A High‐Capacitance Salt‐Free Dielectric for Self‐Healable, Printable, and Flexible Organic Field Effect Transistors and Chemical Sensor

Printable and flexible electronics attract sustained attention for their low cost, easy scale up, and potential application in wearable and implantable sensors. However, they are susceptible to scratching, rupture, or other damage from bending or stretching due to their “soft” nature compared to their rigid counterparts (Si‐based electronics), leading to loss of functionality. Self‐healing capability is highly desirable for these “soft” electronic devices. Here, a versatile self‐healing polymer blend dielectric is developed with no added salts and it is integrated into organic field transistors (OFETs) as a gate insulator material. This polymer blend exhibits an unusually high thin film capacitance (1400 nF cm−2 at 120 nm thickness and 20–100 Hz). Furthermore, it shows pronounced electrical and mechanical self‐healing behavior, can serve as the gate dielectric for organic semiconductors, and can even induce healing of the conductivity of a layer coated above it together with the process of healing itself. Based on these attractive properties, we developed a self‐healable, low‐voltage operable, printed, and flexible OFET for the first time, showing promise for vapor sensing as well as conventional OFET applications.

[1]  A. Dodabalapur,et al.  A soluble and air-stable organic semiconductor with high electron mobility , 2000, Nature.

[2]  D. Spurgeon.  Call for tighter controls on transgenic foods , 2001, Nature.

[3]  S. Nutt,et al.  A Thermally Re-mendable Cross-Linked Polymeric Material , 2002, Science.

[4]  Takao Someya,et al.  A large-area, flexible pressure sensor matrix with organic field-effect transistors for artificial skin applications. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[5]  Jaime C. Grunlan,et al.  Conductive Thin Films on Functionalized Polyethylene Particles , 2006 .

[6]  J. Loos,et al.  Cross-linked epoxy composites filled with intrinsically conductive phthalocyanine nanocrystals. influence of filler amount, layer thickness, and cross-linkers used on the percolation threshold and conductivity level of the composites , 2006 .

[7]  Girish M. Joshi,et al.  Effect of molecular weight on dielectric properties of polyvinyl alcohol films , 2006 .

[8]  Zhanqing Li,et al.  Investigation into the vapor sensing behavior and mechanism of a reactive hydroxyl-terminated polybutadiene liquid rubber/carbon black conductive film , 2006 .

[9]  Kyle A. Williams,et al.  Towards electrically conductive, self-healing materials , 2007, Journal of The Royal Society Interface.

[10]  J. Lewis,et al.  Self-healing materials with microvascular networks. , 2007, Nature materials.

[11]  Jiyoul Lee,et al.  Printable ion-gel gate dielectrics for low-voltage polymer thin-film transistors on plastic. , 2008, Nature materials.

[12]  P. Cordier,et al.  Self-healing and thermoreversible rubber from supramolecular assembly , 2008, Nature.

[13]  R. Wool.  Self-healing materials: a review. , 2008, Soft matter.

[14]  John A. DeFranco,et al.  Orthogonal Patterning of PEDOT:PSS for Organic Electronics using Hydrofluoroether Solvents , 2009 .

[15]  Kevin C. See,et al.  Solution-deposited sodium beta-alumina gate dielectrics for low-voltage and transparent field-effect transistors. , 2009, Nature materials.

[16]  Nancy R. Sottos,et al.  Restoration of Conductivity with TTF‐TCNQ Charge‐Transfer Salts , 2010 .

[17]  Guohua Deng,et al.  Covalent cross-linked polymer gels with reversible sol-gel transition and self-healing properties , 2010 .

[18]  Yang Li,et al.  Bioinspired self-healing superhydrophobic coatings. , 2010, Angewandte Chemie.

[19]  Benjamin C. K. Tee,et al.  Highly sensitive flexible pressure sensors with microstructured rubber dielectric layers. , 2010, Nature materials.

[20]  Tobin J Marks,et al.  High-k organic, inorganic, and hybrid dielectrics for low-voltage organic field-effect transistors. , 2010, Chemical reviews.

[21]  Il Ki Han,et al.  The response characteristics of a gas sensor based on poly-3-hexylithiophene thin-film transistors , 2010 .

[22]  T. Someya,et al.  Flexible organic transistors and circuits with extreme bending stability. , 2010, Nature materials.

[23]  D. Brett,et al.  Highly conductive low nickel content nano-composite dense cermets from nano-powders made via a continuous hydrothermal synthesis route , 2010 .

[24]  Justin R. Kumpfer,et al.  Optically healable supramolecular polymers , 2011, Nature.

[25]  H. Dallaporta,et al.  Autonomic self-healing lipid monolayer: a new class of ultrathin dielectric. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[26]  Hon Hang Fong,et al.  Orthogonal Processing and Patterning Enabled by Highly Fluorinated Light‐Emitting Polymers , 2011, Advanced materials.

[27]  T. J. McCarthy,et al.  A surprise from 1954: siloxane equilibration is a simple, robust, and obvious polymer self-healing mechanism. , 2012, Journal of the American Chemical Society.

