Improving the mobility of CuPc OFETs by varying the preparation conditions

In this work, three different preparation conditions were used for testing the performance of p-conducting copper phthalocyanine (CuPc) organic field-effect transistors (OFETs). The charge carrier mobility (μ _sat=(1.5±0.6)×10^?3 cm²/V?s) of the CuPc OFETs with the CuPc film deposited while keeping the substrate at room temperature could be improved when the gate dielectric was modified by a self-assembled monolayer of n-octadecyltrichlorosilane (μ _sat=(3.8±0.4)×10^?3 cm²/V?s) or when elevated temperatures were applied to the substrate (T _S,av=127 ^°C) during the deposition of the organic film (μ _sat=(6.5±0.8)×10^?3 cm²/V?s). For the latter case, the dependence of the mobility and threshold voltage with increasing thickness of the organic film was tested—above 13 nm film thickness, no further significant increase of the hole mobility or change in the threshold voltage could be observed. The environmental stability of the OFETs was checked by performing ex situ measurements immediately as the sample was exposed to atmosphere and after 40 days of exposure. The effect of the different preparation conditions on the morphology of the organic films prepared in this work is also discussed in this context.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Calorimetric study of proton ordering in hexagonal ice catalyzed by hydrogen fluoride

Heat capacities of hexagonal ices doped with 2.6, 26 and 260 m mol dm^?3 HF were measured with an adiabatic calorimeter. The HF doping accelerated proton ordering which has been known to take place sluggishly around 100 K. The ice containing 26 m mol dm^?3 HF showed the largest excess entropy ((0.102±0.01) J K^?1 mol^?1) and the shortest relaxation time. The relaxation time at 90 K was about $\text{1}\text{30}$ of that of the pure ice I_h at the same temperature. The activation enthalpies obtained were the same for all of the doped ices, (23.5±2.0) J mol^?1, which is approximately equal to the activation energy of the mobility of the Bjerrum L-defect.     

Electrical properties of proton conducting solid biopolymer electrolytes based on starch–chitosan blend

Two systems (salted and plasticized) of starch–chitosan blend-based electrolytes incorporated with ammonium chloride (NH₄Cl) are prepared via solution cast technique. The incorporation of 25 wt% NH₄Cl has maximized the room temperature conductivity of the electrolyte to (6.47?±?1.30)?×?10^?7 S cm^?1. Conductivity is enhanced to (5.11?±?1.60)?×?10^?4 S cm^?1 on addition of 35 wt% glycerol. The temperature dependence of conductivity for all electrolytes is Arrhenian, and the value of activation energy (E _a ) decreases with increasing conductivity. Conductivity is found to be influenced by the number density (n) and mobility (μ) of ions. The complexation between the electrolytes components is proven by Fourier transform infrared analysis. The relaxation time (t _r ) for selected electrolytes is found to decrease with increasing conductivity and temperature. Conduction mechanism for the highest conducting electrolyte in salted and plasticized systems is determined by employing Jonscher’s universal power law.     

The analysis of symmetric rotor Raman spectra: The pure rotational spectrum of 11BF3

The pure rotational Raman spectrum of ¹¹BF₃ has been photographed. Great care was taken in the analysis to consider all the unresolved components under each observed Raman line profile. If this is ignored, systematic errors result. The final set of molecular constants obtained was B₀ = 0.34502(±3 × 10^?5)cm^?1, D_J = 4.38(±0.10) × 10^?7cm^?1, and D_JK = ?9.1(±1.0) × 10^?7cm^?1.     

