Chemical bonding and electronic structures at magnesium/copper phthalocyanine interfaces

Chemistry, electronic structure and electrical behavior at the interfaces between copper phthalocyanine (CuPc) and Mg with a reverse formation sequence were investigated using X-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), and current-voltage (I-V) measurements. A chemical reaction occurs between CuPc and Mg irrespective of the deposition sequence. Despite having different reaction zone thicknesses, both the CuPc-on-Mg and the Mg-on-CuPc interfaces exhibit chemistry-induced gap states and identical carrier injection barriers, which are confirmed by the symmetric electrical behavior obtained from I-V characteristics of devices with a structure of Mg/CuPc/Mg. These findings contrast with those expected from physisorptive noble metal-CuPc interfaces and suggest that strong local chemical bonding is a primary factor determining molecular level alignment at reactive metal-CuPc interfaces.     

Chemisorption at interfaces between organic semiconductors and metals: role of the electron affinity

Chemisorption is a well-known phenomenon for many interfaces between organic semiconductors and metals. It is shown that many published data indicate that the occurrence of chemisorption can be rationalized upon the consideration of the metal work function versus the electron affinity of the organic semiconductor.     

Temperature dependence of the current-voltage characteristics of the Al/Rhodamine-101/p-Si(1 0 0) contacts

The current-voltage (I-V) characteristics of Al/Rhodamine-101/p-Si/Al contacts have been measured at temperatures ranging from 280 to 400 K at 20 K intervals. A barrier height (BH) value of 0.817 eV for the Al/Rh101/p-Si/Al contact was obtained at the room temperature that is significantly larger than the value of 0.58 eV of the conventional Al/p-Si Schottky diode. While the barrier height Φ_b0 decreases the ideality factors (n) become larger with lowering temperature. The high values of n depending on the sample temperature may be ascribed to decrease of the exponentially increase rate in current due to space-charge injection into Rh101 thin film at higher voltage. Therefore, at all temperatures, it has been seen that the I-V characteristics show three different regions, the ohmic behavior at low voltages, and the space charge limited current with an exponential distribution of traps at high voltages.     

The electronic structure of alkali-metal layers on semiconductor surfaces

Alkali-metal layers on semiconductor surfaces are model systems for metal-semiconductor contacts, Schottky barriers, and metallization processes. The strong decrease of the work function as a function of alkali-metal coverage is also technically made use of. Recently, however, interest in these systems is growing owing to ongoing controversial discussions about questions like: Is the adsorbate system at monolayer coverage metallic or semiconducting, and does the metallization take place in the alkali overlayer or in the top layer of the semiconductor? Is the bonding ionic or covalent? What ist the absolute coverage at saturation? What are the adsorption sites? Do all alkali metals behave similar on the same semiconductor surface? We try to answer some of the questions for Li, Na, K and Cs on Si(111)(2×1), K and Cs on Si(111)(7×7) and on GaAs(110), and Na and K on Si(100)(2×1) employing the techniques of direct and inverse photoemission.     

Investigation of electrical properties of organic 4-tricyanovinyl-N,N-diethylaniline thin film

Thin films of 4-tricyanovinyl-N,N-diethylaniline (TCVA) with different thickness were prepared using thermal evaporation technique. A relative permittivity, ?_r, of 3.04 was estimated from the dependence of capacitance on film thickness. The current density-voltage (J-V) characteristics of TCVA thin films have been investigated at different temperatures. At low-voltage region, the current conduction in the Au/TCVA/Au sandwich structures obeys Ohm's law. At the higher-voltage regions, the charge transport phenomenon appears to be space-charge-limited current (SCLC) dominated by an exponential distribution of traps with total trap concentration of 1.21 × 10²² m⁻³. In addition, various electrical parameters were determined.     

