Interface control of conventional n-type silicon/metal by n-channel organic semiconductor

The rectifying and interface state density properties of n-Si/violanthrone-79/Au metal-diode have been investigated by current-voltage and capacitance-conductance-frequency methods. The ideality factor, barrier height and average series resistance of the diode were found to be 2.07, 0.81 eV and 5.04 kΩ respectively. At higher voltages, the organic layer contributes to I-V characteristics of the diode due to space-charge injection into the organic semiconductor layer and the trapped-charge-limited current mechanism is dominant mechanism for the diode. The barrier height obtained from C-V measurement is lower than the barrier height obtained I-V measurement and the organic layer creates an excess physical barrier for the diode. The interface state density of the diode was found to be 1.70 × 10¹¹ eV⁻¹ cm⁻² at 0.2 V and 1.72 × 10¹¹ eV⁻¹ cm⁻² at 0.4 V.The obtained electronic parameters indicate that the organic layer provides the conventional n-type silicon/metal interface control option.     

Interface electronic structure between organic semiconductor film and electrode metal probed by photoelectron yield spectroscopy

We present an investigation of the interface between organic semiconductor films and metal substrates (organic/metal interface) using photoelectron yield spectroscopy (PYS) as the probing technique. PYS studies were conducted on the pentacene/Au, copper phthalocyanine (CuPc)/Au, and perfluorinated zinc phthalocyanine (F₁₆ZnPc)/Au, and the results were compared with literature results obtained using conventional ultraviolet photoemission spectroscopy (UPS). PYS is advantageous for probing the electronic structure of the organic/metal interface because of the relatively long mean free path of photoexcited electrons with very low kinetic energy in PYS, which enables the detection of the photoelectrons from the metal substrate buried deep in the organic film. We demonstrate herein that the use of PYS reduces the significance of the final state effect of the electronic density surrounding the photohole at the organic molecule generated after the photoemission; this effect is known as the electric polarization effect. Although this effect has a significant influence on the results obtained using conventional UPS, the reduced influence of the final state effect in PYS makes it possible to construct an energy level diagram at the organic/metal interface with greater accuracy than can be achieved with UPS. In addition, a novel mechanism of the photoelectron detection for PYS enables us to apply PYS to very thick organic films, and therefore, PYS provides a reliable value of ionization energy for organic films without the influence of the substrate.Because the interface electronic structure has a significant influence on the carrier injection properties of organic devices, the increased reliability of the information obtained by PYS will render it very useful for the improvement of device performance as well for understanding their operation principles.     

Modification of metal/semiconductor junctions by self-assembled monolayer organic films

Two new metal/molecule/semiconductor contacts, Au/n-Si/TDA/Au and Au/p-Si/ODM/Au, were fabricated to understand effect of organic compounds, tridecylamine and octadecylmercaptan self-assembled monolayer (SAM) films, on electrical charge transport properties of the metal/semiconductor junctions. The morphology of the organic monolayers deposited on Si substrates was investigated by atomic force microscopy. The molecular coverage of ODM deposited on p-Si is poorer than that of TDA on n-Si substrate. The ideality factors of the p-Si/ODM and n-Si/TDA diodes were found to be 1.66 and 1.48, respectively. The electrical results show that the tridecylamine monolayer passivated junction has a lower ideality factor. The ideality factor indicates clear dependence on two different type functional groups R-SH (Thiol) and R-NH₂ (Amin) groups and it increases with different functional groups of organic molecule. The barrier height φ_b value of the n-Si/TDA diode is smaller than that of p-Si/ODM diode, as a result of chain length of the SAM organic molecules. The interface state density D_it values of the diodes were determined using conductance technique. The n-Si/TDA diode has the smaller interface state density according to p-Si/ODM diode.We have evaluated that the organic molecules control the electronic parameters of metal/semiconductor diodes and thus, organic modification helps to get one step closer towards to new organic assisted silicon based microelectronic devices.     

Improving solution-processed n-type organic field-effect transistors by transfer-printed metal/semiconductor and semiconductor/semiconductor heterojunctions

Solution-processed n-type organic field effect transistors (OFETs) are in need of proper metal contact for improving injection and mobility, as well as balanced hole mobility for building logic circuit units. We address the two distinct problems by a simple technique of transfer-printing. Transfer-printed Au contacts on a terrylene-based semiconductor (TDI) significantly reduced the inverse subthreshold slope by 5.6 V/dec and enhanced the linear mobility by over 5 times compared to evaporated Au contacts. Hence, devices with a high-work-function metal (Au) are comparable with those with low-work-function metals (Al and Ca), indicating a fundamental advantage of transfer-printed electrodes in electron injection. We also transfer-printed a poly(3-hexylthiophene) (P3HT) layer onto TDI to construct a double-channel ambipolar transistor by a solution process for the first time. The transistor exhibits balanced hole and electron mobility (3.0 × 10⁻³ and 2.8 × 10⁻³ cm² V⁻¹ s⁻¹) even in a coplanar structure with symmetric Au electrodes. The technique is especially useful for reaching intrinsic mobility of new materials, and enables significant enlargement of the material tanks for solution-processed functional heterojunction OFETs.     

