Photoconductivity Experiments Research Articles

Boosting Photoconductivity by Increasing the Structural Complexity of Multivariate Covalent Organic Frameworks.

The assessment of the photoconductivity of Donor-Acceptor (D-A) ordered bulk heterojunctions is gaining attention for the development of innovative organic semiconductors in optoelectronics. Here, the synthesis of pyrene-based (D) Covalent Organic Frameworks, achieve through a multivariate reaction involving two distinct acceptors is reported (A). The products are characterized using powder x-ray diffraction, N2 sorption isotherms, electronic microscopy, and in silico calculations, among other techniques. These characterizations reveal that the multicomponent synthesis enables the modification of properties (e.g., bandgap) of the framework while preserving its structural features, such as crystallinity and porosity. The ordered D-A arrays position these materials as promising candidates for photoconductive semiconductors, particularly regarding the variation in the composition of isotopological frameworks. Photoconductivity experiments demonstrate a volcano-type correlation with respect to the A moiety content, with the optimal value reaching 7.9 × 10-5 cm2 V-1 s-1 for the bare NIP25%-COF. This study illustrates how introducing diverse acceptor units through multivariate synthesis can enhance the photoconductivity of these materials via "defect" engineering, without sacrificing their crystalline or porous characteristics and avoiding the need for de novo synthesis.

Nucleation kinetics, chemical etching, hirshfeld surface, and photoluminescence of Rubidium hydrogen oxalate dihydrate NLO single crystal

The nucleation dynamics of a semi-organic Rubidium hydrogen oxalate dihydrate (RbHOH) crystal were assessed using double-distilled water as a solvent medium to obtain good quality crystal using the solution growth technique. Gravimetric analysis of solubility revealed that it has a positive temperature coefficient of solubility, which is appropriate for bulk growth. Other nucleation parameters such as metastable zonewidth, induction period, and interfacial energy were carried out using the classical theory of nucleation. The photoconductivity experiments reveal that the grown crystal exhibits a positive photoconductivity nature. Chemical etching and atomic force microscopy (AFM) experiments were performed on the produced crystal surface. From AFM experiments, effectively assessed amplitude parameters were calculated. Etching studies showed the presence of etch pit patterns such as tiny hillocks and rectangular shapes. Intermolecular interactions were analysed by using Hirshfeld surface analysis. In the photoluminescence (PL) studies, the grown crystal indicates green emission peaks at 519 nm, and the bandgap energy is found to be 4.8 eV. At room temperature, the refractive index of the RbHOH crystal was determined to be 1.669. The nonlinear optical (NLO) efficiency of the grown crystal was examined using a second harmonic generation efficiency test, and it was determined to be 0.58 times that of KDP.

Photoconductivity on K-feldspar

In the development of most phenomenological models used to explain the infrared excited luminescence, a major assumption is usually made in the degree of freedom the excited charge has. One of the two extremes is normally assumed: charge is free to move anywhere over the whole crystal, or it is confined close to the trap and the centers immediately adjacent to it. Determining which of these extremes is more reasonable is difficult to do on the basis of the temporal behavior of the luminescence intensity alone. However, this assumption has important consequences for the understanding of the dynamics of the luminescence process because of the difference in the number of recombination and trapping centers available to the excited charge. Additional experimental evidence was thus sought on this aspect of charge movement. One such experiment is the detection of photoconductivity in which an electrical current is measured during optical excitation or shortly there-after. In this paper, the details of photoconductivity experiments on K crystal are presented. Photoconductivity measurements were inconclusive as to whether or not there was a current flowing during the 850 nm excitation of a feldspar sample. However, there was a clear current when exciting the same sample with 515 nm light, but there was a complex relationship between the magnitude of the current and the number of emission photons counted. A model was developed to explain the photoconductivity results where electrons migrate through the conduction band aided by thermal excitation and tunneling.