Iodine as a donor in CdS

Iodine doped single crystals of CdS were grown from the vapor phase. High temperature Hall effect measurements for the crystals equilibrated with Cd and S₂ vapors at temperatures between 700 and 1000°C gave the free electron concentration as a function of p_Cd or p_S2 and temperature. The results can be explained on the basis of a model in which the CdS is saturated with iodine at low p_Cd (=high p_S2) but unsaturated at high p_Cd.The solubility of iodine in CdS is given by c_t=1·73×10²²p_S2^?1/8 exp (?1·045 eV/kT) cm^?3 atm^?1/8=4·62×10¹⁹p_Cd^1/4 exp (?0·195 eV/kT) cm^?3 atm^1/4The formation of pairs (I_SV_Cd)′ from I_S^· and V_Cd″ is governed by the equilibrium constant K_{P(I, V)}=4 exp (≤1·1 eV/kT)If Cd diffusion occurs primarily by free vacancies, the Cd^* tracer self diffusion leads to a vacancy mobility of (1·2±0·5)×10^?5 cm² sec^?1 at 900°C, in agreement with results reported by Woodbury [12], but (7±3) times larger than reported by Kumar and Kroger [10].     

Coherent Stokes and anti-Stokes Raman spectra of the ν1 (A1) and ν2 (E) bands of SF6 and UF6

Coherent Stokes and anti-Stokes Raman scattering are used to study the ν₁ and ν₂ spectral band profiles of UF₆ and SF₆. Most of the observed SF₆ “hot” bands are assigned, leading to evaluations of the anharmonicity constants X_ij: X₁₂ = ?(2.80 ± 0.30) cm^?1, X₁₄ = ?(1.00 ± 0.15) cm^?1, X₁₅ = ?(1.00 ± 0.15) cm^?1. For UF₆, a tentative assignment of the “hot” bands is made: X₁₂ = ?(1.80 ± 0.30) cm^?1, X₁₃ = ?(1.60 ± 0.30) cm^?1, X₁₄ = ?(0.20 ± 0.10) cm^?1, X₁₅ = ?(0.25 ± 0.10) cm^?1, and X₁₆ = ?(0.10 ± 0.05) cm^?1. Parameters such as the vibration-rotation coupling constants are determined. For SF₆: α = (7 ± 2) × 10^?5 cm^?1 for the ν₂ band and α = ?(1.02 ± 0.01) 10^?4 cm^?1 for the ν₁ band. The calculated spectral profiles of the coherent Stokes or anti-Stokes spectra, which are in good agreement with experimental results, give values for the resonant and nonresonant parts of the susceptibility in both molecules. They also show, in some cases, the influence of neighboring combination bands.     

Orientational and positional disorder of ions and its freezing in the CsNO2-TlNO2 system2

The heat capacities of Cs_0.695Tl_0.305NO₂ (Specimen I) and Cs_0.385Tl_0.615NO₂ (Specimen II) have been measured between 14 and 350 K. Specimen I underwent a phase transition at (197.7 ± 0.1) K, with ΔS = (19.2 ± 1.5) JK^?mol^?, and specimen II at (214.5 ± 0.2) K, with ΔS = (5.4 ± 1.0) JK^?1mol^?1, respectively. Above the phase transition, an exothermic temperature drift due to phase separation was observed. Annealing of the sample at 203 K for 300 hr brought about complete phase separation. The solid solution system annealed at 203 K gave two heat capacity peaks at (203.3 ± 0.1) K, with ΔS = (13.8 ± 0.8) JK^?1 mol^?1, and (242.4 ± 0.2) K, with ΔS = (10.6 ± 1.3) JK^?1 for Specimen I, and at (203.0 ± 0.1) K with ΔS = (6.7 ± 0.5) JK^?1 mol^?1, and (257.5 ± 0.2) K with ΔS = (17.9 ± 1.7) JK^?1 mol^?1 for Specimen II. The phase diagram of the CsNO₂-TlNO₂ binary system was constructed on the basis of DTA, heat capacity and dielectric measurements. In the metastable phase, the existence of a residual entropy due to the freezing of a random distribution of Cs⁺₁ and Tl⁺ cations in addition to the orientational disorder of the NO₂^?1 ion was confirmed by a comparison of entropies of the stable and the metastable phases.     

