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Formation of continuous and adherent diamond films on practical substrates presents a formidable challenge due to lack of diamond nucleation sites needed for diamond growth. This problem has been solved through the formation of interfacial Q-carbon layers by nanosecond laser melting of carbon layers in a highly undercooled state and subsequent quenching. The Q-carbon layer provides ready nucleation sites for epitaxial films on planar matching substrates such as sapphire, and polycrystalline films on amorphous substrates such as glass. Each laser pulse converts about a one-cm-square area, which can be repeated with a 100–200 Hz laser to produce potentially 100–200 cm2s-1 of diamond films. This is essentially a low-temperature processing, where substrate stays close to ambient temperature, because the total heat input is quite small. The Q-carbon layer is also responsible for improved adhesion of diamond films on sapphire and glass substrates. It is also argued that the formation of Q-carbon layer is also responsible for efficient diamond nucleation during negatively biased MPCVD diamond depositions.

We report formation of self-organized nanodiamond ring structures due to dynamical heterogeneity in super undercooled carbon, created by nanosecond laser melting of amorphous carbon layers. We envisage that diamond tetrahedra self-organize and lead to formation of string and ring structures on which nanodiamonds nucleate and grow. Denser ring structures are formed in Q-carbon due to higher undercooling and enhanced diamond nucleation. The average size is larger under heterogeneous nucleation compared to homogeneous nucleation due to lower critical size and free energy, allowing more time for growth. With nanosecond laser melting, growth velocities range 5–10 ms−1 and even higher for Q-carbon.

We report pseudo-topotactic growth of single-crystal diamond fibers by nanosecond laser melting of amorphous carbon nanofibers (CNFs) and crystalline multi-wall carbon nanotubes (MWCNTs). A rapid laser melting in a super undercooled state and subsequent quenching convert the tips of CNFs and MWCNTs into phase-pure nanodiamonds along the growth directions. Subsequent laser pluses melt regions below nanodiamonds that provide seeds for epitaxial growth. By repeating this process, the length of nanodiamond fibers can be increased, as each pulse results in ∼50 nm nanodiamond region, depending upon the initial size of CNFs and MWCTs. This conversion process can be carried at ambient temperature and pressure in air. The epitaxial nature of nanodiamond fibers has been confirmed by systematic electron-back-scatter-diffraction studies along the fiber in high-resolution scanning electron microscopy, and high-resolution TEM imaging and diffraction. The nature of C–C bonding characteristics was studied by high-resolution electron-energy-loss spectroscopy to establish the formation of diamond phase by the characteristic peak at 292 eV for sp3 bonding (σ∗), and absence of 284 eV peak for sp2 (π∗) graphitic bonding. The characteristic diamond Raman peak at 1332 cm−1 is found to downshift to 1321 cm−1 because of phonon confinement in nanodiamonds associated with nanofibers. These nanodiamond structures can be doped with both n- and p-type dopants with concentrations far higher than thermodynamic solubility limit due to solute trapping during quenching from the liquid phase. Thus, these nanodiamond structures provide ideal platform for nanosensing, computing and communication, including efficient field emitting devices.

We report the spectroscopic demonstration of the shallow-level energy states in the recently discovered B-doped Q-carbon Bardeen-Cooper-Schrieffer (BCS) high-temperature superconductor. The Q-carbon is synthesized by ultrafast melting and quenching, allowing for high B-doping concentrations which increase the superconducting transition temperature (Tc) to 36 K (compared to 4 K for B-doped diamond). The increase in Tc is attributed to the increased density of energy states near the Fermi level in B-doped Q-carbon, which give rise to superconducting states via strong electron-phonon coupling below Tc. These shallow-level energy states, however, are challenging to map due to limited spatial and energy resolution. Here, we use ultrahigh energy resolution monochromated electron energy-loss spectroscopy (EELS), to detect and visualize the newly formed shallow-level energy states (vibrational modes) near the Fermi level (ranging 30–100 meV) of the B-doped Q-carbon. With this study, we establish the significance of high-resolution EELS in understanding the superconducting behavior of BCS superconducting C-based materials, which demonstrate a phenomenal enhancement in the presence of shallow-level energy states.

We present 1D, 2D and 3D structures of boron-doped Q-carbon with a higher superconducting transition temperature than the current value of 55 K in 25 at% B-doped amorphous Q-carbon. The higher transition temperature is predicted for 1D and 2D crystalline structures with increasing density of states near the Fermi level through dopant trapping in substitutional sites. We have synthesized 50at% B-doped Q-carbon where diamond tetrahedra are arranged randomly and packed with over 80% efficiency to generate an amorphous structure. Detailed EELS measurements show higher density of states near the Fermi level above 90 K and preliminary transport data show signature of Tc above 100 K.

A prerequisite condition for next-generation quantum sensing, communication, and computing is the precise modulation of the charge states of nitrogen-vacancy (NV) centers in diamond. We have achieved tuning of these centers in highly concentrated NV-diamonds using photons, phonons, and electrons. These NV-diamonds are synthesized employing a unique nanosecond laser processing technique which results in ultrafast melting and subsequent quenching of nitrogen-doped molten carbon films. Substitutional nitrogen atoms and vacancies are incorporated into diamond during rapid liquid-phase growth, where dopant concentrations can exceed thermodynamic solubility limits through solute trapping. This ultrafast synthesis technique generates fewer surface traps thereby forming ∼75% NV− centers at room-temperature, which are optically and magnetically distinct as compared to NV0 centers. We dramatically increase the NV− concentration in NV-diamonds by ∼53% with decreasing temperature from 300 to 80 K. With negative electrical biasing, the Fermi level in NV-diamond rises and crosses the NV0/- level, thereby promoting an exponential conversion of NV0 to NV− centers. We have also photonically enhanced the photoluminescence signal from NV− centers, thereby ascertaining the conversion of NV0 into NV− via absorption of electrons (excited by 532 nm photons) from the valence band in NV-diamond. These NV-centers in diamonds also reveal large excitation lifetime, which ultimately leads to ∼65% quantum efficiency at room-temperature. With these results, we believe that the precise tuning of charge states in these uniquely prepared highly concentrated NV-diamonds will lead to superior quantum devices.

