Semiconductor Single Crystals Research Articles

Strong anisotropy of momentum-relaxation time induced by intermolecular vibrations of single-crystal organic semiconductors

We present a theoretical study of the relationships between intermolecular vibrations and anisotropic transport properties of pentacene and rubrene single-crystal organic semiconductors. Using our wave-packet approach based on the Kubo formula beyond the effective-mass approximation with the assumption of an isotropic momentum-relaxation time, we find that the intermolecular vibrations induce a strong anisotropic momentum-relaxation time but moderate the anisotropy of carrier mobility much more than that of the effective mass. This clarifies the mechanism behind the deviation of the anisotropic ratio of mobility from that of effective mass observed in angle-resolved photoelectron spectroscopy experiments.

Sputtering of Si, SiC, InAs, InP, Ge, GaAs, GaSb, and GaN by electrosprayed nanodroplets

This article presents a characterization of the damage caused by energetic beams of electrosprayed nanodroplets striking the surfaces of single-crystal semiconductors including Si, SiC, InAs, InP, Ge, GaAs, GaSb, and GaN. The sputtering yield (number of atoms ejected per projectile's molecule), sputtering rate, and surface roughness are measured as functions of the beam acceleration potential. The maximum values of the sputtering yields range between 1.9 and 2.2 for the technological important but difficult to etch SiC and GaN respectively, and 4.5 for Ge. The maximum sputtering rates for the non-optimized beam flux conditions used in our experiments vary between 409 nm/min for SiC and 2381 nm/min for GaSb. The maximum sputtering rate for GaN is 630 nm/min. Surface roughness increases modestly with acceleration voltage, staying within 2 nm and 20 nm for all beamlet acceleration potentials and materials except Si. At intermediate acceleration potentials, the surface of Si is formed by craters orders of magnitude larger than the projectiles, yielding surface roughness in excess of 60 nm. The effect of projectile dose is studied in the case of Si. This parameter is correlated with the formation of the large craters typical of Si, which suggests that the accumulation of damage following consecutive impacts plays an important role in the interaction between beamlet and target.

Simultaneous Measurement of Absorbance and Quantum Yields for Photocurrent Generation at Dye-Sensitized Single-Crystal ZnO Electrodes

It is often assumed that the photoresponse or incident photon-to-current conversion efficiency (IPCE) spectrum of a sensitized semiconductor electrode is directly correlated with the amount of sensitizing species present on the semiconductor surface. In reality, the various forms of adsorbed species, such as dye aggregates or dye molecules bound to different adsorption sites, such as terrace edges, can have significantly different electron injection yields and carrier recombination rates. To provide information about the amounts of the various adsorbed dye species and their effectiveness as sensitizers, we report the simultaneous acquisition of IPCE and attenuated total reflectance (ATR) UV-vis spectra for a thiacyanine dye bound to a single-crystal oxide semiconductor electrode surface. ZnO single crystals were fashioned into internal-reflection elements to act both as a waveguide for the internally reflected probe beam for UV-vis spectra and as the substrate for dye sensitization using dyes with distinct spectral signatures for monomers and aggregates. Strong agreement was observed between the quantum efficiency and ATR UV-vis spectra, suggesting that, under the conditions employed, both monomers and aggregates of the dye studied generate photocurrent with the same efficiency.

(Invited) Sensitization Of Single Crystal Semiconductor Electrodes With Dyes, Quantum Dots and Polymers

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Logic-Gate Devices Based on Printed Polymer Semiconducting Nanostripes

The applications of organic semiconductors in complex circuitry such as printed CMOS-like logic circuits demand miniaturization of the active structures to the submicrometric and nanoscale level while enhancing or at least preserving the charge transport properties upon processing. Here, we addressed this issue by using a wet lithographic technique, which exploits and enhances the molecular order in polymers by spatial confinement, to fabricate ambipolar organic field effect transistors and inverter circuits based on nanostructured single component ambipolar polymeric semiconductor. In our devices, the current flows through a precisely defined array of nanostripes made of a highly ordered diketopyrrolopyrrole-benzothiadiazole copolymer with high charge carrier mobility (1.45 cm(2) V(-1) s(-1) for electrons and 0.70 cm(2) V(-1) s(-1) for holes). Finally, we demonstrated the functionality of the ambipolar nanostripe transistors by assembling them into an inverter circuit that exhibits a gain (105) comparable to inverters based on single crystal semiconductors.