Electron paramagnetic resonance of Dy3+ in cubic ZnSe and Tm3+ in hexagonal CdS single crystals

Electron paramagnetic resonance has been observed for Dy³⁺ in ZnSe and Tm³⁺ in CdS. For Dy³⁺ doped ZnSe, an isotropic spectrum was observed having well resolved hyperfine lines due to ¹⁶¹Dy and ¹⁶³Dy. The g value obtained was 6.577 ± 0.002 and ¹⁶¹A was 191 ± 1 × 10⁴ cm^?1 and ¹⁶³A was 265 ± 3 × 10^?4 cm^?1. The agreement of the observed g value to g(τ₆) = 6.667 and the point-charge calculations suggest that Dy³⁺ occupies an interstitial (II) site with no local charge compensation. For Tm³⁺ doped in hexagonal CdS, an axial spectrum consistent with g_⊥ = 0, g_∥ = 10.722 ± 0.007, D = 2.57 GHz (crystal field splitting) and ¹⁶⁹A = 1207 ± 5 × 10^?4cm^?1. The large g_∥ value indicates that the Tm ion exits in the trivalent state. This is in reasonable agreement with previous reports of the non-Kramer's state of Tm³⁺.     

Determination of A0 for CH335Cl and CH337Cl from the ν4 infrared and Raman bands

The ν₄ infrared and Raman bands of CH₃Cl were analyzed simultaneously. A direct fit yielded a complete set of constants for CH₃³⁵Cl, including A₀ = 5.20530 ± 0.00010 cm^?1 and D_K = (8.85 ± 0.13) × 10^?5cm^?1. For CH₃³⁷Cl an incomplete set of constants was obtained from the infrared band, and A₀ = 5.2182 ± 0.0010 cm^?1 was estimated by curve fitting of the Raman spectrum. The resulting equilibrium structure is $\text{r(}\text{CH) = 1.0854 ± 0.0005}\text{A}\text{?}$, $\text{r(}\text{CCl) = 1.7760 ± 0.0003}\text{A}\text{?}$, and <(HCH) = 110°.35 ± 0°.05.     

Mössbauer studies of europium and ytterbium hydrides

Mössbauer absorption spectra were obtained for the 21·6 ke V transition of ¹⁵¹Eu in EuH₂ at various temperatures and for the 84·3 keV transition of ¹⁷⁰Yb in YbH₂ at 4·1°K. The isomer shift of EuH₂ relative to Eu³⁺: Sm₂O₃ is ? 12·1 ± 0·3 mm. sec^?1, and the magnetic hyperfine field equals ? 305 ± 5 kOe at saturation. The Curie temperature is found to be 16·2 ± 0·05°K, and the critical parameters of the transition are D = 1·17 ± 0·02 and β = 0·35 ± 0·01. The magnetic field is perpendicular to the principal axis of the electric field gradient and the values of the quadrupole hyperfine interaction e²qQ₀(3 cos² θ ? 1)/8 is ? 28 ± 4 Mc . sec^?1. A large increase of the resonance area (21%) occurs at the transitio to the ferromagnetic state. The isomer shift of YbH₂ relative to Yb: TmAl₂ is ?0·11 ± 0·01 mm . sec^?1. The value of the quadrupole coupling constant e²qQ_c/4is ? 91·5 ± 2 Mc . sec^?1 and the asymmetry parameter of the electric field gradient equals 0·89 ± 0·05. The data for EuH₂ and YbH₂ is shown to be consistent with the hydridic model for the rare earth hydrides.     

The vibrational numbering and improved constants of the A3Π1u state of I2

The A-X system of I₂ has been recorded in absorption, under conditions of medium resolution, over the region 8000 – 13 400 Å. Bandheads in progressions based on v″ = 6 through 18 have been measured and assigned. A new vibrational numbering for the A state is proposed, which leads to more reliable values for the important constants of the A state: T_e = 10 906 ± 3 cm^?1, D_e = 1641 ± 3 cm^?1, ω_e = 92.5 ± 0.5 cm^?1, ω_ex_e = 1.20 ± 0.08 cm^?1, ω_ey_e = ?0.062 ± 0.006 cm^?1.     