We have created nanostructured Si (∼3 nm) with a direct band gap of 1.37 eV on electrically conducting reduced graphene oxide (rGO) for a highly efficient photosensor. This robust photosensor is fabricated using a nonequilibrium processing route, where nanosecond excimer laser pulses melt the alternating layers of Si and amorphous carbon to form micropillars and nanoreceptors of Si on rGO layers. The incident white light generates free carriers in the Si microstructures and nanoreceptors which are ballistically transported (via rGO layers) to the external circuit under the application of a voltage bias. The responsivity of rGO-Si devices to light (resistance vs time) and I–V measurements indicate an exponential drop in resistance with the incidence of white light and nonrectifying nature, respectively. Photoresponsivity of the rGO-Si devices is calculated to be 3.55 A/W at room temperature, which is significantly larger than the previously fabricated graphene-based ohmic photosensors. Temperature-dependen...

While hot-filament assisted chemical vapor deposition (HFCVD) is a well-established technique to synthesize diamond thin films using microdiamond seeds, the quality of grown diamond thin films is often compromised due to the presence of contaminants, i.e. graphitic entities and the eroded tungsten filament remnants, at the film-substrate interface. Here, we present a novel approach to form high-quality, contamination-free diamond thin films with HFCVD using Q-carbon precursor. The Q-carbon is a metastable phase which is formed by nanosecond laser melting of amorphous carbon and rapid quenching from the superundercooled state and consists of ∼75% sp3 and rest sp2 hybridized carbon. Using Q-carbon seeds in HFCVD, we demonstrate the growth of polycrystalline diamond film with a clean interface without any tungsten filament impurities. With large-area vibrational Raman mode analysis, we also observe a significant reduction in the presence of overall graphitic entities in the diamond film. With the realization of such a high-quality interface, we present a pathway to fabricate significantly improved diamond coatings and solid-state devices.

We report a pulsed laser annealing method to convert carbon fibers and nanotubes into diamond fibers at ambient temperature and pressure in air. The conversion of carbon nanofibers and nanotubes into diamond nanofibers involves melting in a super undercooled state using nanosecond laser pulses, and quenching rapidly to convert into phase-pure diamond. The conversion process occurs at ambient temperature and pressure, and can be carried out in air. The structure of diamond fibers has been confirmed by selected-area electron diffraction in transmission electron microscopy, electron-back-scatter-diffraction in high-resolution scanning electron microscopy, all showing characteristic diffraction lines for the diamond structure. The bonding characteristics were determined by Raman spectroscopy with a strong peak near 1332 cm-1, and high-resolution electron-energy-loss spectroscopy in transmission electron microscopy with a characteristic peak at 292 eV for σ* for sp3 bonding and the absence of π* for sp2 bonding. The Raman peak at 1332 cm-1 downshifts to 1321 cm-1 for diamond nanofibers due to the phonon confinement in nanodiamonds. These laser-treated carbon fibers with diamond seeds are used to grow larger diamond crystallites further by using standard hot-filament chemical vapor deposition (HFCVD). We compare these results with those obtained without laser treating the carbon fibers. The details of diamond conversion and HFCVD growth are presented in this paper.

Here, we report the detailed structure-property correlations in phase-pure B-doped Q-carbon high-temperature superconductor having a superconducting transition temperature (Tc) of 55 K. This superconducting phase is a result of nanosecond laser melting and subsequent quenching of a highly super undercooled state of molten B-doped C. The temperature-dependent resistivity in different magnetic fields and magnetic susceptibility measurements indicate a type-II Bardeen-Cooper-Schrieffer superconductivity in B-doped Q-carbon thin films. The magnetic measurements indicate that the upper and lower critical fields follow Hc2(0)[1 - (T/Tc)1.77] and Hc1(0)[1 - (T/Tc)1.19] temperature dependence, respectively. The structure-property characterization of B-doped Q-carbon indicates a high density of electronic states near the Fermi-level and large electron-phonon coupling. These factors are responsible for s-wave bulk type superconductivity with enhanced Tc in B-doped Q-carbon. The time-dependent magnetic moment measurements indicate that B-doped Q-carbon thin films follow the Anderson-Kim logarithmic decay model having high values of pinning potential at low temperatures. The crossover from the two-dimensional to the three-dimensional nature of Cooper pair transport at T/Tc = 1.02 also indicates a high value of electron-phonon coupling which is also calculated using the McMillan formula. The superconducting region in B-doped Q-carbon is enclosed by Tc = 55.0 K, Jc = 5.0 × 108 A cm-2, and Hc2 = 9.75 T superconducting parameters. The high values of critical current density and pinning potential also indicate that B-doped Q-carbon can be used for persistent mode of operation in MRI and NMR applications. The Cooper pairs which are responsible for the high-temperature superconductivity are formed when B exists in the sp3 sites of C. The electron energy loss spectroscopy and Raman spectroscopy indicate a 75% sp3 bonded C and 70% sp3 bonded B in the superconducting phase of B-doped Q-carbon which has 27 at% B and rest C. The dimensional fluctuation and magnetic relaxation measurements in B-doped Q-carbon indicate its practical applications in frictionless motors and high-speed electronics. This discovery of high-temperature superconductivity in strongly-bonded and light-weight materials using non-equilibrium synthesis will provide the pathway to achieve room-temperature superconductivity.

Nano- and microstructures of phase-pure cubic boron nitride (c-BN) are synthesized by employing nanosecond pulsed-laser annealing techniques at room temperature and atmospheric pressure. In a highly non-equilibrium synthesis process, nanocrystalline h-BN is directly converted into phase-pure twinned c-BN from a highly undercooled melt state of BN. By changing nucleation and growth rates, we have synthesized a wide range of sizes (90 nm to 25 μm) of c-BN. The electron diffraction patterns show the formation of twinned c-BN with [11[combining macron]1] as the twin axis. The twinning density in c-BN can be controlled by the degree of undercooling and quenching rates. The formation of twins predominantly occurs prior to the formation of amorphous quenched BN (Q-BN). Therefore, the defect density in nano c-BN formed under higher undercooling conditions is considerably larger than that in micro c-BN, which is formed under lower undercooling conditions. The temperature-dependent Raman studies show a considerable blue-shift of ∼6 cm-1 with a decrease in temperature from 300 to 78 K in nano c-BN as compared to micro c-BN. The size-effects of c-BN crystals in Raman spectra are modeled using spatial correlation theory, which can be used to calculate the correlation length and twin density in c-BN. It has also been found that the Raman blue-shift in nano c-BN is caused by anharmonic effects, and the decrease in Raman linewidth with decreasing temperature (300 to 78 K) is caused by three- and four-phonon decay processes. The bonding characteristics and crystalline nature of the synthesized c-BN are also demonstrated by using electron energy-loss spectroscopy and electron backscatter diffraction, respectively. We envisage that the controlled growth of phase-pure nano and microstructures of twinned c-BN and their temperature-dependent Raman-active vibrational mode studies will have a tremendous impact on low-temperature solid-state electrical and mechanical devices.

