Determination of electron affinity of electron accepting molecules

The unoccupied π ^* states of the solid film of electron accepting organic molecules, 7,7,8,8-tetracyanoquinodimethane (TCNQ), fluorinated TCNQ derivatives, 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (TNAP), C₆₀, and 6,6-phenyl-C₆₁-butyric acid methyl ester (PCBM) have been studied by inverse photoemission spectroscopy. The assignment of the π ^* affinity levels of these typical electron accepting molecules provides the basic information for the organic electronics and the new electronic functional molecular design. The comparison with density functional theory calculations enables understanding how the electron affinity evolves in terms of molecular orbitals. The correlation between the film morphology and the irradiation damage on the TCNQ derivative samples by electron impact during the inverse photoemission measurements is also discussed.     

Impurity band in SnBi<Subscript>4</Subscript>Se<Subscript>7</Subscript>: thermoelectric power and electrical resistivity measurements

Thermoelectric power and electrical resistivity measurements on polycrystalline samples of Bi₂Se₃ and stoichiometric ternary compound in the quasi-binary system SnSe–Bi₂Se₃ in the temperature range of 90–420 K are presented and explained assuming the existence of an impurity band. The variation of the electron concentration with temperature above 300 K is explained in terms of the thermal activation of a shallow donor, by using a single conduction band model. The density of states effective mass m ^*=0.15m ₀ of the electrons, the activation energy of the donors, their concentration, and the compensation ratio are estimated. The temperature dependence of the electron mobility in conduction band is analyzed by taking into account the scattering of the charge carriers by acoustic phonon, optical phonon, and polar optical phonon as well as by alloy and ionized impurity modes. On the other hand, by considering the two-band model with electrons in both the conduction and impurity bands, the change in the electrical resistivity with temperature between 420 and 90 K is explained.     

Unoccupied electronic states and the interface formation between oligo(phenylene-vinylene) films and a Ge(111) surface

Thin films of tri-oligo(phenylene-vinylene) end-terminated by di-butyl-thiole (tOPV) were thermally deposited in UHV on Ge(111) substrates. The surface potential and the structure of unoccupied electron states (DOUS) located 5–20 eV above the Fermi level (E _F) were monitored during the film deposition using an incident beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. The electronic work function of the surface changed during the film deposition until it reached a stable value of 4.3±0.1 eV at a tOPV film thickness of 8–10 nm. Deposition of the tOPV under 3 nm led to the formation of intermediate DOUS structures that were replaced by another DOUS structure along with an increase in the tOPV deposit thickness up to 8–10 nm. The occurrence of the intermediate DOUS structure is indicative of a substantial reconfiguration of the electronic structure of the tOPV molecules due to the interaction with the Ge(111) surface. Analysis of the TCS data allowed us to assign the unoccupied electronic bands in tOPV located at 5.5–6.5 and 7.5–9.5 eV above the E _F as π* bands and at 11–14 and 16–19 eV above E _F as σ* bands.     

Azobenzene-functionalized alkanethiols in self-assembled monolayers on gold

Self-assembled monolayers (SAMs) of 4-trifluoromethyl-azobenzene-4′-methyleneoxy-alkanethiols (CF₃– C₆H₄–N=N–C₆H₄–O–(CH₂) _n –SH on (111)-oriented poly-crystalline gold films on mica were examined by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The spectra are analyzed with the help of density-functional-theory calculations of the isolated molecule. Only one doublet is detected in the sulphur 2p spectra of the investigated SAMs, consistent with a thiolate bond of the molecule to the gold surface. The C 1s XP spectra and the corresponding XAS π ^* resonance exhibit a rich structure which is assigned to the carbon atoms in the different chemical surroundings. Comparing XPS binding energies of the azobenzene moiety and calculated initial-state shifts reveals comparable screening of all C 1s core holes. While the carbon 1s XPS binding energy lies below the π ^*-resonance excitation-energy, the reversed order is found comparing core ionization and neutral core excitation of the nitrogen 1s core-hole of the azo group. This surprising difference in core-hole binding energies is interpreted as site-dependent polarization screening and charge transfer among the densely packed aromatic moieties. We propose that a quenching of the optical excitation within the molecular layer is thus one major reason for the low trans to cis photo-isomerization rate of azobenzene in aromatic-aliphatic SAMs.     