Interface engineering to enhance charge injection and transport in solution-deposited organic transistors

Soluble small molecule organic semiconductors combine the high-performance of small molecule organic semiconductors with the versatile processability of polymeric materials, but the control of device performance and uniformity is challenged by the complex film microstructure formed in these materials, and its strong dependence on processing conditions. These films crystallize via a nucleation and growth mechanism that can be difficult to control. In this study we used highly fluorinated self-assembled monolayers (SAMs) to modify the surface of the source and drain contacts and improve the performance of organic thin-film transistors (OTFTs) through controlling film microstructure and lowering the contact resistance. We reached charge carrier mobilities as high as 5.7 cm²/V in 2,8-Difluoro-5,11-bis(triethylsilylethynyl) anthradithiophene (diF-TES ADT), one order of magnitude greater than what we obtained in devices on untreated substrates, and on par with the value reported for single crystal devices. Kelvin probe measurements distinguished an increase in the work function between 0.28 eV and 0.5 eV, depending on the molecular structure of the SAM. Selected area electron diffraction (SAED) confirmed the preferential “edge-on” molecular orientation of the semiconductor. We discuss the device performance in relation to the film morphology and contact resistance.     

The metal/organic monolayer interface in molecular electronic devices

The metal/molecules/metal is the basic device used to measure the electronic properties of organic molecules envisioned as the key components in molecular-scale devices (molecular diode, molecular wire, molecular memory, etc.). This review paper describes the main techniques used to fabricate a metal/molecules/metal device (or more generally electrode/molecules/electrode junctions, with electrodes made of metal or semiconductor). We discuss several problems encountered for the metallization of organic monolayers. The organic/electrode interface plays a strong role in the electronic properties of these molecular devices. We review some results on the relationships between the nature of the electrode/molecule interface (physisorbed or chemisorbed, evaporated metal electrode, mechanical contact, etc.) and the electronic transport properties of these molecular-scale devices. We also discuss the effects of symmetric versus asymmetric coupling of the two ends of the molecules with the electrodes.     

Electrical analysis of organic dye-based MIS Schottky contacts

In this work, we prepared metal/interlayer/semiconductor (MIS) diodes by coating of an organic film on p-Si substrate. Metal(Al)/interlayer(Orange GOG)/semiconductor(p-Si) MIS structure had a good rectifying behavior. By using the forward-bias I-V characteristics, the values of ideality factor (n) and barrier height (BH) for the Al/OG/p-Si MIS diode were obtained as 1.73 and 0.77 eV, respectively. It was seen that the BH value of 0.77 eV calculated for the Al/OG/p-Si MIS diode was significantly larger than the value of 0.50 eV of conventional Al/p-Si Schottky diodes. Modification of the potential barrier of Al/p-Si diode was achieved by using thin interlayer of the OG organic material. This was attributed to the fact that the OG organic interlayer increased the effective barrier height by influencing the space charge region of Si. The interface-state density of the MIS diode was found to vary from 2.79 × 10¹³ to 5.80 × 10¹² eV⁻¹ cm⁻².     

Electrical and interface state density properties of the 4H-nSiC/[6,6]-phenyl C61-butyric acid methyl ester/Au diode

The electrical and interface state density properties of the Ni/4H-nSiC/PCBM/Au diode have been investigated by current-voltage, capacitance-voltage and conductance-frequency methods. The ideality factor, barrier height and series resistance values of the diode were found to be 2.28, 1.10 eV and 3.76 × 10⁴ Ω, respectively. The diode shows a non-ideal I-V behaviour with an ideality factor greater than unity that could be ascribed to the interfacial layer, interface states and series resistance. The obtained barrier height (1.10 eV) of the Ni/4H-nSiC/PCBM/Au diode is lower than that of Ni/4H-nSiC diode (1.32 eV). This indicates that the PCBM organic layer induces a change of 160 meV in the barrier height of the Ni/4H-nSiC diode. The interface state density of the diode was determined from G_p/ω-f plots and was of order of 5.61 × 10¹² eV⁻¹ cm⁻².     