We provide insights pertaining the dependence of undercooling in the formation of graphite, nanodiamonds, and Q-carbon nanocomposites by nanosecond laser melting of diamond-like carbon (DLC). The DLC films are melted rapidly in a super-undercooled state and subsequently quenched to room temperature. Substrates exhibiting different thermal properties-silicon and sapphire, are used to demonstrate that substrates with lower thermal conductivity trap heat flow, inducing larger undercooling, both experimentally and theoretically via finite element simulations. The increased undercooling facilitates the formation of Q-carbon. The Q-carbon is used as nucleation seeds for diamond growth via laser remelting and hot-filament chemical vapor deposition.

A new phase of carbon named Q-carbon is found to be over 40% harder than diamond. This phase is formed by nanosecond laser melting of amorphous carbon and rapid quenching from the super-undercooled state. Closely packed atoms in molten metallic carbon are quenched into Q-carbon with 80-85% sp3 and the rest sp2. The number density of atoms in Q-carbon can vary from 40% to 60% higher than diamond cubic lattice, as the tetrahedra packing efficiency increases from 70% to 80%. Using this semiempirical approach, the corresponding increase in Q-carbon hardness is estimated to vary from 48% to 70% compared to diamond.

We report extraordinary Hall effect and room-temperature ferromagnetism in undoped Q-carbon, which is formed by nanosecond pulsed laser melting and subsequent quenching process. Through detailed structure–property correlations in Q-carbon thin films, we show the excess amount of unpaired electrons near the Fermi energy level give rise to interesting magnetic and electrical properties. The analysis of the extraordinary Hall effect in Q-carbon follows nonclassical “side-jump” electronic scattering mechanism. The isothermal field-dependent magnetization plots confirm room-temperature ferromagnetism in Q-carbon with a finite coercivity at 300 K and a Curie temperature of 570 K, obtained by the extrapolation of the fits to experimental data using modified Bloch’s law. High-resolution scanning electron microscopy and transmission electron microscopy clearly illustrate the formation of Q-carbon and its subsequent conversion to single-crystalline diamond. Further, we found n-type conductivity in Q-carbon in the e...

This article provides insights pertaining to the first-order phase transformation involved in the growth of densely packed Q-carbon and nanodiamonds by nanosecond laser melting and quenching of diamond-like carbon (DLC) thin films. DLC films with different sp3 content were melted rapidly in a controlled way in super-undercooled state and quenched, leading to formation of distinct nanostructures, i.e., nanodiamonds, Q-carbon, and Q-carbon nanocomposites. This analysis provides direct evidence of the dependence of the super-undercooling on the structural evolution of Q-carbon. Finite element heat flow calculations showed that the super-undercooling varies monotonically with the sp3 content. The phenomenon of solid–liquid interfacial instability during directional solidification from the melt state is studied in detail. The resulting lateral segregation leads to formation of cellular filamentary Q-carbon nanostructures. The dependence of the cell size and wavelength at the onset of instability on the sp3 content of DLC thin films was modeled based on perturbation theory.

We report the synthesis and characterization of quenched (Q-carbon and Q-BN) and crystalline (diamond and c-BN) phases using a non-equilibrium technique. These phases are formed as a result of the melting and subsequent quenching of amorphous carbon and nanocrystalline h-BN in a super undercooled state by using high-power nanosecond laser pulses. Pulsed laser annealing also leads to the formation of nanoneedles, microneedles and single-crystal thin films of diamond and c-BN. This formation is dependent on the nucleation and growth times, which are controlled by laser energy density and thermal conductivities of substrate and as-deposited thin film. The diamond nuclei present in the Q-carbon structure (~ 80% sp3) can also be grown to larger sizes using the equilibrium hot filament chemical vapor deposition process. The texture of diamond and c-BN crystals is 〈111〉 under epitaxial growth and 〈110〉 under rapid unseeded crystallization. Our nanosecond laser processing opens up a roadmap to the fabrication of novel phases on heat-sensitive substrates.

We have achieved a superconducting transition temperature (Tc) of 55 K in 27 at% B-doped Q-carbon. This value represents a significant improvement over previously reported Tc of 36 K in B-doped Q-carbon and is the highest Tc for conventional BCS (Bardeen–Cooper–Schrieffer) superconductivity in bulk carbon-based materials. The B-doped Q-carbon exhibits type-II superconducting characteristics with Hc2(0) ∼ 10.4 T, consistent with the BCS formalism. The B-doped Q-carbon is formed by nanosecond laser melting of B/C multilayered films in a super undercooled state and subsequent quenching. It is determined that ∼67% of the total boron exists with carbon in a sp3 hybridized state, which is responsible for the substantially enhanced Tc. Through the study of the vibrational modes, we deduce that higher density of states near the Fermi level and moderate to strong electron–phonon coupling lead to a high Tc of 55 K. With these results, we establish that heavy B doping in Q-carbon is the pathway for achieving high-te...

