Eun Kwang Lee

Nitrogenated holey two-dimensional structures

Recent graphene research has triggered enormous interest in new two-dimensional ordered crystals constructed by the inclusion of elements other than carbon for bandgap opening. The design of new multifunctional two-dimensional materials with proper bandgap has become an important challenge. Here we report a layered two-dimensional network structure that possesses evenly distributed holes and nitrogen atoms and a C2N stoichiometry in its basal plane. The two-dimensional structure can be efficiently synthesized via a simple wet-chemical reaction and confirmed with various characterization techniques, including scanning tunnelling microscopy. Furthermore, a field-effect transistor device fabricated using the material exhibits an on/off ratio of 107, with calculated and experimental bandgaps of approximately 1.70 and 1.96 eV, respectively. In view of the simplicity of the production method and the advantages of the solution processability, the C2N-h2D crystal has potential for use in practical applications.

Nitrogen-Doped Graphene Nanoplatelets from Simple Solution Edge-Functionalization for n-Type Field-Effect Transistors

The development of a versatile method for nitrogen-doping of graphitic structure is an important challenge for many applications, such as energy conversions and storages and electronic devices. Here, we report a simple but efficient method for preparing nitrogen-doped graphene nanoplatelets via wet-chemical reactions. The reaction between monoketone (C═O) in graphene oxide (GO) and monoamine-containing compound produces imine (Shiff base) functionalized GO (iGO). The reaction between α-diketone in GO and 1,2-diamine (ortho-diamine)-containing compound gives stable pyrazine ring functionalized GO (pGO). Subsequent heat-treatments of iGO and pGO result in high-quality, nitrogen-doped graphene nanoplatelets to be designated as hiGO and hpGO, respectively. Of particular interest, hpGO was found to display the n-type field-effect transistor behavior with a charge neutral point (Dirac point) located at around -16 V. Furthermore, hpGO showed hole and electron mobilities as high as 11.5 and 12.4 cm(2)V(-1)s(-1), respectively.

Two-dimensional polyaniline (C3N) from carbonized organic single crystals in solid state

Significance Two-dimensional (2D) polyaniline (PANI) has been realized for the first time, to our knowledge, by direct solid-state reaction of organic single crystals. The 2D PANI framework consists of six nitrogen atoms that periodically surround a phenyl ring. Pristine 2D PANI (undoped) has electrical conductivity of 0.72 S/cm, which is 1010 times higher than its linear analog (undoped, 6.28 × 10−11 S/cm). When it is doped by hydrochloric acid (HCl), its conductivity jumps to almost 1,960 times (1.41 × 103 S/cm). Due to its highest conductivity among organic materials, we very strongly believe that this well-defined 2D PANI and its heterogeneity with C and N elements will open up a new research field of layered 2D materials beyond linear PANI and other organic/inorganic 2D materials. The formation of 2D polyaniline (PANI) has attracted considerable interest due to its expected electronic and optoelectronic properties. Although PANI was discovered over 150 y ago, obtaining an atomically well-defined 2D PANI framework has been a longstanding challenge. Here, we describe the synthesis of 2D PANI via the direct pyrolysis of hexaaminobenzene trihydrochloride single crystals in solid state. The 2D PANI consists of three phenyl rings sharing six nitrogen atoms, and its structural unit has the empirical formula of C3N. The topological and electronic structures of the 2D PANI were revealed by scanning tunneling microscopy and scanning tunneling spectroscopy combined with a first-principle density functional theory calculation. The electronic properties of pristine 2D PANI films (undoped) showed ambipolar behaviors with a Dirac point of –37 V and an average conductivity of 0.72 S/cm. After doping with hydrochloric acid, the conductivity jumped to 1.41 × 103 S/cm, which is the highest value for doped PANI reported to date. Although the structure of 2D PANI is analogous to graphene, it contains uniformly distributed nitrogen atoms for multifunctionality; hence, we anticipate that 2D PANI has strong potential, from wet chemistry to device applications, beyond linear PANI and other 2D materials.

Direct Solvothermal Synthesis of B/N‐Doped Graphene

Heteroatom-doping into graphitic networks has been utilized for opening the band gap of graphene. However, boron-doping into the graphitic framework is extremely limited, whereas nitrogen-doping is relatively feasible. Herein, boron/nitrogen co-doped graphene (BCN-graphene) is directly synthesized from the reaction of CCl4 , BBr3 , and N2 in the presence of potassium. The resultant BCN-graphene has boron and nitrogen contents of 2.38 and 2.66 atom %, respectively, and displays good dispersion stability in N-methyl-2-pyrrolidone, allowing for solution casting fabrication of a field-effect transistor. The device displays an on/off ratio of 10.7 with an optical band gap of 3.3 eV. Considering the scalability of the production method and the benefits of solution processability, BCN-graphene has high potential for many practical applications.