Room-temperature ferromagnetism of all-epitaxial β-Fe–Ge/diamond–Ge/β-Fe–Ge trilayers

We report on the first all-epitaxial ferromagnet/inorganic semiconductor/ferromagnet hybrid heterostructure that exhibits (i) a Ge barrier of diamond crystal structure, (ii) room-temperature ferromagnetic electrodes and (iii) very smooth interfaces. Both bottom- and top-Fe–Ge electrodes exhibit tiny in-plane magnetic anisotropies dominated by a magnetocrystalline contribution of six-fold symmetry originating from the hexagonal symmetry of the B82 (Ni2In) β-Fe–Ge phase. A key result is the absence of any magnetic coupling between these soft-magnetic electrodes for Ge barrier thickness as low as ∼2.5 nm, which allows us to easily tune the parallel and antiparallel magnetic alignments by applying suitably small magnetic fields. This confirms the beneficial use of H-surfactant in order to drastically reduce the roughness of the Ge barrier, as revealed by our scanning tunneling microscopy and transmission electron microscopy measurements. This new all-epitaxial ferromagnet/semiconductor hybrid system appears, therefore, to be a promising candidate for the realization of magnetic tunnel junctions with a single crystal semiconductor barrier that are fully compatible with Si-based technology.

Amplified Spontaneous Emission: Amplified Spontaneous Emission and Electroluminescence from Thiophene/Phenylene Co‐Oligomer‐Doped p‐bis(p‐Styrylstyryl)Benzene Crystals (Advanced Optical Materials 6/2013)

On page 422, dye molecular doping of an organic semiconductor single crystal enables H. Nakanotani and C. Adachi to tune its light amplification characteristics, significantly reducing the amplified spontaneous emission threshold via an enhancement of the photoluminescence quantum efficiency. The dye-doped organic semiconductor crystal maintains high ambipolar carrier mobilities and shows bright, self-waveguided emission from the crystal edge under both optical and electrical excitation.

Rubrene-Based Single-Crystal Organic Semiconductors: Synthesis, Electronic Structure, and Charge-Transport Properties

Correlations among the molecular structure, crystal structure, electronic structure, and charge-carrier transport phenomena have been derived from six congeners (2–7) of rubrene (1). The congeners were synthesized via a three-step route from known 6,11-dichloro-5,12-tetracenedione. After crystallization, their packing structures were solved using single-crystal X-ray diffraction. Rubrenes 5–7 maintain the orthorhombic features of the parent rubrene (1) in their solid-state packing structures. Control of the packing structure in 5–7 provided the first series of systematically manipulated rubrenes that preserve the π-stacking motif of 1. Density functional theory calculations were performed at the B3LYP/6-31G(d,p) level of theory to evaluate the geometric and electronic structure of each derivative and reveal that key properties of rubrene (1) have been maintained. Intermolecular electronic couplings (transfer integrals) were calculated for each derivative to determine the propensity for charge-carrier tran...

Photoconductive response in organic charge transfer interfaces with high quantum efficiency

Organic semiconductors have unique optical, mechanical and electronic properties that can be combined with customized chemical functionality. In the crystalline form, determinant features for electronic applications, such as molecular purity, the charge mobility or the exciton diffusion length, reveal a superior improved performance when compared with materials in a more disordered form. However, the use of organic single crystals in devices is still limited to a few applications, such as field-effect transistors. Here we report the first example of photoconductive behaviour of single-crystal charge-transfer interfaces. The system composed of rubrene and 7,7,8,8-tetracyanoquinodimethane presents a responsivity reaching 1 AW(-1), corresponding to an external quantum efficiency of nearly 100%. This result opens the possibility of using organic single-crystal interfaces in photonic applications.

Diamond turning of small Fresnel lens array in single crystal InSb

A small Fresnel lens array was diamond turned in a single crystal (0 0 1) InSb wafer using a half-radius negative rake angle (−25°) single-point diamond tool. The machined array consisted of three concave Fresnel lenses cut under different machining sequences. The Fresnel lens profiles were designed to operate in the paraxial domain having a quadratic phase distribution. The sample was examined by scanning electron microscopy and an optical profilometer. Optical profilometry was also used to measure the surface roughness of the machined surface. Ductile ribbon-like chips were observed on the cutting tool rake face. No signs of cutting edge wear was observed on the diamond tool. The machined surface presented an amorphous phase probed by micro Raman spectroscopy. A successful heat treatment of annealing was carried out to recover the crystalline phase on the machined surface. The results indicated that it is possible to perform a ‘mechanical lithography’ process in single crystal semiconductors.