Here, we report the detailed structure-property correlations in phase-pure B-doped Q-carbon high-temperature superconductor having a superconducting transition temperature (Tc) of 55 K. This superconducting phase is a result of nanosecond laser melting and subsequent quenching of a highly super undercooled state of molten B-doped C. The temperature-dependent resistivity in different magnetic fields and magnetic susceptibility measurements indicate a type-II Bardeen-Cooper-Schrieffer superconductivity in B-doped Q-carbon thin films. The magnetic measurements indicate that the upper and lower critical fields follow Hc2(0)[1 - (T/Tc)1.77] and Hc1(0)[1 - (T/Tc)1.19] temperature dependence, respectively. The structure-property characterization of B-doped Q-carbon indicates a high density of electronic states near the Fermi-level and large electron-phonon coupling. These factors are responsible for s-wave bulk type superconductivity with enhanced Tc in B-doped Q-carbon. The time-dependent magnetic moment measurements indicate that B-doped Q-carbon thin films follow the Anderson-Kim logarithmic decay model having high values of pinning potential at low temperatures. The crossover from the two-dimensional to the three-dimensional nature of Cooper pair transport at T/Tc = 1.02 also indicates a high value of electron-phonon coupling which is also calculated using the McMillan formula. The superconducting region in B-doped Q-carbon is enclosed by Tc = 55.0 K, Jc = 5.0 × 108 A cm-2, and Hc2 = 9.75 T superconducting parameters. The high values of critical current density and pinning potential also indicate that B-doped Q-carbon can be used for persistent mode of operation in MRI and NMR applications. The Cooper pairs which are responsible for the high-temperature superconductivity are formed when B exists in the sp3 sites of C. The electron energy loss spectroscopy and Raman spectroscopy indicate a 75% sp3 bonded C and 70% sp3 bonded B in the superconducting phase of B-doped Q-carbon which has 27 at% B and rest C. The dimensional fluctuation and magnetic relaxation measurements in B-doped Q-carbon indicate its practical applications in frictionless motors and high-speed electronics. This discovery of high-temperature superconductivity in strongly-bonded and light-weight materials using non-equilibrium synthesis will provide the pathway to achieve room-temperature superconductivity.

Here, we show the direct conversion of carbon nanofibers (CNFs) into diamond nanofibers (DNFs) by irradiating CNFs with an ArF nanosecond laser at room temperature and atmospheric pressure. The nanosecond laser pulses melt the tips of CNFs into a highly undercooled state, and their subsequent quenching results in the formation of DNFs. This formation of DNFs is dependent on the degree of undercooling which is controlled by nanosecond laser energy density and one-dimensional heat flow characteristics in CNFs. The conversion process starts at the top and extends with the number of pulses. Therefore, our highly non-equilibrium nanosecond laser processing opens a new avenue for the synthesis of exciting pure and doped diamond structures at ambient temperatures and pressures for a variety of applications.

We review the discovery of a new phase BN (named Q-BN) which has been created by nanosecond laser melting in the super undercooled state and quenching rapidly with rates exceeding several billion degrees per second. This phase, sequel to our earlier discovery of Q-Carbon, has amorphous structure from which phase-pure c-BN is formed in the form of nanodots, microcrystals, nanoneedles, and microneedles. Large-area single c-BN are formed by providing a template for epitaxial growth during quenching of super undercooled liquid BN. Since there is a rapid crystal growth from liquid, both n- and p-type dopants can be incorporated into electrically active substitutional sites with concentrations exceeding solubility limits through the phenomenon of solute trapping. We have grown diamond on c-BN by pulsed laser deposition of carbon at 500°C without the presence of hydrogen, and created c-BN and diamond epitaxial composites. We discuss the mechanism of epitaxial c-BN and diamond growth on lattice matching c-BN template under pulsed laser evaporation of amorphous carbon. This discovery on direct conversion of h-BN into phase-pure c-BN at ambient temperatures and pressures in air, represents a seminal contribution to the field of boron nitride, which is quite complementary to our discovery of graphite to diamond conversion. We have bypassed thermodynamics with the help of kinetics and time control. This research represents a major breakthrough for c-BN and diamond based high-power electronic and photonic devices, and host of other applications related to high-speed machining, deep-sea drilling, field-emission displays and biomedical applications.

Q-carbon is a metastable phase of carbon formed by melting and subsequently quenching amorphous carbon films by a nanosecond laser in a super undercooled state. As Q-carbon is a material harder than diamond, it makes an excellent reinforcing component inside the softer matrix of a composite coating. In this report, we present a single-step strategy to fabricate adherent coatings of hard and lubricating Q-carbon nanocomposites. These nanocomposites consist of densely-packed sp 3-rich Q-carbon (82% sp 3), and sp 2-rich α-carbon (40% sp 3) amorphous phases. The nanoindentation tests show that the Q-carbon nanocomposites exhibit a hardness of 67 GPa (Young's modulus ~ 840 GPa) in contrast to the soft α-carbon (hardness ~ 18 GPa). The high hardness of Q-carbon nanocomposites results in 0.16 energy dispersion coefficient, in comparison with 0.74 for α-carbon. The soft α-carbon phase provides lubrication, resulting in low friction and wear coefficients of 0.09 and 1 × 10−6, respectively, against the diamond tip. The nanoscale dispersion of hard Q-carbon and soft α-carbon phases in the Q-carbon nanocomposites enhances the toughness of the coatings. We present detailed structure-property correlations to understand enhancement in the mechanical properties of Q-carbon nanocomposites. This work provides insights into the characteristics of Q-carbon nanocomposites and advances carbon-based superhard materials for longer lasting protective coatings and related applications.

Dimensional fluctuations and magnetic relaxations in high-temperature superconductors are key considerations for practical applications in high-speed electronic devices. We report the creep of trapped magnetic flux and three-dimensional critical fluctuations near the superconducting transition temperature (Tc = 36 K) in B-doped amorphous Q-carbon. The superconducting phase in B-doped Q-carbon is formed by nanosecond pulsed laser melting in a super undercooled state followed by subsequent quenching. Time-dependent magnetic moment measurements in the B-doped Q-carbon follow the Anderson–Kim logarithmic decay model with the calculated value of pinning potential to be 0.75 eV at 1 T near Tc. There is also strong evidence of three-dimensional (3D) critical fluctuations near Tc in B-doped Q-carbon. The crossover from 2D to 3D critical fluctuations is seen at T/Tc = 1.01 as compared to T/Tc = 1.11 in conventional Bardeen–Cooper–Schrieffer (BCS) high-temperature superconductors. These critical fluctuations indicate moderate to strong electron–phonon coupling in B-doped Q-carbon. The isomagnetic temperature-dependent resistivity measurements reveal a broadening of superconducting transition width with increasing magnetic field. The upper critical field (Hc2(0)) is calculated to be 5.6 T using the power law. Finally, the superconducting region is determined in B-doped Q-carbon, as the three vertices of the superconducting region are calculated as Tc = 36.0 K, Jc = 2.9 × 109 A cm−2 and Hc2 = 5.6 T. The temperature-dependent magnetic moment and resistivity measurements also validate B-doped Q-carbon as a BCS type-II superconductor. B concentration in Q-carbon can be increased up to 50 at% by a nanosecond laser melting and quenching technique, thus providing an ideal platform for near room-temperature superconductivity.

