): 2345–2351

[99] Wu G J, Wang X M, Guan N J, , . Palladium on graphene as efficient catalyst for solvent-free aerobic oxidation of aromatic alcohols: role of graphene support. Applied Catalysis B: Environmental, 2013, 136–137: 177–185

[100] Chen Y, Zhou L, Wei J, . Direct ink writing of flexible electronics on paper substrate with graphene/polypyrrole/carbon black ink.Journal of Electronic Materials, 2019, 48(5): 3157–3168

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