CeO2 Doping of Hf0.5Zr0.5O2 Thin Films for High Endurance Ferroelectric Memories

AbstractFerroelectric switching is demonstrated in CeO2‐doped Hf0.5Zr0.5O2 (HZCO) thin films with application in back‐end‐of‐line compatible embedded memories. At low cerium oxide doping concentrations (2.0–5.6 mol%), the ferroelectric orthorhombic phase is stabilized after annealing at temperatures below 400 °C. HZCO ferroelectrics show reliable switching characteristics beyond 1011 cycles in TiN/HZCO/TiN capacitors, several orders of magnitude greater than identically processed Hf0.5Zr0.5O2 (HZO) capacitors, without sacrificing polarization and retention. Internal photoemission and photoconductivity experiments show that CeO2‐doping introduces in‐gap states in HZCO that are nearly aligned with TiN Fermi level, facilitating electron injection through these states. The enhanced average bulk conduction, which may lead to more uniform thermal dissipation in the HZCO films, delays irreversible degradation via breakdown that leads to device failure after repeated programming cycles.

Influences of vacuum annealing induced oxygen defects on the transfer characteristics of a-ITO thin-film transistors

Amorphous indium–tin-oxide (a-ITO) films are fabricated by pulsed laser deposition at room temperature and annealed in vacuum. Although vacuum annealing could ameliorate the carrier mobility and subthreshold swing, the threshold voltage shows a negative shift upon vacuum annealing at 450 K, and a hump emerges in the subthreshold region. The density of electronic states extracted by Grünewald method demonstrate that the hump is caused by shallow donor-like states. Furthermore, the X-ray photoelectron spectra and the photoconductivity experiment reveal that the shallow donors are ascribed to the increased oxygen defects upon thermal annealing.

Defects induced persistent photoconductivity in monolayer MoS2

Understanding the relaxation mechanisms of photoexcited charge carriers in two-dimensional materials is indispensable from the fundamental point of view and for future optoelectronic applications. Through the photoconductivity and electronic transport experiments, we probe the mechanisms behind the persistent photoconductivity (PPC) in monolayer molybdenum disulfide (MoS2). The temperature (T) and power-dependent photoresponse studies reveal that the relaxation of excited charge carriers is strongly affected by the random fluctuations of local potentials. The relaxation time (τ) increases from τ ≃ 12 s at T = 16.5 K to τ ≃ 1235 s at T = 297 K, indicating PPC is a high T phenomenon in monolayer MoS2. The transport measurements demonstrate that the defect states with the density ≃4.43 × 1014 eV−1 cm–2 in a low gate voltage regime, originating from the sulfur vacancies, are responsible for these fluctuations. With a rise in temperature, the defect states undergo a transition from localization to extended states at T ≥ 100 K and thereby form the percolation network, which profoundly influences the relaxation mechanism. Our meticulous experiments and quantitative analysis provide newer insight into the origin of PPC in monolayer MoS2.

About electron transfer over long distances with tunable sub/supersonic velocities.

Provided in this paper is a theory of long-range electron transfer with near sound (supersonic or subsonic) velocity along one-dimensional crystal lattices. The theory represents the development of an earlier work by introducing Marcus formulation. To illustrate its application to a realistic case, the theory is used to offer an explanation of two puzzling observations made by Donovan and Wilson in transient photoconduction experiments with non-dopable perfectly crystalline polydiacetylene crystals in the presence of an electric field: transport velocity value close to sound velocity being independent of field for four orders of magnitude of field (102 V/m-106 V/m) and, in the low field values, an ultra-high mobility greater than 20 m2/V s. We also study factors eventually leading to lowering of the transport velocity.

