C60 sputtering of organics: A study using TOF-SIMS, XPS and nanoindentation

Sputtering of organic materials using a C₆₀ primary ion beam has been demonstrated to produce significantly less accumulated damage compared to sputtering with monatomic and atomic-cluster ion beams. However, much about the dynamics of C₆₀ sputtering remains to be understood. We introduce data regarding the dynamics of C₆₀ sputtering by evaluating TOF-SIMS depth profiles of bulk poly(methyl methacrylate) (PMMA). Bulk PMMA provides an ideal test matrix with which to probe C₆₀ sputter dynamics because there is a region of steady-state secondary ion yield followed by irreversible signal degradation. C₆₀ sputtering of PMMA is evaluated as a function of incident ion kinetic energy using 10 keV C₆₀⁺, 20 keV C₆₀⁺ and 40 keV C₆₀⁺⁺ primary ions. Changes in PMMA chemistry, carbon accumulation and graphitization, and topography as a function of total C₆₀ ion dose at each accelerating potential is addressed.     

Negative group velocity in C60 due to RSA effect

We experimentally observed negative group velocity in C₆₀ toluene solution at the wavelength of 532 nm for the first time. The observed time advancement of the modulated signal appears to be due to the RSA (reverse saturable absorption) effect of the C₆₀ molecule. The largest time advancement of 71.65 ms was obtained with a C₆₀ sample of 1.5-mm length with the concentration of 1.39×10^-3 mol/l; the corresponding group velocity was -0.021 m/s. We could control the group velocity by adjusting the modulation frequency and the input intensity. PACS 42.65.-k; 42.50.Ct; 41.20.Jb     

EPR of C60 thermal/photochemical reactions with polystyrene and polymethyl methacrylate

Thermal and photochemical free radical reaction products of C₆₀ with polymethyl methacrylate (PMMA) and polystyrene (PS) in orthodichlorobenzene solution were detected by EPR (electron paramagnetic resonance). Thermal radicals (<100°C) of C₆₀/PMMA and C₆₀/PS samples gave single line first-derivative EPR spectra withg=2.0029. Ultraviolet photolysis of a C₆₀/PMMA solid phase sample gave two radical species; whereas, photolysis of a C_60/PS solid phase sample gave only one free radical. EPR signals were also recorded for UV and thermal C₆₀ reaction with free radical initiator, azobis(isobutyronitrile).     

Sputtering yields of PMMA films bombarded by keV C60 ions

A quartz crystal microbalance (QCM) has been used to determine total-mass sputtering yields of PMMA films by 1-16 keV C₆₀^+,2+ ion beams. Quantitative sputtering yields for PMMA are presented as mass loss per incident ion Y_m. Mass-lost rate QCM data show that a 13 keV C₆₀ cluster leads to emission equivalent to 800 PMMA molecules per ion. The power law obtained for the increase in sputtering yield with primary ion energy is in good agreement those predicted by “thermal spike” regime and MD models, when crater sizes are used to estimate sputtering.     

A high mobility C60 field-effect transistor with an ultrathin pentacene passivation layer and bathophenanthroline/metal bilayer electrodes

C₆₀ field-effect transistor (OFET) with a mobility as high as 5.17 cm²/V·s is fabricated. In our experiment, an ultrathin pentacene passivation layer on poly-(methyl methacrylate) (PMMA) insulator and a bathophenanthroline (Bphen)/Ag bilayer electrode are prepared. The OFET shows a significant enhancement of electron mobility compared with the corresponding device with a single PMMA insultor and an Ag electrode. By analysing the C₆₀ film with atomic force microscopy and X-ray diffraction techniques, it is shown that the pentacene passivation layer can contribute to C₆₀ film growth with the large grain size and significantly improve crystallinity. Moreover, the Bphen buffer layer can reduce the electron contact barrier from Ag electrodes to C₆₀ film efficiently.     