Graphene–Ruthenium Complex Hybrid Photodetectors with Ultrahigh Photoresponsivity

The maximum responsivity of a pure monolayer graphene-based photodetector is currently less than 10 mA W(-1) because of small optical absorption and short recombination lifetime. Here, a graphene hybrid photodetector functionalized with a photoactive ruthenium complex that shows an ultrahigh responsivity of ≈1 × 10(5) A W(-1) and a photoconductive gain of ≈3 × 10(6) under incident optical intensity of the order of sub-milliwatts is reported. This responsivity is two orders of magnitude higher than the precedent best performance of graphene-based photodetectors under a similar incident light intensity. Upon functionalization with a 4-nm-thick ruthenium complex, monolayer graphene-based photodetectors exhibit pronounced n-type doping effect due to electron transfer via the metal-ligand charge transfer (MLCT) from the ruthenium complex to graphene. The ultrahigh responsivity is attributed to the long lifetime and high mobility of the photoexcited charge carriers. This approach is highly promising for improving the responsivity of graphene-based photodetectors.

Chemically Robust Ambipolar Organic Transistor Array Directly Patterned by Photolithography

Organic ambipolar transistor arrays for chemical sensors are prepared on a flexible plastic substrate with a bottom-gate bottom-contact configuration to minimize the damage to the organic semiconductors, for the first time, using a photolithographically patternable polymer semiconductor. Well-balanced ambipolar charge transport is achieved by introducing graphene electrodes because of the reduced contact resistance and energetic barrier for electron transport.

Toward Environmentally Robust Organic Electronics: Approaches and Applications

Recent interest in flexible electronics has led to a paradigm shift in consumer electronics, and the emergent development of stretchable and wearable electronics is opening a new spectrum of ubiquitous applications for electronics. Organic electronic materials, such as π-conjugated small molecules and polymers, are highly suitable for use in low-cost wearable electronic devices, and their charge-carrier mobilities have now exceeded that of amorphous silicon. However, their commercialization is minimal, mainly because of weaknesses in terms of operational stability, long-term stability under ambient conditions, and chemical stability related to fabrication processes. Recently, however, many attempts have been made to overcome such instabilities of organic electronic materials. Here, an overview is provided of the strategies developed for environmentally robust organic electronics to overcome the detrimental effects of various critical factors such as oxygen, water, chemicals, heat, and light. Additionally, molecular design approaches to π-conjugated small molecules and polymers that are highly stable under ambient and harsh conditions are explored; such materials will circumvent the need for encapsulation and provide a greater degree of freedom using simple solution-based device-fabrication techniques. Applications that are made possible through these strategies are highlighted.

Tuning polarity and improving charge transport in organic semiconductors

Although state-of-the-art ambipolar polymer semiconductors have been extensively reported in recent years, highperformance ambipolar polymers with tunable dominant polarity are still required to realize on-demand, target-specific, high-performance organic circuitry. Herein, dithienyl-diketopyrrolopyrrole (TDPP)-based polymer semiconductors with engineered side-chains have been synthesized, characterized and employed in ambipolar organic field-effect transistors, in order to achieve controllable and improved electrical properties. Thermally removable tert-butoxycarbonyl (t-BOC) groups and hybrid siloxane-solubilizing groups are introduced as the solubilizing groups, and they are found to enable the tunable dominant polarity and the enhanced ambipolar performance, respectively. Such outstanding performance based on our molecular design strategies makes these ambipolar polymer semiconductors highly promising for low-cost, large-area, and flexible electronics.

Reduced Pyronin B as a solution-processable and heating-free n-type dopant for soft electronics

Air-stable and heating-free doping processes are highly desirable for realizing advanced flexible electronics on plastic substrates. A synthetic protocol for a high-performance n-type organic dopant using an organic cationic dye, Pyronin B, via a simple chemical reduction method with NaBH4 in various organic non-polar solvents is developed, in which the cationic dye Pyronin B is transformed into its leuco form. The reduced Pyronin B (rPyB, leuco form) spontaneously interacts with carbon nanomaterials, such as graphene and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), via hydride-mediated electron transfer doping, which is confirmed by electron spin resonance (ESR) analysis. After coating rPyB onto graphene, the non-polar solvents are removed by simple evacuation (∼1 × 10−3 Torr) without an annealing step. The work function of graphene is reduced from 4.52 eV to 3.98 eV after doping. Multiple coatings of rPyB on graphene field-effect transistors (FETs) result in air stability for 90 days under ambient conditions. Selective n-type doping using a polydimethylsiloxane (PDMS) stamp and rPyB has also been performed on a large-area 16 × 16 graphene FET array. Our findings demonstrate a viable methodology for the cost-effective synthesis of an n-type dopant and its application in soft electronics.