Current transport mechanism in Al/Si3N4/p-Si (MIS) Schottky barrier diodes at low temperatures

The current-voltage (I-V) and capacitance-voltage (C-V) characteristics of metal-insulator-semiconductor (Al/Si₃N₄/p-Si) Schottky barrier diodes (SBDs) were measured in the temperature range of 80-300 K. By using the thermionic emission (TE) theory, the zero-bias barrier height Φ_B0 calculated from I-V characteristics was found to increase with increasing temperature. Such temperature dependence is an obvious disagreement with the negative temperature coefficient of the barrier height calculated from C-V characteristics. Also, the ideality factor decreases with increasing temperature, and especially the activation energy plot is nonlinear at low temperatures. Such behaviour is attributed to Schottky barrier inhomogeneties by assuming a Gaussian distribution of barrier heights (BHs) at interface. We attempted to draw a Φ_B0 versus q/2kT plot to obtain evidence of a Gaussian distribution of the BHs, and the values of Φ_Bo = 0.826 eV and α_o = 0.091 V for the mean barrier height and standard deviation at zero-bias, respectively, have been obtained from this plot. Thus, a modified ln(I_o/T²) − q²σ_o²/2(kT)² versus q/kT plot gives Φ_B0 and Richardson constant A^* as 0.820 eV and 30.273 A/cm² K², respectively, without using the temperature coefficient of the barrier height. This value of the Richardson constant 30.273 A/cm² K² is very close to the theoretical value of 32 A/cm² K² for p-type Si. Hence, it has been concluded that the temperature dependence of the forward I-V characteristics of the Al/Si₃N₄/p-Si Schottky barrier diodes can be successfully explained on the basis of TE mechanism with a Gaussian distribution of the barrier heights. In addition, the temperature dependence of energy distribution of interface state density (N_SS) profiles was determined from the forward I-V measurements by taking into account the bias dependence of the effective barrier height and ideality factor.     

The effect of interface states, excess capacitance and series resistance in the Al/SiO2/p-Si Schottky diodes

The current-voltage (I-V) characteristics of Al/SiO₂/p-Si metal-insulator-semiconductor (MIS) Schottky diodes were measured at room temperature. In addition the capacitance-voltage (C-V) and conductance-voltage (G-V) measurements are studied at frequency range of 10 kHz-1 MHz. The higher value of ideality factor of 3.25 was attributed to the presence of an interfacial insulator layer between metal and semiconductor and the high density of interface states localized at Si/SiO₂ interface. The density of interface states (N_ss) distribution profile as a function of (E_ss − E_v) was extracted from the forward bias I-V measurements by taking into account the bias dependence of the effective barrier height (Φ_e) at room temperature for the Schottky diode on the order of ≅4 × 10¹³ eV⁻¹ cm⁻²_. These high values of N_ss were responsible for the non-ideal behaviour of I-V and C-V characteristics. Frequency dispersion in C-V and G-V can be interpreted only in terms of interface states. The N_ss can follow the ac signal especially at low frequencies and yield an excess capacitance. Experimental results show that the I-V, C-V and G-V characteristics of SD are affected not only in N_ss but also in series resistance (R_s), and the location of N_ss and R_s has a significant on electrical characteristics of Schottky diodes.     

Near-Infrared Emission from Organic Light-Emitting Diodes Based on Copper Phthalocyanine with a Periodically Arranged Alq3：CuPc/DCM Multilayer Structure

We demonstrate near-infrared organic light-emitting devices with a periodically arranged tris（8-quinolinolato）aluminum （Alq3）：copper phthalocyanine （CuPc）/4-（dicyanomethylene）-2-methyl-6-（4-dimethylaminost-yry）-4H-pyran （DCM） multilayer structure. DCM and Alq3 doped with CuPc were periodically deposited. Room-temperature electrophosphorescence was observed at about 1.1 μm due to transitions from the first excited triplet state to the singlet ground state （T1 - S0） of CuPc. In this device, we utilize the overlap between the Q band πr - π^＊ at about 625nm of the absorption spectra of CuPc and the PL spectra of the DCM. The near-infrared emission intensity of the CuPc-doped Alq3 device with DCM increases about 2.5 times larger than that of the device without DCM. We attribute the efficiency enhancement to the better overlap between the PL spectra of DCM and the absorption spectra of CuPc.     