The effect of gamma irradiation on electrical and dielectric properties of Al-TiW-Pd2Si/n-Si Schottky diode at room temperature

The effects of ⁶⁰Co (γ-ray) irradiation on the electrical and dielectric properties of Al-TiW-Pd₂Si/n-Si Schottky diodes (SDs) have been investigated by using capacitance-voltage (C-V) and conductance-voltage (G/ω-V) measurements at room temperature and 500 KHz. The corrected capacitance and conductance values were obtained by eliminating the effect of series resistance (R_s) on the measured capacitance (C_m) and conductance (G_m) values. The high-low frequency capacitance (CHF-CLF) method given in [12] as N_ss = (1/qA) [((1/C_LF) − (1/C_ox))⁻¹ −  ((1/C_HF) − (1/C_ox))⁻¹] was successfully adapted to the before-after irradiation capacitance given in this report as N_ss = (1/qA) [((1/C_bef) − (1/C_ox))⁻¹ − ((1/C_after) − (1/C_ox))⁻¹] for the analyzing the density of interface states. The N_ss-V plots give a distinct peak corresponding to localized interface states regions at metal and semiconductor interface. The experimental values of the ac electrical conductivity (σ_ac), the real (M′) and imaginary (M″) parts of the electrical modulus were found to be strong functions of radiation and applied bias voltage, especially in the depletion and accumulation regions. The changes in the dielectric properties in the depletion and accumulation regions stem especially from the restructuring and reordering of the charges at interface states and surface polarization whereas those in the accumulation region are caused by series resistance effect.     

The role of adsorption of dodecylethyldimethylammonium bromide and benzyldimethyldodecylammonium bromide surfactants in wetting of polytetrafluoroethylene and poly(methyl methacrylate) surfaces

The role of adsorption of dodecylethyldimethylammonium bromide (C₁₂(EDMAB)) and benzyldimethyldodecylammonium bromide (BDDAB) at water-air and polytetrafluoroethylene (PTFE)-water and poly(methyl methacrylate) (PMMA)-water interface, in wetting of PTFE and PMMA surface, was established from the measured values of the contact angle (θ) of aqueous C₁₂(EDMAB) and BDDAB solutions in PTFE (PMMA)-solution drop-air system, and from the measured values of the surface tension of aqueous C₁₂(EDMAB) and BDDAB solutions. Adsorption of C₁₂(EDMAB) and BDDAB at water-air interface was determined earlier from the Gibbs equation. Adsorption at solid-water interface was deduced from the Lucassen-Reynders equation based on the relationship between adhesion tension (γ_LV cos θ) and surface tension (γ_LV). The slope of the γ_LV cos θ-γ_LV curve was found to be constant and equal to −1, and about −0.3 for PTFE and PMMA surface, respectively (in the case of both surfactant studied: C₁₂(EDMAB) and BDDAB, and in the whole range of surfactants concentration in solution). It means that the amount of the surfactant adsorbed at the PTFE-water interface, Γ_SL, was essentially equal to its amount adsorbed at water-air interface, Γ_LV. However, Γ_SL at the PMMA-water interface was about three times smaller as compared to that at water-air interface. By extrapolating the linear dependence between γ_LV cos θ-γ_LV and dependence between cos θ-γ_LV and cos θ = 1 we determined the value of the critical surface tension of PTFE and PMMA surface wetting, γ_c. The obtained values of γ_c for PTFE surface were equal 23.4 and 23.8 mN/m, 23.1 and 23.2 mN/m for C₁₂(EDMAB) and BDDAB, respectively and they were higher than the surface tension of PTFE (20.24 mN/m). On the other hand, the obtained values of γ_c for PMMA surface were equal 31.4 and 30.9 mN/m, 31.7 and 31.3 mN/m for C₁₂(EDMAB) and BDDAB, respectively and they were smaller than the surface tension of PMMA (39.21 mN/m). Using the values of PTFE and PMMA surface tension and the measured values of the surface tension of aqueous C₁₂(EDMAB) and BDDAB solutions in the Young equation, the PTFE (PMMA)-solution interfacial tension, γ_SL, was also determined. Next, the work of adhesion (W_A) was deduced, and it occurred that the dependence between the W_A and the surface tension (γ_LV) for both studied solids was linear. However, the values of the W_A for PMMA change as a function of log C (C—surfactant concentration) changed from 91.7 to 68.5 mJ/m² and from 91.8 to 65.1 mJ/m² for C₁₂(EDMAB) and BDDAB, respectively. On the other hand, the work of adhesion of both studied surfactants solutions to the PTFE surface was practically constant (an average value was equal 45.8 and 45.4 mJ/m², respectively). These values were close to the value of the work of water adhesion to PTFE surface (45.5 mJ/m²).     