The mechanism of defects effect on carrier transport by employing multi-wavelength sub-bandgap lights on CdZnTe crystal

The effect of different point defects in CdZnTe (CZT) crystals on carrier transport performance were discussed. The energy level and concentration of the traps were determined by the photo-induced current transient spectroscopy (PICTS). By adding the infrared light illumination into the PICTS experiment, the effect of sub-bandgap light on defects was observed. Meanwhile, several DC photoconductive experiments were done under different wavelength lights were used to explore the effect of the different defects on carrier transport properties of CZT crystals. Furthermore, the energy spectrum test was used to investigate the effect of sub-bandgap light on the energy resolution of CZT detectors. The data results showed that sub-bandgap light could effectively change the ionization state of defects. The doubly ionized Te antisite (TeCd2+) had the greatest effect on mobility-lifetime product(μτ) of electrons owing to its stronger ability of capturing electrons and energy level located around the midgap. While the secondary ionized Cd vacancy (VCd2−), as considered as a hole trap, had the greatest effect on μτ-product of holes. Consequently, choosing suitable infrared light can improve the detection performance of CZT crystal effectively.

Solid-State Infrared Upconversion in Perylene Diimides Followed by Direct Electron Injection.

In this contribution we demonstrate a solid-state approach to triplet–triplet annihilation upconversion for application in a solar cell device in which absorption of near-infrared light is followed by direct electron injection into an inorganic substrate. We use time-resolved microwave photoconductivity experiments to study the injection of electrons into the electron-accepting substrate (TiO2) in a trilayer device consisting of a triplet sensitizer (fluorinated zinc phthalocyanine), triplet acceptor (methyl subsituted perylenediimide), and smooth polycrystalline TiO2. Absorption of light at 700 nm leads to the almost quantitative generation of triplet excited states by intersystem crossing. This is followed by Dexter energy transfer to the triplet acceptor layer where triplet annihilation occurs and concludes by injection of an electron into TiO2 from the upconverted singlet excited state.

PbI2 Single Crystal Growth and Its Optical Property Study

In this work, we used the chemical vapor transport (CVT) method to grow PbI2 crystals using iodine as a self-transporting agent. The crystals’ structure, composition, and uniformity were confirmed by X-ray diffraction (XRD) and electron probe microanalysis (EPMA) measurements. We investigated the band gap energy using absorption spectroscopy measurements. Furthermore, we explored the temperature dependence of the band gap energy, which shifts from 2.346 eV at 300 K to 2.487 eV at 20 K, and extracted the temperature coefficients. A prototype photodetector with a lateral metal–semiconductor–metal (MSM) configuration was fabricated to evaluate its photoelectric properties using a photoconductivity spectrum (PC) and persistent photoconductivity (PPC) experiments. The resonance-like PC peak indicates the excitonic transition in absorption. The photoresponse ILight/IDark-1 is up to 200%.

Corrections to the Hecht collection efficiency in photoconductive detectors under large signals: non-uniform electric field due to drifting and trapped unipolar carriers

The Hecht collection efficiency η0, and its modified expressions for exponential absorption, have been widely used in time-of-flight type transient photoconductivity experiments as well as in the assessment of the sensitivity of integrating-type radiation detectors. However, the equations apply under small signals in which the internal field remains uniform (unperturbed). We have used Monte Carlo simulation and the numerical solution of the continuity, trapping rate and Poisson equations to calculate the collection efficiency ηr (CE) for various levels of charge injection and deep trapping. The carriers are injected instantaneously very near the radiation receiving electrode and then drift under space charge perturbed conditions. The CE deviation from the ideal Hecht value has been quantified in terms of the injection ratio r and the normalized trapping time τ with respect to the transit time under small signals. The results can be represented by a scaled, compressed exponential with coefficients that depend on τ. A plot is provided for these coefficients. The CE drops significantly below the Hecht value as r increases and the deviation is more pronounced for smaller τ values. The errors in extracting τ from the application of the Hecht equation has been also calculated and mapped as a function of different r and τ values.