We report the formation of single-crystal diamond nanoneedles, microneedles and thin films on sapphire (0001). By using nanosecond excimer laser pulses, we convert amorphous carbon into a new state of Q-carbon by rapid melting and quenching. The Q-carbon consists of amorphous mostly sp3 bonded carbon and rest 10–15% sp2, from which diamonds are nucleated. These nanodiamond nuclei in Q-carbon provide a seed for growth of diamond. These nanoneedles and microneedles are found to be single crystals often oriented along ⟨110⟩ directions. The (111) single-crystal diamond film are formed, when sapphire (0001) provides a seed for diamond growth from super undercooled liquid.

We review the discovery of new phases of carbon (Q-carbon) and BN (Q-BN) and address critical issues related to direct conversion of carbon into diamond and hBN into cBN at ambient temperatures and pressures in air without any need for catalyst and the presence of hydrogen. The Q-carbon and Q-BN are formed as a result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs T) of carbon, and show that by rapid quenching, kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. Similarly, the hBN-cBN-Liquid triple point is shifted from 3500 K/9.5 GPa to as low as 2800 K and atmospheric pressure. It is shown that nanosecond laser heating of amorphous carbon and nanocrystalline BN on sapphire, glass, and polymer substrates can be confined to melt in a super undercooled state. By quenching this super undercooled state, we have created a new state of carbon (Q-carbon) and BN (Q-BN) from which nanocrystals, microcrystals, nanoneedles, microneedles, and thin films are formed depending upon the nucleation and growth times allowed and the presence of growth template. The large-area epitaxial diamond and cBN films are formed, when appropriate planar matching or lattice matching template is provided for growth from super undercooled liquid. The Q-phases have unique atomic structure and bonding characteristics as determined by high-resolution SEM and backscatter diffraction, HRTEM, STEM-Z, EELS, and Raman spectroscopy, and exhibit new and improved mechanical hardness, electrical conductivity, and chemical and physical properties, including room-temperature ferromagnetism and enhanced field emission. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g−1. We have also deposited diamond on cBN by using a novel pulsed laser evaporation of carbon and obtained cBN/diamond composites, where cBN acts as template for diamond growth. Both diamond and cBN grown from super undercooled liquid can be alloyed with both p- and n-type dopants. This process allows carbon to diamond and hBN to cBN conversions and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp3 bonding for diamond and cBN phases.

Localized charge injection by formation of vacancies provides an attractive platform for the development of multifunctional nanomaterials with direct implications in spintronics. However, further progress in spintronics critically depends on a deeper understanding of polaronic interactions between the localized charge states. This report is focused on TiN metallic system, which exhibits Pauli paramagnetism due to the absence of unpaired localized spin states. Nitrogen vacancies (VN) are used as a variable to tune the magnetic properties of epitaxial TiN thin films by thermal annealing in high-vacuum and N2 environment. Systematic introduction of VN generates robust magnetic ordering in vacuum-annealed TiN1-x, with Curie temperature (TC) ~700 K, and saturation magnetization (Ms) of 13.6 emu g-1. The signature spin-glass behavior below the irreversibility temperature (Tir ~40 K) indicates the Ruderman-Kittel-Kasuya-Yosida (RKKY) coupling interactions between the unpaired localized spin-states. Through spatially resolved electron energy-loss spectroscopy, we have determined the generation of unpaired localized spins at Ti 2 polarons with ~12±2 at.% VN in TiN1-x films. Such a large concentration of VN results in increased spin stiffness and high TC. These findings open a definitive pathway for tuning the magnetic nature of metallic materials for spintronic applications.

We have achieved a superconducting transition temperature (T

We report high-temperature superconductivity in B-doped amorphous quenched carbon (Q-carbon). This phase is formed after nanosecond laser melting of B-doped amorphous carbon films in a super-undercooled state and followed by rapid quenching. Magnetic susceptibility measurements show the characteristics of type-II Bardeen–Cooper–Schrieffer superconductivity with a superconducting transition temperature (Tc) of 36.0 ± 0.5 K for 17.0 ± 1.0 atom % boron concentration. This value is significantly higher than the best experimentally reported Tc of 11 K for crystalline B-doped diamond. We argue that the quenching from metallic carbon liquid leads to a stronger electron–phonon coupling due to close packing of carbon atoms with higher density of states at the Fermi level. With these results, we propose that the non-equilibrium undercooling-assisted synthesis method can be used to fabricate highly doped materials that provide greatly enhanced superconducting properties.

Resurgence of copper oxide based thin film solar cells demands exclusive methods of integrating various layers with superior constituents for increased solar-electric conversion efficiency. Exceedingly optically active nanostructured phase mixture of copper oxides was synthesized by an energy efficient hydrothermal process. Comprehensive structural and optical studies of these nanostructured copper oxides reveal its efficacy as a unique solar cell material. Excellent solar cell characteristics have been observed when these nanopowders are integrated with ZnO/CuO based thin films. X-ray diffraction, Raman micro-scattering, scanning electron microscopy, energy dispersive X-ray spectroscopy, UV–vis spectroscopy, atomic force microscopy, and optoelectronic measurements were employed to characterize these unified electronic devices. Solar cell measurements indicate a considerable increase in short circuit current density (Jsc) and open circuit voltage (Voc) in the fabricated nanostructure powder-thin film hybrid solar cell devices. The solar cell efficiency of these nanopowder-thin film devices is found to be 2.88%. The physics behind this enrichment of solar cell properties has also been elucidated in the study. Exhaustive Raman spectroscopic and photoluminescence studies prove that multi-phonon scattering may play a major role for this enhancement. This integration of nanostructures with thin film solar cells can evolve to a new direction in photovoltaic technology.