Processing of C<Subscript>60</Subscript> thin films by Matrix-Assisted Pulsed Laser Evaporation (MAPLE)

Thin films of fullerenes (C₆₀) were deposited onto silicon using matrix-assisted pulsed laser evaporation (MAPLE). The deposition was carried out from a frozen homogeneous dilute solution of C₆₀ in anisole (0.67 wt%), and over a broad range of laser fluences, from 0.15 J/cm² up to 3.9 J/cm². MAPLE has been applied for deposition of fullerenes for the first time and we have studied the growth of thin films of solid C₆₀. The fragmentation of C₆₀ fullerene molecules induced by ns ablation in vacuum of a frozen anisole target with C₆₀ was investigated by matrix-assisted laser desorption/ionization (MALDI). Our findings show that intact fullerene films can be produced with laser fluences ranging from 0.15 J/cm² up to 1.5 J/cm².     

Effect of fast neutron irradiation on magnetic properties of fullerene superconductor Rb3C60

Effects of fast neutron irradiation and post-annealing on magnetic properties of Rb₃C₆₀ were studied through the dc magnetization measurement. Rb₃C₆₀ powder samples were prepared in an evacuated quartz glass tube, and the temperature and the magnetic field dependences of dc magnetization were measured before and after irradiation and after post-annealing. The neutron fluences were 1.0, 1.8 and 3.3 × 10¹⁶ n/cm², and the post-annealing was made at a temperature of 473 K for 3 h. Magnetic hysteresis of the samples irradiated at the fluence of 1.8 and 3.3 × 10¹⁶ n/cm² disappeared, and the hysteresis curves hardly changed at the fluence of 1.0 × 10¹⁶ n/cm². As for the post-annealing effect, the hysteresis curves of the sample irradiated at the fluence of 1.8 × 10¹⁶ n/cm² were completely recovered after annealing, while those of the other samples, which had a magnetic background before irradiation, were not recovered. In this study, it was found that the loss of superconductivity in Rb₃C₆₀ powder is observed when the neutron irradiation fluence exceeds 1.0 × 10¹⁶ n/cm², and the lost superconductivity is completely recovered by the post-annealing at 473 K for 3 h.     

Observation of record flux pinning in melt-textured NEG-123 superconductor doped by Nb, Mo, and Ti nanoparticles

Flux pinning in melt-processed (Nd_0.33Eu_0.33Gd_0.33)Ba₂Cu₃O_y “NEG-123” + 35 mol% Gd₂BaCuO₅ “NEG-211” (70 nm in size) composite doped by TiO₃, MoO₃ and Nb₂O₅ achieved record values. The optimum values of all three dopands were found to be around 0.1 mol%. Transmission electron microscope (TEM) analysis found clouds of <10 nm sized particles in the NEG-123 matrix, shifting the pinning particle size distribution to significantly lower values. TEM by energy dispersive X-ray spectroscopy (EDX) analysis clarified that these nanoparticles contained a significant amount of Nb, Mo, and Ti. Appearance of nanometer-sized defects correlated with a significantly improved flux pining at low and medium magnetic fields, which was particularly significant at high temperatures. In the Nb-doped sample, a record J_c value of 925 kA/cm² at the secondary peak field (4.5 T) was achieved at 65 K, 640 kA/cm² at zero field at 77 K, and 100 kA/cm² at 90.2 K, the last value having been up to now considered as a good standard for REBa₂Cu₃O_y “RE-123” materials at 77 K. The greatly improved J_c–B performance in Nb/Mo/Ti doped samples can be easily translated to large-scale LRE-123 (LRE = light rare earths, Nd, Eu, Gd, Sm) blocks intended for real superconducting super-magnets applications.     