Optical surface absorption by surface-adsorbate charge-transfer excitations

Metal-insulator-silver junctions are well suited to measure genuine surface optical excitations, especially electronic transitions to the lowest unoccupied molecular orbitals (LUMO) of adsorbates on silver. This is demonstrated by the increase of internal photoemission current after monolayer coverage with C₂H₄ (which has π^*-LUMO) by a factor of about 2.5, but a missing change in the case of C₂H₆ (which has no π^*-LUMO ). Received: 26 November 1999 / Published online: 8 March 2000     

Unoccupied surface states on the (111) surface of silver: Evidence for broadening

We have studied Ag(111) withk-resolved inverse photoemission spectroscopy athv=9.7 eV. In normal incidence we find image-state emission atE _vac–(0.4±0.1) eV and the unoccupied part of an intrinsic surface-state band as a huge emission peak cut byE _F. The energy dispersion of the intrinsic surface-state band and in particular its crossing ofE _F predicted by Ho et al. cannot be observed because of broadening effects as is shown by a theoretical simulation. The broadening is due to the vicinity of the surface state to the bulk continuum nearE _F as suggested by Kevan.     

Sensitive detection of temperature behind reflected shock waves using wavelength modulation spectroscopy of CO2 near 2.7?μm

Tunable diode-laser absorption of CO₂ near 2.7 μm incorporating wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) is used to provide a new sensor for sensitive and accurate measurement of the temperature behind reflected shock waves in a shock-tube. The temperature is inferred from the ratio of 2f signals for two selected absorption transitions, at 3633.08 and 3645.56 cm⁻¹, belonging to the ν ₁+ν ₃ combination vibrational band of CO₂ near 2.7 μm. The modulation depths of 0.078 and 0.063 cm⁻¹ are optimized for the target conditions of the shock-heated gases (P∼1–2 atm, T∼800–1600 K). The sensor is designed to achieve a high sensitivity to the temperature and a low sensitivity to cold boundary-layer effects and any changes in gas pressure or composition. The fixed-wavelength WMS-2f sensor is tested for temperature and CO₂ concentration measurements in a heated static cell (600–1200 K) and in non-reactive shock-tube experiments (900–1700 K) using CO₂–Ar mixtures. The relatively large CO₂ absorption strength near 2.7 μm and the use of a WMS-2f strategy minimizes noise and enables measurements with lower concentration, higher accuracy, better sensitivity and improved signal-to-noise ratio (SNR) relative to earlier work, using transitions in the 1.5 and 2.0 μm CO₂ combination bands. The standard deviation of the measured temperature histories behind reflected shock waves is less than 0.5%. The temperature sensor is also demonstrated in reactive shock-tube experiments of n-heptane oxidation. Seeding of relatively inert CO₂ in the initial fuel-oxidizer mixture is utilized to enable measurements of the pre-ignition temperature profiles. To our knowledge, this work represents the first application of wavelength modulation spectroscopy to this new class of diode lasers near 2.7 μm.     

Line strength and collisional broadening studies of hydrogen sulphide in the 1.58 μm region using diode laser spectroscopy

High resolution diode laser spectroscopy has been applied to the detection of hydrogen sulphide at ppm levels utilizing different transitions within the region of the ν ₁+ν ₂+ν ₃ and 2ν ₁+ν ₂ combination bands around 1.58 μm. Suitable lines in this spectral region have been identified, and absolute absorption cross sections have been determined through single-pass absorption spectroscopy and confirmed in the Doppler linewidth regime using cavity enhanced absorption spectroscopy (CEAS). The desire for a sensitive system potentially applicable to H₂S sensing at atmospheric pressure has led to an investigation on suitable transitions using wavelength modulation spectroscopy (WMS). The set-up sensitivity has been calculated as 1.73×10⁻⁸ cm⁻¹ s^1/2, and probing the strongest line at 1576.29 nm a minimum detectable concentration of 700 ppb under atmospheric conditions has been achieved. Furthermore, pressure broadening coefficients for a variety of buffer gasses have been measured and correlated to the intermolecular potentials governing the collision process; the H₂S–H₂S dimer well depth is estimated to be 7.06±0.09 kJ mol⁻¹.     