We report the role of molybdenum (Mo) doping in ferrimagnetism of yttrium iron garnet Y3Fe5O12 (YIG). X-ray diffraction studies in conjunction with Rietveld refinement indicate that the Y3Fe5−5xMo5xO12 (MYIG) crystallizes in the crystal symmetry of inverse cubic spinel phase. Temperature and field dependent magnetization M(H,T) data designate the long range ferromagnetic ordering in MYIG. The calculated cubic anisotropy constant K1(T) and saturation magnetization Ms(T) by the ‘law of approach’ indicate that these parameters decrease with increasing temperature. The magnitude of Ms(T) is dependent on Mo-concentration and the Ms–T functional relationship obeys the Bloch׳s spin wave theory. Initially magnetic moment per Fe atom in the unit cell increases with Mo doping and henceforth it decreases slowly with further Mo doping. XRD and Raman spectroscopic molecular vibrational studies were employed to explain the variation of magnetic moment per Fe atom in MYIG. The occupancy parameter and magnetic moment calculated by Rietveld analysis reveal that Mo ions occupy the Fe position at the octahedral site with low doping and this site occupancy decreases with increase in Mo doping.

With the advent of nanobiotechnology, there will be an increase in the interaction between engineered nanomaterials and biomolecules. Nanoconjugates with cells, organelles, and intracellular structures containing DNA, RNA, and proteins establish sequences of nano–bio boundaries that depend on several intricate complex biophysicochemical reactions. Given the complexity of these interactions, and their import in governing life at the molecular level, it is extremely important to begin to understand such nanoparticle–biomaterial association. Here we report a unique method of probing the kinematics between an energy biomolecule, adenosine triphosphate (ATP), and hydrothermally synthesized ZnO nanostructures using micro Raman spectroscopy, X-ray diffraction, and electron microscopy experiments. For the first time we have shown by Raman spectroscopy analysis that the ZnO nanostructures interact strongly with the nitrogen (N7) atom in the adenine ring of the ATP biomolecule. Raman spectroscopy also confirms the importance of nucleotide base NH2 group hydrogen bonding with water molecules and phosphate group ionization and their pH dependence. Calculation of molecular bond force constants from Raman spectroscopy reinforces our experimental data. These data present convincing evidence of pH-dependent interactions between ATP and zinc oxide nanomaterials. Significantly, Raman spectroscopy is able to probe such difficult to study and subtle nano–bio interactions and may be applied to elegantly elucidate the nano–bio interface more generally.

Here, we report the synthesis and characterization of nano-, micro-, twinned, and lonsdaleite diamonds, which are formed after melting and quenching of amorphous carbon or Q-carbon essentially at room temperature and atmospheric pressure. These conversions depend on the degree of undercooling, which is controlled by the laser parameters and thermal conductivities of the amorphous carbon and the substrate. The laser melting and undercooling provide liquid-phase packing of atoms similar to high-pressure, which facilitate the conversion of amorphous carbon into diamond or Q-carbon without using any catalyst. By changing the nucleation and growth rates, we have synthesized a wide range of sizes (4 nm to 3 μm) of diamond crystals. The formation of twinned and lonsdaleite diamonds is controlled by the quenching rate. Therefore, we have created a “factory of diamonds” at ambient conditions by nanosecond laser annealing, which will pave the pathway to design high-speed mechanical and electrical devices.Here, we report the synthesis and characterization of nano-, micro-, twinned, and lonsdaleite diamonds, which are formed after melting and quenching of amorphous carbon or Q-carbon essentially at room temperature and atmospheric pressure. These conversions depend on the degree of undercooling, which is controlled by the laser parameters and thermal conductivities of the amorphous carbon and the substrate. The laser melting and undercooling provide liquid-phase packing of atoms similar to high-pressure, which facilitate the conversion of amorphous carbon into diamond or Q-carbon without using any catalyst. By changing the nucleation and growth rates, we have synthesized a wide range of sizes (4 nm to 3 μm) of diamond crystals. The formation of twinned and lonsdaleite diamonds is controlled by the quenching rate. Therefore, we have created a “factory of diamonds” at ambient conditions by nanosecond laser annealing, which will pave the pathway to design high-speed mechanical and electrical devices.

The optical absorption coefficient is a crucial parameter in determining solar cell efficiency under operational conditions. It is well known that inorganic nanocrystals are a benchmark model for solar cell nanotechnology, given that the tunability of optical properties and stabilization of specific phases are uniquely possible at the nanoscale. A hydrothermal method was employed to fabricate nanostructured copper oxides where the shape, size and phase were tailored by altering the growth parameters, namely the base media used, the reaction temperature, and the reaction time. The nano crystalline structures, phases, morphology, molecular vibrational modes, and optical properties were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, photoluminescence (PL), and UV-vis spectroscopy. A significantly large optical absorption coefficient, of the order of twice that of Si in the visible range, was observed in a particular phase mixture of nanostructured copper oxides. An optical absorption coefficient of 7.05 10(+5) cm(-1) at 525 nm was observed in a particular nanostructured phase mixture of copper oxides which is appreciably larger than commercially pure CuO (1.19 10(+5) cm(-1)) and Si (1.72 10(+5) cm(-1)). A possible mechanism of formation of phase mixtures and morphology of copper oxides has also been discussed, which opens up a roadmap in synthesis of similar morphology nanostructures for efficient solar cells.

This article reviews the discovery of new phases of carbon (Q-carbon) and BN (Q-BN) and addresses critical issues related to direct conversion of carbon into diamond and h-BN into c-BN at ambient temperatures and pressures in air without any need for catalyst and presence of hydrogen. The Q-carbon and Q-BN are formed as a result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs. T) of carbon, and show that by rapid quenching kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled (4000 K) carbon at atmospheric pressure in air. Similarly, the hBN-cBN-Liquid triple point is shifted from 3500 K/9.5 GPa to as low as 2800 K and atmospheric pressure. It is shown that nanosecond laser heating of amorphous carbon and nanocrystalline BN on sapphire, glass and polymer substrates can be confined to melt in a super undercooled state. By quenching this super undercooled state, we have created a new state of carbon (Q-carbon) and BN (Q-BN) from which nanocrystals, microcrystals, nanoneedles, microneedles and thin films are formed. The large-area epitaxial diamond and c-BN films are formed, when appropriate planar matching or lattice matching template is provided for growth from super undercooled liquid state. Scale-up processing of diamond, c-BN and diamond/c-BN heterostructures and related nanostructures such as nanodots, microdots, nanoneedles, microneedles and large-area single-crystal thin films will have tremendous impact on applications ranging from abrasive and tool coatings to high-power devices and myriad of biomedical applications.