Wheat starch + NaI: a high conducting environment friendly electrolyte system for energy devices

Energy storage devices are the lifeline of today’s society, and hence, researchers are trying to achieve 3Es (economical, environment friendly, and easy to prepare) along with other required technical data. Here, a new wheat starch + NaI system is synthesized which not only have good technical data such as high ionic conductivity (_˜3.61 × 10⁻² S/cm), very low dielectric relaxation time (_˜13.2 μs), and wide electrochemical stability window (_˜2.6 V) but it also satisfies 3Es conditions because it uses starch which is very cheap and abundant biopolymer available in large variety. The approximate cost of preparing 1 cm² of the sample is approximately INR 15. The prepared material is flexible, free standing film which can be easily stretched to 1.9 times to its length, and can be easily twisted up to 90°. The phase angle value approaches to −73° and maintains its value from 10 Hz to 9 kHz frequency range. The ESR value (of sample having thickness 0.48 mm and area 1.21 cm²) is very low (1.10 Ω). Parallel capacitance (C_p) to series capacitance (C_s) ratio is >0.9, and the value is maintained up to a wide frequency range (10 Hz to 10 kHz). Self-resonance frequency (the frequency limit below which energy can be stored efficiently) is also quite high (_˜0.1 MHz) for the present system. Hence, the studied system is a potential candidate for future electrochemical applications.

     

Molecular ion emission from single large cluster impacts

We investigated the emission of the secondary ions stimulated by single impacts of 136 keV Au₄₀₀⁴⁺ projectiles. The study was carried out on targets of glycine, phenylalanine, and C₆₀. In addition, a target of C₆₀ was examined with 18 keV C₆₀⁺ projectiles. The experiments were performed in the event-by-event bombardment/detection mode. The secondary ions were identified with linear time-of-flight mass spectrometer equipped with an 8-anode detector. The Au₄₀₀⁴⁺ projectile induces abundant multi-ion emission, for instance the average number of detected ions (atomic, fragment, molecular and cluster ions) emitted per event from glycine target is 12.5. The glycine intact molecular ion (Gly⁻) yield is 1.14. The bombardment of a C₆₀ target results in the efficient emission of multiple intact C₆₀⁻ (total yield is 0.15).     

Yb掺杂C60薄膜的x射线光电子能谱研究

在超高真空系统中制备了C₆₀的Yb填隙化合物薄膜.用x射线光电子能谱研究了Yb和C₆₀结合过程中C 1s，Yb 4f和Yb 4d的变化.利用Yb 4f和C 1s的谱峰强度确定出相纯样品的化学组分接近Yb_2.75C₆₀，这一结果与晶体x射线衍射结果一致.Yb 4f和Yb 4d的峰形与峰位表明化合物中Yb的价态为Yb²⁺.相纯样品（Yb_2.75C₆₀）的C 关键词： 60的Yb填隙化合物薄膜')" href="#">C₆₀的Yb填隙化合物薄膜 x射线光电子能谱 Yb价态     

Third-order optical nonlinearities of an organometallic complex: Bis(tetra-n-propylammonium)bis(2-thioxo-1,3-dithiole-4,5-dithiolato)cuprate(II) doped in solid PMMA films

An organometallic complex, bis(tetra-n-propylammonium)bis(2-thioxo-1,3-dithiole-4,5-dithiolato)cuprate(II), [(C₃H₇)₄N]₂[Cu(dmit)₂] (dmit^2?=4,5-dithiolate-1,3-dithiole-2-thione), abbreviated as PrCu, was synthesized. The films of PrCu were prepared using spin coating method. The third-order nonlinear optical properties of PrCu in acetone solution and PMMA films were investigated by Z-scan technique at 1064 nm with laser duration of 20 ps. The Z-scan spectra reveal that the composite films exhibit large negative nonlinear refractive indices of the order of 10^?15 m²/W, which are three orders larger than that in acetone solution. The nonlinear absorption coefficients were calculated to be 9.416×10^?10 m/W. For the composite films, the figure of merit, W and T, meet the requirement of all-optical switching devices. The experimental results show that the PrCu-doped PMMA films have potential applications for nonlinear optical devices.     