Magnetotransport properties of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> with different grain sizes

The magnetotransport and magnetoresistive (MR) properties of manganese-based La_0.67Ca_0.33MnO₃ perovskite with different grain sizes are reported. The electrical resistivity was measured as a function of temperature in magnetic fields of 0.5 and 1 T. The insulator–metal transition temperature, T _IM, shifted to a higher temperature with the application of the magnetic field. In zero field, T _IM is almost constant (∼271 K) for all samples except for the sample with the largest grain size, where T _IM=265 K. The temperature dependence of resistivity was fitted with several equations in the metallic (ferromagnetic) region and the insulating (paramagnetic) region. The density of states at the Fermi level, N(E _F), and the activation energy of electron hopping were estimated by fitting the resistivity versus temperature curves. The ρ–T ² curves are nearly linear in the metallic regime, but the ρ–T ^2.5 curves exhibit a deviation from linearity. The variable range hopping model and small polaron hopping model fit the data well in the high-temperature region, indicating the existence of the Jahn–Teller distortion that localizes the charge carriers. MR was found to increase with an increase in the magnetic field, an effect which is attributed to the intergrain spin tunneling effect.     

3s- and 3p-core level excitations in 3d-transition metal oxides from electron-energy-loss spectroscopy

3s- and 3p-core level excitations for a large number of 3d-transition metal oxides, with a formal 3d occupation from 3d⁰ to 3d¹⁰, have been measured by electron energy loss spectroscopy in reflection geometry (REELS) with primary energies 200 eV≤E ₀≤1600 eV. Their intensities decrease systematically with the formal 3d-count, classifying them as transitions to empty 3d-states. The structure of the 3s excitations is analysed in detail and is compared to the 3s-XPS photoemission spectra of the samples. This 3s-REELS structure and its change with the 3d occupation can be explained by the assumption that the excitation arises mainly from a 3s²3dⁿ→3s¹3dⁿ⁺¹ quadrupole transition.     

Synthesis of nanometric iron oxide films by RPLD and LCVD for thermo–photo sensors

Iron oxide films were deposited on <100> Si substrates by reactive pulsed laser deposition (RPLD) using a KrF laser (248 nm). These films were deposited too by laser (light) chemical vapor deposition (LCVD) using continuous ultraviolet photodiode radiation (360 nm). The deposited films demonstrated semiconducting properties. These films had large thermo-electromotive force (e.m.f.) coefficient (S) and high photosensitivity (F). For films deposited by RPLD the S coefficient varied in the range 0.8–1.65 mV/K at 205–322 K. This coefficient depended on the band gap (E _g ) of the semiconductor films, which varied in the range 0.43–0.93 eV. The largest F value found was 44 V_c/W for white light at power density I≅0.006 W/cm². Using LCVD, iron oxide films were deposited from iron carbonyl vapor. For these films, the S coefficient varied in the range −0.5 to 1.5 mV/K at 110–330 K. The S coefficient depended on E _g of the semiconductor films, which varied in the range 0.44–0.51 eV. The largest F value of these films was about 40 V_c/W at the same I≅0.006 W/cm². Our results showed that RPLD and LCVD can be used to synthesize iron oxide thin films with variable stoichiometry and, consequently, with different values of E _g . These films have large S coefficient and high photosensitivity F and therefore can be used as multi-parameter sensors: thermo–photo sensors.     

New search for processes violating the Pauli exclusion principle in sodium and in iodine

In this paper a new search for non-Paulian nuclear processes, i.e. processes normally forbidden by the Pauli Exclusion Principle (PEP), is presented. It has been carried out at the Gran Sasso National Laboratory of the INFN by means of the highly radiopure DAMA/LIBRA set-up (sensitive mass of about 250 kg highly radiopure NaI(Tl)). In particular, a new improved upper limit for the spontaneous non-Paulian emission rate of protons with energy E _p ≥ 10 MeV in ²³Na and ¹²⁷I has been obtained: 1.63 × 10⁻³³ s⁻¹ (90% C.L.). The corresponding limit on the relative strength (δ ²) for the searched non-Paulian transition is δ ²≲(3–4)×10⁻⁵⁵ (90% C.L.). Moreover, PEP-violating electron transitions in iodine atoms have also been investigated. Lifetimes shorter than 4.7×10³⁰ s are excluded at 90% C.L.; this allows us to derive the limit δ _e ²<1.28×10⁻⁴⁷ (90% C.L.). This latter limit can also be related to a possible finite size of the electron in composite models of quarks and leptons providing superficial violation of the PEP; the obtained upper limit on the electron size is r ₀<5.7×10⁻¹⁸ cm (energy scale of E≳3.5 TeV).     

Precise determination of?optical properties of?pentacene thin films grown on various substrates: Gauss–Lorentz model with effective medium approach

Spectroscopic ellipsometry measurements are performed on thin pentacene films grown on glass, SiO₂, and n-Si substrates. The Gauss–Lorentz oscillator model is shown to be effective in modeling the π–π ^∗ transitions found in organic compounds. The effective medium approximation that considers the surface roughness of the films, which can be significant in case of pentacene, is also shown to be a key factor in precisely determining their dielectric functions. The proposed method reveals that there are some quantitative differences in the optical properties of the pentacene films prepared on different substrates.     