Photoelectrochemical Transients for Chlorine/Hypochlorite Formation at “Roll-On” Nano-WO3 Film Electrodes

Commercial nano-WO3 (10–100 nm average particle size) is dispersed in n-hexanol and applied to tin-doped indium oxide (ITO) substrates in a simple “roll-on” process. As-deposited and annealed (500 °C) films are compared and shown to be photoactive for the formation of hypochlorite in neutral aqueous NaCl (e.g., seawater). Annealing at 500 °C in air improves photocurrents most likely due to improved interparticle charge transport (e.g., removal of hydration or n-hexanol surface layers). In phototransients (interpreted here in the limiting case of a weakly associated nanoparticle aggregate as opposed to the limiting case of a single-crystal semiconductor), evidence for the presence of both holes (as O(-I), fast moving) and electrons (as W(V), slow moving) is obtained in particular in as-deposited films. Bipotentiostat experiments reveal the presence of chlorine as a reaction intermediate close to the photoanode when immersed in 3 M NaCl. A “molecular conduit” effect with adsorbed Co(II/III) sepulchrate is observed to significantly enhance the photocurrents at as-deposited electrodes (but not at annealed electrodes).

Surface chemistry mediates thermal transport in three-dimensional nanocrystal arrays

Arrays of ligand-stabilized colloidal nanocrystals with size-tunable electronic structure are promising alternatives to single-crystal semiconductors in electronic, optoelectronic and energy-related applications. Hard/soft interfaces in these nanocrystal arrays (NCAs) create a complex and uncharted vibrational landscape for thermal energy transport that will influence their technological feasibility. Here, we present thermal conductivity measurements of NCAs (CdSe, PbS, PbSe, PbTe, Fe3O4 and Au) and reveal that energy transport is mediated by the density and chemistry of the organic/inorganic interfaces, and the volume fractions of nanocrystal cores and surface ligands. NCA thermal conductivities are controllable within the range 0.1-0.3 W m(-1) K(-1), and only weakly depend on the thermal conductivity of the inorganic core material. This range is 1,000 times lower than the thermal conductivity of silicon, presenting challenges for heat dissipation in NCA-based electronics and photonics. It is, however, 10 times smaller than that of Bi2Te3, which is advantageous for NCA-based thermoelectric materials.

Sensitization of Single Crystal Semiconductors with Dyes and Quantum Dots

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Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance

Mesoporous ceramics and semiconductors enable low-cost solar power, solar fuel, (photo)catalyst and electrical energy storage technologies. State-of-the-art, printable high-surface-area electrodes are fabricated from thermally sintered pre-formed nanocrystals. Mesoporosity provides the desired highly accessible surfaces but many applications also demand long-range electronic connectivity and structural coherence. A mesoporous single-crystal (MSC) semiconductor can meet both criteria. Here we demonstrate a general synthetic method of growing semiconductor MSCs of anatase TiO2 based on seeded nucleation and growth inside a mesoporous template immersed in a dilute reaction solution. We show that both isolated MSCs and ensembles incorporated into films have substantially higher conductivities and electron mobilities than does nanocrystalline TiO2. Conventional nanocrystals, unlike MSCs, require in-film thermal sintering to reinforce electronic contact between particles, thus increasing fabrication cost, limiting the use of flexible substrates and precluding, for instance, multijunction solar cell processing. Using MSC films processed entirely below 150 °C, we have fabricated all-solid-state, low-temperature sensitized solar cells that have 7.3 per cent efficiency, the highest efficiency yet reported. These high-surface-area anatase single crystals will find application in many different technologies, and this generic synthetic strategy extends the possibility of mesoporous single-crystal growth to a range of functional ceramics and semiconductors.

Influence of Morphology on the Optical Properties of Self-Grown Nanowire Arrays

Nanostructured materials such as nanowire arrays often absorb light more strongly than thin films, so they can be used to improve the performance of solar cells. In this study, a series of self-grown Cu2S nanowire arrays with different diameters, lengths, and morphologies is prepared by solid–gas reaction between Cu foil and a mixture of H2S and O2. The structure of the arrays is characterized by XRD, TEM, XPS, and Raman. Their light absorption performance is investigated systematically by diffuse reflectance and photoluminescence spectroscopy. The nanowire arrays are single-crystal Cu2S semiconductors, and their band gap can be adjusted by changing the morphology, diameter, and length of nanowires in the arrays. The light-absorption ability is enhanced from 70% for a planar Cu2S film to 93.5% for a Cu2S nanowire arrays and is less sensitive to both the wavelength and incident angle of light because of the morphology and distribution of the nanowires. The light absorption is high (about 92–95%) over a wide range of wavelengths (240–670 nm) and only decreases by 3% as the incident angle increases from 10 to 40°. This research shows the potential of Cu2S nanowire arrays for use in solar energy applications.