Here, we report the electrochromic effect in undoped Q-carbon. This unique phase of carbon, Q-carbon, is formed by pulsed laser melting of amorphous carbon and subsequent ultrafast quenching process. The excess amount of unpaired electrons near the Fermi energy level in the Q-carbon causes a 48% increase in the optical absorption at 265 nm with an applied electric field of 10 V. The Kelvin probe force microscopy (KPFM) also indicates that the Fermi level of Q-carbon is situated ∼40 meV higher than that in the neighboring diamond-like carbon region. It is also observed that, with an increase in the tip voltage from 0 to 10 V in KPFM, there occurs an increase in the image phase contrast thereby indicating an increase in the concentration of electrons. This causes an increase in optical absorbance with the application of an electric field in Q-carbon. The direct and indirect optical band gaps in Q-carbon are calculated to be 3.82 and 2.93 eV, respectively, using the Tauc analysis. High-resolution scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction pattern depict the formation and amorphous nature of Q-carbon. Raman and electron energy-loss spectroscopy of Q-carbon reveal over 75% sp3-bonded carbon (rest sp2) and excess electrons near the Fermi level. This discovery of electrochromic effect in Q-carbon shows that highly non-equilibrium synthesis can be elegantly used to fabricate smart windows with immense energy-saving applications.Here, we report the electrochromic effect in undoped Q-carbon. This unique phase of carbon, Q-carbon, is formed by pulsed laser melting of amorphous carbon and subsequent ultrafast quenching process. The excess amount of unpaired electrons near the Fermi energy level in the Q-carbon causes a 48% increase in the optical absorption at 265 nm with an applied electric field of 10 V. The Kelvin probe force microscopy (KPFM) also indicates that the Fermi level of Q-carbon is situated ∼40 meV higher than that in the neighboring diamond-like carbon region. It is also observed that, with an increase in the tip voltage from 0 to 10 V in KPFM, there occurs an increase in the image phase contrast thereby indicating an increase in the concentration of electrons. This causes an increase in optical absorbance with the application of an electric field in Q-carbon. The direct and indirect optical band gaps in Q-carbon are calculated to be 3.82 and 2.93 eV, respectively, using the Tauc analysis. High-resolution scanning el...

Following a brief report on high-temperature superconductivity in B-doped Q-carbon [Bhaumik et al., ACS Nano 11(6), 5351–5357 (2017)], we present detailed structure-property correlations to understand the origin of superconductivity in strongly bonded lightweight materials and methods to further enhance the superconducting transition temperature (Tc). Nanosecond melting of carbon in a super undercooled state and rapid quenching result in a strongly bonded unique phase of B-doped Q-carbon. The temperature-dependent resistivity and magnetic susceptibility measurements demonstrate type II superconductivity in this material with a transition temperature of 36.0 ± 0.5 K and an upper critical field of 5.4 T at ∼0 K. It has also been shown that in B-doped Q-carbon, the upper critical magnetic field (Hc2(T)) follows Hc2(0) [1-(T/Tc)2.1] temperature dependence and is consistent with the Bardeen–Cooper–Schrieffer formalism. In the present study, B-doped Q-carbon thin films are formed on sapphire substrates by emplo...

Physical properties of reduced graphene oxide (rGO) are strongly dependent on the ratio of sp2 to sp3 hybridized carbon atoms and the presence of different functional groups in its structural framework. This research for the very first time illustrates successful wafer scale integration of graphene-related materials by a pulsed laser deposition technique, and controlled conversion of p to n-type 2D rGO by pulsed laser annealing using a nanosecond ArF excimer laser. Reduced graphene oxide is grown onto c-sapphire by employing pulsed laser deposition in a laser MBE chamber and is intrinsically p-type in nature. Subsequent laser annealing converts p into n-type rGO. The XRD, SEM, and Raman spectroscopy indicate the presence of large-area rGO onto c-sapphire having Raman-active vibrational modes: D, G, and 2D. High-resolution SEM and AFM reveal the morphology due to interfacial instability and formation of n-type rGO. Temperature-dependent resistance data of rGO thin films follow the Efros-Shklovskii variable...

The present study details facile synthesis of hollow Cu2O nanospheres decorated with Ag nanoparticles using a simple surfactant technique for enhanced photocatalytic activity. The morphology and structure is studied via XRD and SEM. Cu2O hollow nanospheres with a diameter of 500-800 nm were synthesized via Ostwald ripening using CuSO4 aqueous solution. The catalytic activity of Cu2O is studied in the presence of UV and visible light using Methyl Orange (MO) as a model pollutant. Ag decorated Cu2O particles showed a 49% increase in photocatalytic activity over the undecorated Cu2O. The improved photocatalytic activity is achieved by surface plasmon resonance effects in the silver nanoparticles, allowing utilization of the lower energy portion of the solar spectrum.

Physical properties of reduced graphene oxide (rGO) strongly depend on the ratio of sp2 to sp3 hybridized carbon atoms, the presence of different functional groups, and the characteristics of the substrates. This research for the very first time illustrates successful wafer scale integration of 2D rGO with Cu/TiN/Si, employing pulsed laser deposition followed by laser annealing of carbon-doped copper layers using nanosecond excimer lasers. The XRD, SEM, and Raman spectroscopy measurements indicate the presence of large area rGO onto Si having Raman active vibrational modes: D, G, and 2D. A high resolution SEM depicts the morphology and formation of rGO from zone-refined carbon formed after nanosecond laser annealing. Temperature-dependent resistance data of rGO thin films follow the Efros-Shklovskii variable range hopping (VRH) model in the low-temperature region and Arrhenius conduction in the high-temperature regime. The photoluminescence spectra also reveal a less intense and broader blue fluorescence ...