Light-driven molecular motion modifying the electronic structure and spin properties of solid organic superstructure

The polarized light acted as one of the non-contacted media could effectively tune the crystal structure to improve the physical properties. In this work, under polarized laser excitation, the molecular motion is driven inside the crystals, where the electronic structure of the crystal is affected to further change the spin and optical properties. However, decreasing the temperature to 77 K, the external polarized laser cannot produce direct molecular motion. Moreover, switching the incident laser from the linearly to circularly polarized state, the dependence of the molecular motion on the spin and optical properties show pronounced difference.     

Determination of diffusion lengths in organic semiconductors: Correlation with solar cell performances

Organic semiconductors are promising candidates for future applications in solar energy conversion. Recent investigations of bulk heterojunction (BHJ) semiconductors have suggested a density of states and transport mechanisms by multiple trapping close to those observed in disordered inorganic thin films. That is why we have applied to BHJ thin films experiments that are currently used for disordered semiconductors. In addition to the steady state photoconductivity we have tested the ability of the steady state photocarrier grating (SSPG) technique to provide information on the minority carrier diffusion length. We found that SSPG can be applied to P3HT:PCBM thin films leading, for the best sample, to a diffusion length of the order of 125 nm. From the comparison of the transport parameters obtained on thin films with the performances of the devices integrating the latter, we conclude that SSPG is a very powerful tool for optimizing the BHJ thin film properties before their incorporation in solar devices.     

Modifying organic/metal interface via solvent treatment to improve electron injection in organic light emitting diodes

By simply spin-coating the solvents, such as ethanol and methanol, on top of the organic active layer, the performance of polymer organic light-emitting diodes is significantly enhanced. The quantum efficiency is increased by as large as 58% for low work function Ba/Al cathode devices after solvent treatment. An interface dipole between the organic layer and the metal layer induced by the solvent, either from the intrinsic dipole or the interaction between the solvent and the cathode metal, is responsible for the device performance improvement. The interface dipole layer, which is confirmed by the Kelvin Probe Force Microscopy and the photovoltaic measurements, lifts the vacuum level on the metal side, thereby reducing the electron injection barrier at the organic/metal interface, and leading to better device performance.     

Facile conversion of polymer organic thin film transistors from ambipolar and p-type into unipolar n-type using polyethyleneimine (PEI)-modified electrodes

We report here a successful polarity conversion of organic thin film transistors (OTFTs) based on several polymer semiconductors with low-lying LUMO (lowest unoccupied molecular orbital) energy levels (?−4 eV) from ambipolar and even p-type into unipolar n-type devices using an ultrathin layer (∼2–5 nm) of polyethyleneimine (PEI) to modify the source and drain contacts. The work function of gold is substantially reduced with the PEI layer on its surface, which effectively suppresses the injection of holes and thus enables electron-only charge transport of these polymers in OTFTs. This general approach of electrode work function modification broadens the scope of available polymer semiconductors for use in printed electronics where n-channel OTFTs are needed.     

XPS Analysis of Surface and Interface States for PTCDA/p-Si Heterojunction

The surface and interface of heterojunction (HJ) formed with organic semiconductor (3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and inorganic semiconductor p-Si were measured and analyzed by X-ray photoelectron spectroscopy(XPS).The results indicate that ,in PTCDA molecule, the binding energy(Eb) of C is 284.6eV and 288.3eV, corresponding to C of the perylene and Cof the anhydride, respectively, and the binding energy of O is 531.3 eV and 531.1eV, corresponding to C of C=O in the anhydrides and C of C-O-C, respectively.Moreover, PTCDA lost its anhydrides and only its perylenes were left in the HJ interface.     

In situ monitoring of photovoltaic properties in organic solar cells during thermal annealing

This paper reports a simple and useful technique that monitors the changes of poly(3-hexylthiophene) (P3HT):1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C₆₁-based organic solar cells (OSCs) during thermal annealing in situ. Thermal annealing was divided into five stages in which the variations of the cell parameters were obtained in detail. Annealing temperature that was higher than the glass transition temperature of P3HT (127 °C) was found critical to the improvement of open-circuit voltage. The initial rise of the short-circuit current was explained by in situ monitoring of the transport behaviors of electrons and holes. Finally, in situ monitoring was adopted to compare OSCs that were or were not solvent-annealed, indicating the effectiveness in optimizing, modeling and understanding in depth the effects of the thermal annealing of OSC with a blended active layer.     

NTC and electrical properties of nickel and gold doped n-type silicon material

iconductor deep level energy are basically consistent with the experimental results.     