[28]  Benjamin C. K. Tee,et al.  Transparent, Optical, Pressure‐Sensitive Artificial Skin for Large‐Area Stretchable Electronics , 2012, Advanced materials.

[29]  Yang Li,et al.  Polyelectrolyte Multilayers Impart Healability to Highly Electrically Conductive Films , 2012, Advanced materials.

[30]  P. Chiu,et al.  High mobility flexible graphene field-effect transistors with self-healing gate dielectrics. , 2012, ACS nano.

[31]  Martha E. Grady,et al.  Autonomic Restoration of Electrical Conductivity , 2012, Advanced materials.

[32]  Feng Yan,et al.  Solution Processable Low‐Voltage Organic Thin Film Transistors with High‐k Relaxor Ferroelectric Polymer as Gate Insulator , 2012, Advanced materials.

[33]  B. Blaiszik,et al.  A Self‐healing Conductive Ink , 2012, Advanced materials.

[34]  Aaron M Kushner,et al.  Multiphase design of autonomic self-healing thermoplastic elastomers. , 2012, Nature chemistry.

[35]  Yong-Young Noh,et al.  Remarkable Enhancement of Hole Transport in Top‐Gated N‐Type Polymer Field‐Effect Transistors by a High‐k Dielectric for Ambipolar Electronic Circuits , 2012, Advanced materials.

[36]  T. Lodge,et al.  “Cut and Stick” Rubbery Ion Gels as High Capacitance Gate Dielectrics , 2012, Advanced materials.

[37]  Benjamin C. K. Tee,et al.  An electrically and mechanically self-healing composite with pressure- and flexion-sensitive properties for electronic skin applications. , 2012, Nature nanotechnology.

[38]  Timo Meyer-Friedrichsen,et al.  The relationship between threshold voltage and dipolar character of self-assembled monolayers in organic thin-film transistors. , 2012, Journal of the American Chemical Society.

[39]  Cheolmin Park,et al.  High Performance Multi‐Level Non‐Volatile Polymer Memory with Solution‐Blended Ferroelectric Polymer/High‐k Insulators for Low Voltage Operation , 2013 .

[40]  Zhenan Bao,et al.  Thiol–ene Cross-Linked Polymer Gate Dielectrics for Low-Voltage Organic Thin-Film Transistors , 2013 .

[41]  Y. Lvov,et al.  Self-healing coatings based on halloysite clay polymer composites for protection of copper alloys. , 2013, ACS applied materials & interfaces.

[42]  Zhenan Bao,et al.  Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries. , 2013, Nature chemistry.

[43]  Xiaohong Yang,et al.  RNA sequencing reveals the complex regulatory network in the maize kernel , 2013, Nature Communications.

[44]  Thomas J. Dawidczyk,et al.  Reducing leakage currents in n-channel organic field-effect transistors using molecular dipole monolayers on nanoscale oxides. , 2013, ACS applied materials & interfaces.

[45]  Ion Dependence of Gate Dielectric Behavior of Alkali Metal Ion-Incorporated Aluminas in Oxide Field-Effect Transistors , 2013 .

[46]  M. Kaltenbrunner,et al.  An ultra-lightweight design for imperceptible plastic electronics , 2013, Nature.

[47]  Mihai Irimia-Vladu,et al.  Hydrogen‐Bonded Semiconducting Pigments for Air‐Stable Field‐Effect Transistors , 2013, Advanced materials.

[48]  N. Yoshie,et al.  Bio-Based Furan Polymers with Self-Healing Ability , 2013 .

[49]  Yonggang Huang,et al.  Ultrathin conformal devices for precise and continuous thermal characterization of human skin. , 2013, Nature materials.

[50]  N. Tai,et al.  Fast process to decorate silver nanoparticles on carbon nanomaterials for preparing high-performance flexible transparent conductive films. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[51]  H. Katz,et al.  Diverse Organic Field‐Effect Transistor Sensor Responses from Two Functionalized Naphthalenetetracarboxylic Diimides and Copper Phthalocyanine Semiconductors Distinguishable Over a Wide Analyte Range , 2013 .

[52]  Zhibin Yu,et al.  User-interactive electronic skin for instantaneous pressure visualization. , 2013, Nature materials.

[53]  W. Shi,et al.  Hysteresis mechanism and control in pentacene organic field-effect transistors with polymer dielectric , 2013 .

[54]  Changhyun Pang,et al.  Recent advances in flexible sensors for wearable and implantable devices , 2013 .

[55]  Sanat S Bhole,et al.  Soft Microfluidic Assemblies of Sensors, Circuits, and Radios for the Skin , 2014, Science.

[56]  A. Everett,et al.  Label-free brain injury biomarker detection based on highly sensitive large area organic thin film transistor with hybrid coupling layer , 2014 .

[57]  A. Lasia.  Electrochemical Impedance Spectroscopy and its Applications , 2014 .

[58]  S. Hsu,et al.  Gigahertz flexible graphene transistors for microwave integrated circuits. , 2014, ACS nano.