Solid polymeric electrolyte of PVC–ENR–LiClO<Subscript>4</Subscript>

The ionic conductivity of PVC–ENR–LiClO₄ (PVC, polyvinyl chloride; ENR, epoxidized natural rubber) as a function of LiClO₄ concentration, ENR concentration, temperature, and radiation dose of electron beam cross-linking has been studied. The electrolyte samples were prepared by solution casting technique. Their ionic conductivities were measured using the impedance spectroscopy technique. It was observed that the relationship between the concentration of salt, as well as temperature, and conductivity were linear. The electrolyte conductivity increases with ENR concentration. This relationship was discussed using the number of charge carrier theory. The conductivity–temperature behaviour of the electrolyte is Arrhenian. The conductivity also varies with the radiation dose of the electron beam cross-linking. The highest room temperature conductivity of the electrolyte of 8.5 × 10⁻⁷ S/cm was obtained at 30% by weight of LiClO₄. The activation energy, E _a and pre-exponential factor, σ _o, are 1.4 × 10⁻² eV and 1.5 × 10⁻¹¹ S/cm, respectively.     

Er<Superscript>3+</Superscript> as glass structure modifier of Ga–Ge–S chalcogenide system

Er³⁺ clustering phenomenon in Ga–Ge–S chalcogenide system is studied using Raman spectroscopy. The Raman spectra from 10 to 500 cm⁻¹ for glasses (100−y)[15Ga₂S₃–85GeS₂]–yEr₂S₃ (y=0.08−5.00 mol. %) have been analyzed. To reveal the influence of the chemical composition on the glass structure the intensity of the peak corresponding to Ge–Ge (Ga–Ga) homopolar bonds has been examined. The peak intensity increase with Er₂S₃ concentration change in the region 0<C(Er₂S₃)<2 mol. % has been interpreted in terms of the sulphur deficiency in the glass resulting in the formation of S₃Ge–GeS₃ (S₃Ga-GaS₃) structural units. The further increase in concentration beyond 2 mol. % reduces the sulphur deficiency, which can be attributed to the formation of the ternary compound Er₃GaS₆. The structural units Er₃GaS₆ contain a large mol. fraction of Er³⁺ or, in other words, Er³⁺ clusters. The data obtained from the low-frequency Raman spectra (boson band) indicate strong variations of the medium-range order (MRO) in the glasses induced by Er³⁺. The observed behavior of the MRO size (the correlation length) with increasing of Er₂S₃ concentration provides for additional evidence of the Er³⁺ clustering.     

Cooperative downconversion and near-infrared luminescence of Tb<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> codoped lanthanum borogermanate glasses

In the present paper, we investigate the near-infrared (NIR) luminescence of Tb³⁺–Yb³⁺ codoped lanthanum borogermanate (LBG) glasses under visible and ultraviolet light excitation. The results indicate that NIR quantum cutting occurs through cooperative energy transfer from Tb³⁺ to Yb³⁺ ions when only 4f ⁸ levels of Tb³⁺ ions are excited in the wavelength region of 300–490 nm. The highest quantum efficiency under the excitation ⁵ D ₄ level of Tb³⁺ at 484 nm is 146%. Ultraviolet excitation that populates the charge transfer band (CTB) of Yb³⁺ near 270 nm does not result in quantum cutting as the fast nonradiative decay from CTB to ² F _5/2 level dominates. These materials are expected to be used as a converting layer for silicon solar cells to enhance their efficiency by splitting each high-energy photon into two NIR photons.     

Kinetic analysis of the photochemically and thermally induced isomerization of an azobenzene derivative on Au(111) probed by two-photon photoemission

Two-photon photoemission (2PPE) spectroscopy is employed to quantify the photochemically and thermally induced trans ⇌ cis isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on an Au(111) surface. The isomerization of TBA is accompanied by significant changes in the electronic structure, namely different energetic positions of the lowest unoccupied molecular orbital of both isomers and the appearance of an unoccupied final state for cis-TBA. A quantitative analysis of these effects allows the calculation of cross sections for the reversible isomerization and determination of the ratio between both isomers in the photostationary state, where 55±5% of the molecules are switched to cis-TBA. The cross section for the photoinduced trans → cis isomerization is 3.3±0.5×10⁻²² cm², while for the back reaction, a value of 2.7±0.5×10⁻²² cm² is obtained. Furthermore a pronounced reduction of the activation energy by a factor of four compared to the free molecule is found for the thermally activated cis → trans isomerization of the surface-adsorbed TBA. This demonstrates that the potential energy landscape of the adsorbed TBA is remarkably different from the liquid phase.     