The conductance and capacitance-frequency characteristics of Au/pyronine-B/p-type Si/Al contacts

The rectifying junction characteristics of the organic compound pyronine-B (PYR-B) film on a p-type Si substrate have been studied. The PYR-B has been evaporated onto the top of p-Si surface. The barrier height and ideality factor values of 0.67 ± 0.02 eV and 2.02 ± 0.03 for this structure have been obtained from the forward bias current-voltage (I-V) characteristics. The energy distribution of the interface states and their relaxation time have been determined from the forward bias capacitance-frequency and conductance-frequency characteristics in the energy range of ((0.42 ± 0.02) − E_v)-((0.66 ± 0.02) − E_v) eV. The interface state density values ranges from (4.21 ± 0.14) × 10¹³ to (3.82 ± 0.24) × 10¹³ cm⁻² eV⁻¹. Furthermore, the relaxation time ranges from (1.65 ± 0.23) × 10⁻⁵ to (8.12 ± 0.21) × 10⁻⁴ s and shows an exponential rise with bias from the top of the valance band towards the midgap.     

Hydrogen Sensors Based on AlGaN/AlN/GaN Schottky Diodes

Pt/AlGaN/AlN/GaN Schottky diodes are fabricated and characterized for hydrogen sensing. The Pt Schottky contact and the Ti/Al/Ni/Au ohmic contact are formed by evaporation. Both the forward and reverse currents of the device increase greatly when exposed to hydrogen gas. A shift of 0.3 V at 300 K is obtained at a fixed forward current after switching from N2 to 10%H2＋N2. The sensor responses under different concentrations from 50ppm H2 to 10%H2＋N2 at 373K are investigated. Time dependences of the device forward current at 0.5 V forward bias in N2 and air atmosphere at 300 and 373K are compared. Oxygen in air azcelerates the desorption of the hydrogen and the recovery of the sensor. Finally, the decrease of the Schottky barrier height and sensitivity Of the sensor are calculated.     

Resistance switching in Fe-doped P0.7Ca0.3MnO3 thin films

An enhanced electric-pulse-induced resistance (EPIR) switching effect is observed in the Ag/P_0.7Ca_0.3Mn_1 − xFe_xO₃/YBa₂Cu₃O₇ (Ag/PCMFO/YBCO) and Ag/(PCMFO/PCMO)/YBCO structures. Unlike in the PCMO-based EPIR devices, where the Ag/PCMO interface plays a crucial role, both the Ag/PCMFO interface and the bulk PCMFO are found to have significant contributions to the EPIR switching of the PCMFO-based device. A possible explanation is to extend the pulse-driven oxygen ion/vacancy motion model at the metal/PCMO interface region to the bulk PCMFO.     

Rapid thermal annealing induced changes on the contact of Ni/Au to N-doped ZnO

N-doped p-type ZnO (p ∼ 10¹⁸cm^-3) was grown on sapphire(0 0 0 1) substrate by metal-organic chemical vapor deposition method. Ni/Au metal was evaporated on the ZnO film to form contacts. As-deposited contacts were rectifying while ohmic behavior was achieved after thermally annealing the contacts in nitrogen environment. Specific contact resistance was determined by circular transmission line method and a minimum specific contact resistance of 8 × 10⁻⁴ Ω cm² was obtained for the sample annealed at 650 °C for 30 s. However, Hall effect measurements indicate that, as the rapid thermal annealing temperature increased up to 550 °C or higher the samples’ conductive type have changed from p-type to n-type, which may be due to the instability nature of the present-day p-type N-doped ZnO or the dissociation of ZnO caused by annealing process in N₂ ambient. Evolution of the sample's electric characteristics and the increment of metal/semiconductor interface states induced by rapid thermal annealing process are supposed to be responsible for the improvement of electrical properties of Au/Ni/ZnO.     