Effect of lithium salt concentration in PVAc/PMMA-based gel polymer electrolytes

Hybrid solid polymer electrolyte films comprising of poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), LiClO₄, and propylene carbonate are prepared by solution casting technique by varying the salt concentration. In this study, PVAc/PMMA polymer blend ratio is fixed as 25:75 on the basis of conductivity and mechanical stability of the film. X-ray diffraction, Fourier transform infrared impedance, thermogravimetry/differential thermal analysis and scanning electron microscopy studies are carried out for the polymer electrolytes. The maximum ionic conductivity is found to be 4.511 × 10⁻⁴ S cm⁻¹ at 303 K for the plasticized polymer electrolyte with 8 wt.% of LiClO₄. The ionic conductivity is found to decrease with an increase of LiClO₄ concentration.     

Synthesis and photophysical properties of polyamides containing in-chain porphyrin and [60]fullerene

Conjugated polyamides containing porphyrin and [60]fullerene (C₆₀) in the main chain were prepared by a direct polycondensation of the 3′H,3″H-dicyclopropa[1, 9:16, 17] [5, 6]fullerene-C₆₀-I _h -3′,3″-dicarboxylic acid and 5,15-bis(4-aminophenyl)-10,20-bis(3,5-dialkoxyphenyl)porphyrin in the presence of triphenyl phosphite and pyridine. Gel permeation chromatography (GPC) analysis of the polyamides showed the weight-average molecular weight was about 23,626–23,736, and the temperature at 5% weight loss determined by thermogravimetric analysis (TGA) was above 216 °C. The transmission electron microscopy (TEM) images displayed the regular one-dimensional linear arrays of the polyamides with lengths exceeded 200 nm. The photoinduced electron transfer from porphyrin to C₆₀ in the polyamides was observed in nanosecond laser-flash photolysis experiments at ambient temperature, which produced a charge-separated state (porphyrin radical cation–C₆₀ radical anion pair) with a lifetime as long as 40 μs. The calculated ratio of k _CS/k _CR was found to be 2.1 × 10⁴. They could have potential applications for photoelectronic devices, organic solar cells and so on.     

Stretching the limits of static SIMS with C60

Pristine and Au-covered molecular films have been analyzed by ToF-SIMS (TRIFT™), using 15 keV Ga⁺ (FEI) and 15 keV C₆₀⁺ (Ionoptika) primary ion sources. The use of C₆₀⁺ leads to an enormous yield enhancement for gold clusters, especially when the amount of gold is low (2 nmol/cm²), i.e. a situation of relatively small nanoparticles well separated in space. It also allows us to extend significantly the traditional mass range of static SIMS. Under 15 keV C₆₀⁺ ion bombardment, a series of clusters up to a mass of about 20,000 Da (Au₁₀₀⁻: 19,700 Da) is detected. This large yield increase is attributed to the hydrocarbon matrix (low-atomic mass), because the yield increase observed for thick metallic films (Ag, Au) is much lower. The additional yield enhancement factors provided by the Au metallization procedure for organic ions (MetA-SIMS) have been measured under C₆₀⁺ bombardment. They reach a factor of 2 for the molecular ion and almost an order of magnitude for Irganox fragments such as C₄H₉⁺, C₁₅H₂₃O⁺ and C₁₆H₂₃O⁻.     