EPR of Cu2+ Impurities in Cytosine Hydrochloride: A Case of Superhyperfine Structure

Electron paramagnetic resonance spectra of Cu²⁺ impurities in cytosine hydrochloride single crystals are observed at liquid nitrogen temperature. Two magnetically equivalent sites for Cu²⁺ have been observed. The parameters of ⁶³Cu obtained with the fitting of spectra to rhombic symmetry spin Hamiltonian are: g _x  = 2.047 ± 0.002, g _y  = 2.187 ± 0.002, g _z  = 2.390 ± 0.002, A _x  = (86 ± 3) × 10^?4 cm^?1, A _y  = (87 ± 3) × 10^?4 cm^?1, and A _z  = (138 ± 3) × 10^?4 cm^?1. The observed bands in optical spectra of the single crystal recorded at room temperature are assigned to various d–d and charge-transfer transitions. Using both EPR and optical data, the nature of bonding of metal ion with different ligands is discussed.     

Infrared diode-laser spectrum of the CH3CN ν2 band: Analysis of local resonances with ν6±1 + 2ν8±2, ν4 + ν7±1 + ν8±1, ν4 + ν6±1, ν4 + ν7±1, and 2ν70 + ν8±1 states

Fifty-one sections of infrared diode-laser spectra of acetonitrile have been measured in the region from 2283.5 to 2235.7 cm^?1. About 450 transitions belonging to the ν₂ band have been assigned for K ≦ 7 and J ≦ 44. Anomalies found in the rotational structure have been proven to be due to five local resonances. Observed transition frequencies have been fitted by a least-squares method to a model which includes Fermi-type resonances (Δk = 0, Δ? = ± 3n) with ν₆^±1 + 2ν₈^±2 and ν₄ + ν₇^±1 + ν₈^±1 states, x, y-type Coriolis resonances (Δk = ±1, Δ? = ?3n ± 1) with ν₄ + ν₆^±1 and ν₄ + ν₇^±1 + ν₈^±1 states, and a centrifugal-distortion-type resonance (Δk = ±2, Δ? = ?3n ± 2) with a 2ν₇⁰ + ν₈^±1 state. The 11 × 11 dimensional energy matrix has been diagonalized in order to obtain the perturbed energy levels. The standard deviation for the fit is 1.075 × 10^?3 cm^?1. The molecular constants determined are also listed.     

Temperature dependence of Mn2+ EPR in Sn2P2S6 near the phase transition

The X-band EPR spectrum of Mn²⁺ in Sn₂P₂S₆ was studied in the temperature rangeT=223–363 K. At room temperature the spin-Hamiltonian constants areg=2.00±0.01,B ₂ ⁰ =(163±3)·10^?4 cm^?1,B ₂ ² =(159±3)·10^?4 cm^?1,A=?(75±1)·10^?4 cm^?1. The effect of the invariance in temperature of the resonance magnetic fields in the narrow temperature rangeT=337–340 K and the model of the paramagnetic centre are discussed. According to EPR data a phase transition occurs atT=337 K. This transition from the paraelectric phase to the ferroelectric one is accompanied by a dramatic change in value of the spin-Hamiltonian constantB ₂ ⁰ .     

Mößbauereffekt in FeCl2, FeSO4 und FeSO4 · 7 H2O

Mößbauereffect measurements were performed with FeCl₂, FeSO₄ and FeSO₄ · 7 H₂O in the temperature range between 5 and 300 ?K. The quadrupole splittings at 5 ?K were determined to be (1.300±0.027) mm/sec, (3.650±0.053) mm/sec, and (3.350±0.053) mm/sec respectively. From the temperature dependence of the quadrupole splittings it follows that in FeCl₂ the energy of the excited 3d-electron-level isδ=150 cm^?1, in FeSO₄ δ ₁=360 cm^?1 andδ ₂=1680 cm^?1 and in FeSO₄ · 7 H₂Oδ ₁=480 cm^?1 andδ ₂=1300 cm^?1. The magnitudes of the magnetic field at the iron nucleus at 5 ?K are (202±8) kOe for FeSO₄ and (0±4) kOe for FeCl₂.     