Effect of CO on Characteristics of AlGaN/GaN Schottky Diode

Pt Schottky diode gas sensors for CO are fabricated using A1GaN/GaN high electron mobility transistor（HEMTs）structure. The diodes show a remarkable sensor signal （3 mA, in N2, 2mA in air ambient） biased 2 V after 1% CO is introduced at 50℃. The Schottky barrier heights decrease for 36meV and 27meV in the two cases respectively. The devices exhibit a slow recovery characteristic in air ambient but almost none in the background of pure N2, which reveals that oxygen molecules could accelerate the desorption of CO and offer restrictions to CO detection.     

Photocarrier injection and the I-V characteristics of La0.8Sr0.2MnO3/SrTiO3:Nb heterojunctions

Oxide heterojunctions made of p-type La_0.8Sr_0.2MnO₃ (LSMO) and niobium-doped n-type SrTiO₃ (STO:Nb) have been fabricated by the pulsed laser deposition (PLD) technique and characterized under UV light irradiation by measuring the current-voltage, photovoltaic properties and the junction capacitance. It is shown that the heterojunctions work as an efficient UV photodiode, in which photogenerated holes in the STO:Nb substrate are injected to the LSMO film. The maximum surface hole density Q/e and external quantum efficiency γ are estimated to be 8.3×10¹² cm⁻² and 11% at room temperature, respectively. They are improved significantly in a p-i-n junction of LSMO/STO/STO:Nb, where Q/e and γ are 3.0×10¹³ cm⁻² and 27%, respectively.     

Electronic structure of AgNbO3 and NaNbO3 studied by X-ray photoelectron spectroscopy

The XPS examinations of the AgNbO₃ and NaNbO₃ single crystals and ceramics allowed estimate their average composition as Ag_1.1Nb_0.9O₃ and Na_1.2Nb_0.9O_2.9. The valence bands of the AgNbO₃ compound, formed mainly of the Nb 4d, Ag 4d and O 2p states, show an energy gap about 3 eV while for the NaNbO₃ compound consist of the O 2p states hybridized with the Nb 3d states and show an energy gap about 4 eV. The chemical shifts of these compounds suggest a mixed ionic and covalent character of the bonds. The broadening of the core level lines of AgNbO₃ suggests a stronger structural disorder in comparison with NaNbO₃ compound.     

Robust Low Voltage Program-Erasable Cobalt-Nanocrystal Memory Capacitors with Multistacked Al2O3/HfO2/Al2O3 Tunnel Barrier

A n atomic-layer-deposited Al2O3/HfO2/Al2O3 （A/H/A） tunnel barrier is in vestigated for Co nanocrystal memory capacitors. Compared to a single Al2O3 tunnel barrier, the A/H/A barrier can significantly increase the hysteresis window, i.e., an increase by 9 V for ±12 V sweep range. This is attributed to a marked decrease in the energy barriers of charge injections for the A/H/A tunnel barrier. Further, the Co-nanocrystal memory capacitor with the A/H/A tunnel barrier exhibits a memory window as large as 4.1 V for 100 μs program/erase at a low voltage of ±7 V, which is due to fast charge injection rates, i.e., about 2.4× 10^16 cm^-2 s^-1 for electrons and 1.9× 1016 cm^-2 s^-1 for holes.     