Electrically conducting film of silver sub-micron particles as mechanical and electrical interfaces for transfer printed micro- and nano-pillar devices

In this paper we report a novel application of electrically conductive film (ECF) of Ag sub-micron particles that includes both isotropic and anisotropic film technologies in providing simultaneous electrical contact and mechanical anchor between fracture transfer-printed (1-D) single crystal semiconductor micro- and nano-pillars and a carrier substrate. We assembled silver sub-micron particles (AgSP) monolayers with varying particle diameters and investigated their optical and electrical characteristics prior to their incorporation into thermoplastic polymers. It was found that transfer-printing of the Si micropillar arrays, into electrically conductive thermoplastic receiver substrates, made of films of AgSP/PMMA blends atop metallic substrates could be effectively achieved to yield electrically interfaced 1-D Si micropillar arrays with retention of their orientation and integrity according to the SEM images. The carrier substrate can potentially be reused to generate additional Si micropillar arrays that can be similarly harvested.

Toward high-mobility organic field-effect transistors: Control of molecular packing and large-area fabrication of single-crystal-based devices

Abstract

Printable organic semiconductor single crystals and high-performance AM-TFTs

Printable organic semiconductor single crystals and high-performance AM-TFTs

Growth of Polycrystalline Indium Phosphide Nanowires on Copper

ABSTRACTOur nation discards more than 50% of the total input energy as waste heat in various industrial processes such as metal refining, heat engines, and cooling. If we could harness a small fraction of the waste heat through the use of thermoelectric (TE) devices while satisfying the economic demands of cost versus performance, then TE power generation could bring substantial positive impacts to our society in the forms of reduced carbon emissions and additional energy. To increase the unit-less figure of merit, ZT, single-crystal semiconductor nanowires have been extensively studied as a building block for advanced TE devices because of their predicted large reduction in thermal conductivity and large increase in power factor. In contrast, polycrystalline bulk semiconductors also indicate their potential in improving overall efficiency of thermal-to-electric conversion despite their large number of grain boundaries. To further our goal of developing practical and economical TE devices, we designed a material platform that combines nanowires and polycrystalline semiconductors which are integrated on a metallic surface. We will assess the potential of polycrystalline group III-V compound semiconductor nanowires grown on low-cost copper sheets that have ideal electrical/thermal properties for TE devices. We chose indium phosphide (InP) from group III-V compound semiconductors because of its inherent characteristics of having low surface states density in comparison to others, which is expected to be important for polycrystalline nanowires that contain numerous grain boundaries. Using metal organic chemical vapor deposition (MOCVD) polycrystalline InP nanowires were grown in three-dimensional networks in which electrical charges and heat travel under the influence of their characteristic scattering mechanisms over a distance much longer than the mean length of the constituent nanowires. We studied the growth mechanisms of polycrystalline InP nanowires on copper surfaces by analyzing their chemical, optical, and structural properties in comparison to those of single-crystal InP nanowires formed on single-crystal surfaces. We also assessed the potential of polycrystalline InP nanowires on copper surfaces as a TE material by modeling based on finite-element analysis to obtain physical insights of three-dimensional networks made of polycrystalline InP nanowires. Our discussion will focus on the synthesis of polycrystalline InP nanowires on copper surfaces and structural properties of the nanowires analyzed by transmission electron microscopy that provides insight into possible nucleation mechanisms, growth mechanisms, and the nature of grain boundaries of the nanowires.

Submicrometre-resolution polychromatic three-dimensional X-ray microscopy

The ability to study the structure, microstructure and evolution of materials with increasing spatial resolution is fundamental to achieving a full understanding of the underlying science of materials. Polychromatic three-dimensional X-ray microscopy (3DXM) is a recently developed nondestructive diffraction technique that enables crystallographic phase identification, determination of local crystal orientations, grain morphologies, grain interface types and orientations, and in favorable cases direct determination of the deviatoric elastic strain tensor with submicrometre spatial resolution in all three dimensions. With the added capability of an energy-scanning incident beam monochromator, the determination of absolute lattice parameters is enabled, allowing specification of the complete elastic strain tensor with three-dimensional spatial resolution. The methods associated with 3DXM are described and key applications of 3DXM are discussed, including studies of deformation in single-crystal and polycrystalline metals and semiconductors, indentation deformation, thermal grain growth in polycrystalline aluminium, the metal–insulator transition in nanoplatelet VO2, interface strengths in metal–matrix composites, high-pressure science, Sn whisker growth, and electromigration processes. Finally, the outlook for future developments associated with this technique is described.