Third-order nonlinear optical properties in [(C4H9)4N]2[Cu(C3S5)2]-doped PMMA thin film using Z-scan technique in picosecond pulse

An organometallic complex, [(C₄H₉)₄N]₂[Cu(C₃S₅)₂], abbreviated as BuCu, was synthesized. Then the BuCu-doped polymethylmethacrylate (PMMA) thin film with a doping concentration 1% by weight (1 wt.%) was fabricated using a spin-coating method and its third-order nonlinear optical properties were characterized using the Z-scan technique with 20 ps pulse duration at 532 and 1064 nm, respectively. The Z-scan curves have revealed that the material exhibits a self-defocusing effect at both wavelengths. Saturable absorption at 532 nm and two-photon absorption at 1064 nm were also found, respectively. Additionally, the calculated results of the material in film were compared with that of acetone solution, which indicated that the values in film were larger than that of acetone solution for about two orders in magnitude. The origins were analyzed of the difference between the two wavelengths. Our results suggest that considerable nonlinear optical properties were confirmed in BuCu-doped PMMA film. The material can easily be doped into PMMA film and forms a waveguide mode. So this material should be considered to be manufactured into devices and applied in all-optical switching, laser locking-mode, optical limiting fields etc.     

Interfacial electronic structure of molybdenum oxide on the fullerene layer,a potential hole-injecting layer in inverted top-emitting organic light-emitting diodes

The interfacial electronic structures of molybdenum oxide (MoO_x) deposited on fullerene (C₆₀) which could be used as a hole-injecting layer in inverted top-emitting organic light-emitting diodes (TE-OLEDs) were investigated by photoemission spectroscopy. The hole-injecting barrier height (Φ_B^h) at each interface investigated by an ultraviolet photoemission spectroscopy was reduced to from 1.4 to 0.1 eV as the thickness of MoO_x (Θ_MoOx) was increased from 0.1 to 5.0 nm on C₆₀. In these interface system, the sign of vacuum-level shift, highest occupied molecular orbital (HOMO)-level shift, and core-level shifts were all positive indicating that the interface mechanism is attributed to the work-function differences due to a band bending at these interfaces. Moreover, the near-edge X-ray absorption fine structure spectra at carbon K-edge did not show any structural modification as well as any chemical reaction at the MoO_x-on-C₆₀ interfaces when Θ_MoOx was changed on C₆₀. From these results, the inverted TE-OLED with C₆₀ (5.0 nm)/MoO_x (5.0 nm) showed the power efficiency of 1.7 lm/W at a luminance of about 1000 cd/m² and the maximum luminance of about 76.000 cd/m² at the bias voltage of 11.0 V. It exhibited the highest performance among the inverted TE-OLEDs fabricated as a function of MoO_x thickness from 0 to 5.0 nm.     

Model multilayer structures for three-dimensional cell imaging

The prospects for SIMS three-dimensional analysis of biological materials were explored using model multilayer structures. The samples were analyzed in a ToF-SIMS spectrometer equipped with a 20 keV buckminsterfullerene (C₆₀⁺) ion source. Molecular depth information was acquired using a C₆₀⁺ ion beam to etch through the multilayer structures at specified time intervals. Subsequent to each individual erosion cycle, static SIMS spectra were recorded using a pulsed C₆₀⁺ ion probe. Molecular intensities in sequential mass spectra were monitored as a function of primary ion fluence. The resulting depth information was used to characterize C₆₀⁺ bombardment of biological materials. Specifically, molecular depth profile studies involving dehydrated dipalmitoyl-phosphatidylcholine (DPPC) organic films indicate that cell membrane lipid materials do not experience significant chemical damage when bombarded with C₆₀⁺ ion fluences greater than 10¹⁵ ions/cm². Moreover, depth profile analyses of DPPC-sucrose frozen multilayer structures suggest that biomolecule information can be uncovered after the C₆₀⁺ sputter removal of a 20 nm overlayer with no appreciable loss of underlying molecular signal. The experimental results support the potential for three-dimensional molecular mapping of biological materials using cluster SIMS.