Auger electron spectroscopy of Au/NiOx contacts on p-GaN annealed in N2 and O2 + N2 ambients

We have designed a promising contact scheme to p-GaN. Au/NiO_x layers with a low concentration of O in NiO_x are deposited on p-GaN by reactive dc magnetron sputtering and annealed in N₂ and in a mixture of O₂ + N₂ to produce low resistivity ohmic contacts. Annealing has been studied of NiO_x layers with various contents of oxygen upon the electrical properties of Au/NiO_x/p-GaN. It has been found that the Au/NiO_x/p-GaN structure with a low content of oxygen in NiO_x layer provides a low resistivity ohmic contact even after subsequent annealing in N₂ or O₂ + N₂ ambient at 500 °C for 2 min.Auger depth profiles and transmission electron microscopy (TEM) micrographs reveal that while annealing in O₂ + N₂ ambient results in reconstruction of the initial deposited Au/NiO_x/p-GaN contact structure into a Au/p-NiO/p-GaN structure, annealing in N₂ brings about reconstruction into Au/p-NiO/p-GaN and Ni/p-NiO/p-GaN structures. Hence, in both cases, after annealing in N₂ as well as in O₂ + N₂ ambient, the ohmic properties of the contacts are determined by creation of a thin oxide layer (p-NiO) on the metal/p-GaN interface. Higher contact resistivities in the samples annealed in O₂ + N₂ ambient are most likely caused by a smaller effective area of the contact due to creation of voids.     

Electronic structure of semiconductor surfaces

Our present understanding of the electronic structure of semiconductor surfaces is reviewed. It is shown that photoemission and inverse photoemission are ideal techniques for probing occupied and unoccupied electronic states, respectively. All quantum numbers of an electron can be determined, i.e., energy, momentum, spin and angular symmetries. For simple systems, such as clean ordered surfaces with a small unit cell it is possible to understand the electronic structure from first-principles calculations. For complex systems, such as encountered during oxidation and dry etching one is restricted to measuring the properties determined by short-range order. Core level spectroscopy with synchrotron radiation is able to determine the oxidation state and the local bonding of surface and interface atoms.     

Electronic conduction properties of Au/C60/p-Si and C60/Au/p-Si sandwich structures: I–V and transducer characteristics

Gold-fullerite [C₆₀]-silicon (p-type) sandwich structures have been fabricated in order to investigate intrinsic cross-sectional and planar electronic conductive properties, in particular the C₆₀/p-Si p–n heterojunction. The turn-on voltage of this p–n heterojunction lies in the range 0.25–0.27 V. The I–V characteristics of the Au/C₆₀/p-Si structure are mostly defined by the bulk specific resistance of the fullerite crystal film itself (6×10⁷ Ω cm). I–V curves in the C₆₀/Au/p-Si structure are shown to be ohmic. Au/C₆₀/p-Si sandwiches irradiated with swift (300 MeV) heavy ions, (⁸⁴Kr¹⁴⁺) to a total fluence 10¹⁰ ion/cm² yield structures which are sensitive to ambient air pressure, specifically in the case of a transverse contact configuration, and if one of the contacts is located on the irradiated part of the fullerite film. The sandwich-structure sensitivity to pressure is 5×10⁻⁶ Pa⁻¹. This exceeds the sensitivity of conventional silicon pressure transducers by almost three orders of magnitude.     

Frequency dependence of the resistive switching effect in Bi2Sr2CaCu2O8+y/Ag film heterocontacts

In this work we have performed the relaxation studies “in situ” of the electron instability effect (EIE) in the heterostructures based on BSCCO single crystals. The new effect of suppression of EIE or colossal electroresistance via application of an alternating low frequency electric field to the heterojunctions in the BSCCO-based single crystals has been found. It has been shown that the top possible frequencies for observation of the effect are of the order of 10³ Hz. This fact is interpreted as accumulation of the oxygen ions driven by the electric field to the interface. On the other hand, it has been shown that the switching events are limited by two time processes: t≈1 ms and about ten seconds. The first ones are caused by rearrangement of a charge net in the degraded surface at the electric field switching. The latter are caused by oxygen diffusion to vacancies under electric field above some threshold value. The considered experimental data confirm the correlation character of the HTSC properties as Mott systems, which appears in extreme sensitivity to the doping level, in the tendency to phase separation under external actions, in the hysteresis character of the metal-insulator transition.