Structure and magnetic properties of Zn<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O nanorods synthesized by a simple sol–gel method using metal acetylacetonate and poly(vinyl alcohol)

Room-temperature ferromagnetism was observed in Zn_0.9Co_0.1O nanorods with diameters and lengths of ∼100–200 nm and ∼200–1000 nm, respectively. Nanorods were synthesized by a simple sol–gel method using metal acetylacetonate powders of Zn and Co and poly(vinyl alcohol) gel. The XRD, FT-IR and SAED analyses indicated that the nanorods calcined at 873–1073 K have the pure ZnO wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. The specific magnetization of the nanorods appeared to increase with a decrease in the lattice constant c of the wurtzite unit cell with the highest value being at 873 K calcination temperature. This magnetic behavior is similar to that of Zn_0.9Co_0.1O nanoparticles prepared by polymerizable precursor method. We suggest that this behavior might be related to hexagonal c-axis being favorable direction of magnetization in Co-doped ZnO and the 873 K (energy of 75 meV) being close to the exciton/donor binding energy of ZnO.     

Vertical electrical conduction in pentacene polycrystalline thin films mediated by Au-induced gap states at grain boundaries

Vertical electrical conduction in Au/(polycrystal-line pentacene)/Al diode structures and the influence of the kinetic energy of incident Au atoms on the conduction property have been comprehensively studied using current–voltage–temperature (I–V–T) measurements, ultraviolet photoelectron spectroscopy (UPS), atomic-force-microscope (AFM) current imaging, etc. In the I–V characteristics, a symmetrical ohmic current component appeared when a low voltage was applied, and a super-linear one appeared when a high positive voltage was applied to Au. The component in the high-forward-voltage region was concluded to be a thermionic emission of holes from Au with a 0.23-eV injection barrier, which is the normal hole conduction through the highest occupied molecular orbital of pentacene. On the other hand, the ohmic component was concluded to be a metal-like electron transport through high-density gap states at grain boundaries which were induced by the Au penetration into pentacene. UPS and I–V–T measurements clearly indicated the generation of the gap states and the enhancement of their density by the reduction of Au kinetic energy. For vertical-type devices with polycrystalline organic films, the ohmic conduction through the grain boundary will increase the leakage current. On the contrary, it possibly enhances the carrier injection in lateral-type transistors in the case of top-contact configuration.     

A natural bond orbital analysis of aryl‐substituted polyfluorinated carbanions: negative hyperconjugation

Aryl‐substituted polyfluorinated carbanions, ArCHR_f^? where R_f = CF₃ ( 1 ), C₂F₅ ( 2 ), i‐C₃F₇ ( 3 ), and t‐C₄F₉ ( 4 ), were analyzed by means of the natural bond orbital (NBO) theory at the B3LYP/6‐311+G(d,p) computational level. A lone pair NBO at the formal anionic center carbon (Cα) was not found in the Lewis structure. Instead, significant donor/acceptor NBO interactions between π(Cα‐C1) and σ*(Cβ‐F) or σ*(Cβ‐Cγ) were observed for 1 , 2 , 3a (strong electron‐withdrawing substituent, from p‐CF₃ to p‐NO₂), and 4 . Their second‐order donor/acceptor perturbation interaction energy, E(2), values decreased with the increase of the stability of carbanions. A larger E(2) value corresponds to longer Cβ‐F and Cβ‐Cγ bonds and a shorter Cα‐Cβ bond, indicating that the E(2) values can be associated with the negative hyperconjugation of the Cβ‐F and Cβ‐Cγ bonds. In accordance with this, the E(2) values for π(Cα‐C1) → σ*(Cβ‐F) were linearly correlated with the ΔG^o_β‐F values (an empirical measure of β‐fluorine negative hyperconjugation obtained from an increased acidity). In 3b (weak electron‐withdrawing substituents, from H to m‐NO₂) very large E(2) values for LP(Fβ) → π*(Cα‐Cβ) were obtained. This was attributed to the Cβ‐F bond cleavage and the Cα‐Cβ double bond formation in the Lewis structure that is caused by the extremely strong negative hyperconjugation of the Cβ‐F bond.