Tunable laser Stark-difference spectra of CD3OH

We present Doppler resolution limited spectra of the P(J) and R(J) multiplets for J ≦ 10 of the 10-μm CO stretch band of ¹²CD₃¹⁶OH using a tunable diode laser. Relative frequencies within the multiplets accurate to ±0.0002–0.0005 cm^?1 are obtained, but no absolute frequencies are given. We are able to assign most of the hindered rotation and K substructure in these multiplets. The assignments are based on analyses of Stark-difference spectra combined with the ground-state microwave data and the intensity variations which are expected theoretically. The ground and excited state A, K = 1 asymmetry splitting parameters are measured to be δ₁″ = (8.5450 ± 0.0080) × 10^?3cm^?1 and δ₁′ = (9.7706 ± 0.0080) × 10^?3cm^?1, respectively. The ground-state value agrees well with the microwave results. A rapid-scan system for recording data and a computer-aided technique for calibrating and plotting the spectra are described.     

Isomer shift in BaSnO3 under a pressure up to 15 GPa

The dependence of the unit cell volume of BaSnO₃ on the pressure up to 15 GPa has been investigated and the constants of the Murnaghan equation of state B ₀ = 178.39 ± 4.09 GPa and B′₀ = 4.68 ± 0.56 have been obtained using the X-ray diffraction method. The change of the isomer shift (IS) in BaSnO₃ with a variation in the pressure P has been examined using the gamma resonance method. This quantity is ?IS(P)/?P = ?(0.00474 ± 0.0002) mm s^?1 GPa^?1 or, taking into account the measurements of the unit cell parameter under pressure, ?IS/?L = 1.42 mm s^?1Å^?1, where L is the tin-oxygen distance.     

Intensities and half-widths at different temperatures for the 201III←000 band of CO2 at 4854 cm−1

Measurements made at temperatures of 197, 233, and 294°K of the absolute intensities and self-broadening coefficients for the vibration-rotation lines of the 201_III←000 band of the ¹²C¹⁶O₂ molecule, are reported. From these measurements, values have been derived for the vibration-rotation interaction factor (F_VR), the purely vibrational transition moment (|R(O)|), and the intensity (S_Band). The results are: E_VR(m) = 1+(2.2±0.7)×10^?3m+(5.6±1.6)×10^×5m², |R(0)| = (2.064±0.017)×10^?3 debye, S_Band = 21,329±69 cm^?1km^?1atm^?1_STP. The results for the self-broadening coefficients are presented in the text.     

Some nuclear and atomic properties of201Hg determined by conversion electron spectroscopy

Conversion electron measurements with an electrostatic spectrometer proved the existence of the 1,565±6 eV transition in²⁰¹Hg. The conversion intensity ratios,N ₁/N ₂ =1.2±0.2,N ₁/N ₃=1.1±0.2,N ₂/N ₃=0.92±0.15,N ₄/N ₃=0.03± 0.02 andN ₅/N ₃=0.04 ±0.02 were determined. These values agree with our calculations for the M1±E2 multipolarity with theE2/M1 mixing ratioδ ²=(l.l±0.3)xl0^?4 and exclude all pure multipolarities withL≦4. The total conversion coefficient for the aboveM1 +E2 mixture was evaluated to be (4.7±0.7)× 10⁴. The reducedB(M1, 1/2→3/2) probability was derived to be (3.9 ±1.2) × 10^?3 (e?/2Mc)². The natural widths of theN-subshell conversion lines in mercury were found to beΓ(N ₁)=8.3± 1.5,Γ(N ₂) =5.8±1.5 and Γ(N ₃) =6.5±1.0 eV. Monte Carlo calculations of electron scattering in matter yielded the conversion line shapes in qualitative agreement with the experiment.