镍、金掺杂n型硅材料的NTC和电学特性

Silicon materials compensated by deep level impurities such as nickel and gold have negative temperature coefficient （NTC） characteristics. In this work, n-type silicon wafers are smeared by nickel chloride ethanol solution and gold chloric acid ethanol solution, and subsequently put in the opening environment to heat. The electrical resistance and B-value of the thermistors made by this silicon material are measured and analyzed. When the silicon surface concentration of gold atoms is 2 × 10-6 mol/cm2, the uniformity of the single-crystal silicon material is optimal. When the diffusion temperature is between 900 and 1000 ℃, a material with high B-value and low electrical resistivity is obtained. The B-T and R-T change laws calculated by the theory of semiconductor deep level energy are basically consistent with the experimental results.     

The relevance of correct injection model to simulate electrical properties of organic semiconductors

In this work we demonstrate how a full comprehensive model can be used to understand the electrical behavior of actual organic devices. We address all the aspects which need to be taken into account for realistic simulations of a wide range of device structures and configurations. In particular we stress the relevance of the correct modeling of contact/organic interfaces. The model is applied to perform predictive simulations of organic light-emitting diodes and to deduce how a full experimental characterization of an organic device should be performed in order to completely grasp its electrical behavior.     

Properties of n-type SnO2 semiconductor prepared by spray ultrasonic technique for photovoltaic applications

Transparent conducting n-type SnO₂ semiconductor films were fabricated by employing an inexpensive, simplified spray ultrasonic technique using an ultrasonic generator at deferent substrate temperatures(300, 350, 400, 450 and 500℃). The structural studies reveal that the SnO₂ films are polycrystalline at 350, 400, 450, 500℃ with preferential orientation along the(200) and(101) planes, and amorphous at 300℃. The crystallite size of the films was found to be in the range of 20.9-72.2 nm. The optical transmittance in the visible range and the optical band gap are 80% and 3.9 eV respectively. The films thicknesses were varied between 466 and 1840 nm. The resistivity was found between 1.6 and 4×10^-2 Ω·cm. This simplified ultrasonic spray technique may be considered as a promising alternative to a conventional spray for the massive production of economic SnO₂ films for solar cells, sensors and opto-electronic applications.     

Annealing temperature effect on electrical and structural properties of Cu/Au Schottky contacts to n-type GaN

Schottky contacts were fabricated on n-type GaN using a Cu/Au metallization scheme, and the electrical and structural properties have been investigated as a function of annealing temperature by current-voltage (I-V), capacitance-voltage (C-V), Auger electron spectroscopy (AES) and X-ray diffraction (XRD) measurements. The extracted Schottky barrier height of the as-deposited contact was found to be 0.69 eV (I-V) and 0.77 eV (C-V), respectively. However, the Schottky barrier height of the Cu/Au contact slightly increases to 0.77 eV (I-V) and 1.18 eV (C-V) when the contact was annealed at 300 °C for 1 min. It is shown that the Schottky barrier height decreases to 0.73 eV (I-V) and 0.99 eV (C-V), 0.56 eV (I-V) and 0.87 eV (C-V) after annealing at 400 °C and 500 °C for 1 min in N₂ atmosphere. Norde method was also used to extract the barrier height of Cu/Au contacts and the values are 0.69 eV for the as-deposited, 0.76 eV at 300 °C, 0.71 eV at 400 °C and 0.56 eV at 500 °C which are in good agreement with those obtained by the I-V method. Based on Auger electron spectroscopy and X-ray diffraction results, the formation of nitride phases at the Cu/Au/n-GaN interface could be the reason for the degradation of Schottky barrier height upon annealing at 500 °C.     

Electrical properties of oxidized polycrystalline silicon as a gate insulator for n-type 4H-SiC MOS devices

MOS capacitors were produced on n-type 4H-SiC using oxidized polycrystalline silicon (polyoxide). The polyoxide samples grown by dry oxidation without an anneal had a high interface state density (D_it) of 1.8 × 10¹² cm⁻² eV⁻¹ and the polyoxide samples grown by wet oxidation had a lower D_it of 1.2 × 10¹² cm⁻² eV⁻¹ (both at 0.5 eV below the conduction band). After 1 h Ar annealing, the D_it of wet polyoxide was reduced significantly to 2.6 × 10¹¹ cm⁻² eV⁻¹ (at 0.5 eV below the conduction band). Dry polyoxide exhibits higher breakdown electric fields than wet polyoxide. The interface quality and breakdown characteristics of polyoxide are comparable to published results of low-temperature CVD deposited oxides.