We review the discovery of new phases of carbon (Q-carbon) and BN (Q-BN) and address critical issues related to direct conversion of carbon into diamond and hBN into cBN at ambient temperatures and pressures in air without any need for catalyst and the presence of hydrogen. The Q-carbon and Q-BN are formed as a result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs T) of carbon, and show that by rapid quenching, kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. Similarly, the hBN-cBN-Liquid triple point is shifted from 3500 K/9.5 GPa to as low as 2800 K and atmospheric pressure. It is shown that nanosecond laser heating of amorphous carbon and nanocrystalline BN on sapphire, glass, and polymer substrates can be confined to melt in a super undercooled state. By quenching this super undercooled state, we have created a new state of carbon (Q-carbon) and BN (Q-BN) from which nanocrystals, microcrystals, nanoneedles, microneedles, and thin films are formed depending upon the nucleation and growth times allowed and the presence of growth template. The large-area epitaxial diamond and cBN films are formed, when appropriate planar matching or lattice matching template is provided for growth from super undercooled liquid. The Q-phases have unique atomic structure and bonding characteristics as determined by high-resolution SEM and backscatter diffraction, HRTEM, STEM-Z, EELS, and Raman spectroscopy, and exhibit new and improved mechanical hardness, electrical conductivity, and chemical and physical properties, including room-temperature ferromagnetism and enhanced field emission. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g−1. We have also deposited diamond on cBN by using a novel pulsed laser evaporation of carbon and obtained cBN/diamond composites, where cBN acts as template for diamond growth. Both diamond and cBN grown from super undercooled liquid can be alloyed with both p- and n-type dopants. This process allows carbon to diamond and hBN to cBN conversions and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp3 bonding for diamond and cBN phases.

We have created a new state of BN (named Q-BN) through rapid melting and super undercooling and quenching by using nanosecond laser pulses. Phase pure c-BN is formed either by direct quenching of super undercooled liquid or by nucleation and growth from Q-BN. Thus, a direct conversion of hexagonal boron nitride (h-BN) into phase-pure cubic boron nitride (c-BN) is achieved by nanosecond pulsed laser melting at ambient temperatures and atmospheric pressure in air. According to the P-T phase diagram, the transformation from h-BN into c-BN under equilibrium processing can occur only at high temperatures and pressures, as the hBN-cBN-Liquid triple point is at 3500 K/9.5 GPa or 3700 K/7.0 GPa with a recent theoretical refinement. Using nonequilibrium nanosecond laser melting, we have created super undercooled state and shifted this triple point to as low as 2800 K and atmospheric pressure. The rapid quenching from super undercooled state leads to the formation of a new phase, named as Q-BN. We present detailed ...

We report the discovery of a new phase of carbon (referred to as Q-carbon) and address fundamental issues related to direct conversion of carbon into diamond at ambient temperatures and pressures in air without any need for catalyst and presence of hydrogen. The Q-carbon is formed as result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs. T) of carbon and show that by rapid quenching kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. It is shown that nanosecond laser heating of diamond-like amorphous carbon on sapphire, glass, and polymer substrates can be confined to melt carbon in a super undercooled state. By quenching the carbon from the super undercooled state, we have created a new state of carbon (Q-carbon) from which nanodiamond, microdiamond, microneedles, and single-crystal thin films are formed depending upon the nucleation and growth times allowed for diamond formation. The Q-carbon quenched from liquid is a new state of solid carbon with a higher mass density than amorphous carbon and a mixture of mostly fourfold sp3 (75%–85%) with the rest being threefold sp2 bonded carbon (with distinct entropy). It is expected to have new and improved mechanical hardness, electrical conductivity, chemical, and physical properties, including room-temperature ferromagnetism (RTFM) and enhanced field emission. Here we present interesting results on RTFM, enhanced electrical conductivity and surface potential of Q-carbon to emphasize its unique properties. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g−1. From the Q-carbon, diamond phase is nucleated and a variety of micro- and nanostructures and large-area single-crystal diamond sheets are grown by allowing growth times as needed. Subsequent laser pulses can be used to grow nanodiamond into microdiamond and nucleate other nanostructures of diamond on the top of existing microdiamond and create novel nanostructured materials. The microstructural details provide insights into the mechanism of formation of nanodiamond, microdiamond, nanoneedles, microneedles, and single-crystal thin films. This process allows carbon-to-diamond conversion and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp3 bonding for diamond formation.We report the discovery of a new phase of carbon (referred to as Q-carbon) and address fundamental issues related to direct conversion of carbon into diamond at ambient temperatures and pressures in air without any need for catalyst and presence of hydrogen. The Q-carbon is formed as result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs. T) of carbon and show that by rapid quenching kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. It is shown that nanosecond laser heating of diamond-like amorphous carbon on sapphire, glass, and polymer substrates can be confined to melt carbon in a super undercooled state. By quenching the carbon from the super undercooled state, we have created a new state of carbon (Q-carbon) from which nanodiamond, microdiamond, microneedles, and single-crystal thin films are formed depending up...

We examine the role of solvents in the performance of pentacene devices using the ferroelectric copolymer poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFe) as a gate insulating layer. High dipole moment solvents, such as dimethyl sulfoxide (DMSO), used to dissolve the copolymer for spincasting, increase the charge carrier mobility in field-effect transistors by nearly an order of magnitude as compared to lower dipole moment solvents. The polarization in Al/PVDF-TrFe/Au metal-ferroelectric-metal devices is also investigated. An increase in remnant polarization of ∼20% is observed in the sample using DMSO as the ferroelectric solvent. The DMSO based sample shows a hysteresis in its displacement curve even at the lowest measured voltage, indicating that the dipoles in the copolymer are more ordered initially.

We report on the ferroelectricity for morphotropic-phase-boundary lead (Pb) free 0.5BaTi0.8Zr0.2O3-0.5Ba0.7Ca0.3TiO3 (0.5BZT-0.5BCT) thin films. Thin films were grown on Pt/Ti/SiO2/Si substrate using pulsed laser deposition. Raman spectroscopic data combined with the X-ray diffraction analyses confirm body centered tetragonal crystallographic structure 0.5BZT-0.5 BCT thin films on Pt/Ti/SiO2/Si. Polarization studies demonstrate that these 0.5BZT-0.5BCT films exhibit a large remnant and saturation polarization of 37 μC/cm2 and 40 μC/cm2, respectively, with a coercive field of 140 kV/cm. A correlation between polarization dynamics, structural distortion, and phonon vibration is established. The splitting of X-ray diffraction peak of the thin film in the 2θ range of 44.5° to 46.5° represents high degree of tetragonality. The tetragonality factor calculated by Rietveld analysis was found to be 0.006 and can be a major cause for the increased remnant polarization value. It is established from Raman spectra that the non-centrosymmetricity due to the displacement of Ti/Zr ions from its octahedral position is related to the peak position as well as the broadening of the A1 (LO) optical phonon mode. This increase of broadness in the thin film causes an increase in the dipole moment of the unit cell and, hence, the net increase in polarization values.