Electron transport and negative streamers in liquid xenon

In this work we investigate electron transport, transition from an electron avalanche into a negative streamer, and propagation of negative streamers in liquid xenon. Our standard Monte Carlo code, initially developed for dilute neutral gases, is generalized and extended to consider the transport processes of electrons in liquids by accounting for the coherent and other liquid scattering effects. The code is validated through a series of benchmark calculations for the Percus–Yevick model, and the results of the simulations agree very well with those predicted by a multi term solution of Boltzmann’s equation and other Monte Carlo simulations. Electron transport coefficients, including mean energy, drift velocity, diffusion tensor, and the first Townsend coefficient, are calculated for liquid xenon and compared to the available measurements. It is found that our Monte Carlo method reproduces both the experimental and theoretical drift velocities and characteristic energies very well. In particular, we discuss the occurrence of negative differential conductivity in the E/n0 profile of the drift velocity by considering the spatially-resolved swarm data and energy distribution functions. Calculated transport coefficients are then used as an input in fluid simulations of negative streamers, which are realized in a 1.5 dimensional setup. Various scenarios of representing the inelastic energy losses in liquid xenon, ranging from the case where the energy losses to electronic excitations are neglected, to the case where some particular excitations are taken into account, and to the case where all electronic excitations are included, are discussed in light of the available spectroscopy and photoconductivity experiments. We focus on the way in which electron transport coefficients and streamer properties are influenced by representation of the inelastic energy losses, highlighting the need for the correct representation of the elementary scattering processes in the modeling of liquid discharges.

The Study of Near-Band-Edge Property in Oxygen-Incorporated ZnS for Acting as an Efficient Crystal Photocatalyst.

A wide gap semiconductor material has attracted attention as a heterophotocatalyst because of its light harvesting nature to be used in alternative energy production for the next generation. We, herein, grow and synthesize ZnS(1–x)Ox series compounds using the chemical vapor transport (CVT) method with I2 serving as the transport agent. Different crystals, such as undoped ZnS and oxygen-doped ZnS0.94O0.06 and ZnS0.88O0.12, revealed different bright palette emissions that were presented in photoluminescence spectra in our previous report. To study the electron–hole pair interaction of this sample series, the near-band-edge transitions of the sample series were characterized in detail by photoconductivity (PC) experiments. Additional results from surface photovoltage (SPV) spectra also detected the surface and defect-edge transitions from the higher oxygen-doped ZnS crystals. PC measurement results showed a red-shift in the bandgap with increasing incorporation of oxygen on ZnS. Consequently, the samples were subjected to photoirradiation by xenon lamp for the degradation of methylene blue (MNB) by acting as heterophotocatalysts. Undoped ZnS emerged as the best photocatalyst candidate with the fastest rate constant value of 0.0277 min–1. In cubic {111} ZnS [{111} c-ZnS], the polarized Zn+ → S– ions may play a vital role as a photocatalyst because of their strong electron–hole polarization, which leads to the mechanism for degradation of the MNB solution.

Thioethyl‐Porphyrazine/Nanocarbon Hybrids for Photoinduced Electron Transfer

AbstractA novel pyrene‐substituted thioethyl‐porphyrazine (PzPy) and the formation of supramolecular assembly with nanocarbons demonstrating photoinduced electron transfer ability are designed. As revealed by spectroscopic and electrochemical studies, PzPy displays wide spectral absorption in the visible range, charge separation upon photoexcitation, as well as bandgap and highest occupied/lowest unoccupied molecular orbital (HOMO/LUMO) energy values, matching the key requirements of organic optoelectronic. Moreover, the presence of a pyrene moiety promotes attractive interactions with π‐conjugated systems. In particular, theoretical calculations show that in the PzPy the HOMO and LUMO are localized on different positions of the molecule, i.e., the HOMO on the pyrene moiety and the LUMO on the macrocycle. Therefore, HOMO–LUMO excitation gives rise to a charge separation, preventing excitons recombination. Two kinds of noncovalent hybrid composites are prepared by mixing the PzPy with single‐wall carbon nanotubes (SWNTs) and graphene nanoflakes (GNFs), respectively, and used for photocurrent generation through charge transfer processes between PzPy and nanocarbons. Photoconduction experiments show photocurrent generation upon visible light irradiation of both PzPy/SWNT and PzPy/GNF composites (0.78 and 0.71 mA W−1 at 500 nm, respectively), demonstrating their suitability for optoelectronic applications and light harvesting systems.

Synthesis and experimental investigations on the photoconductivity of p-aminoazobenzene based non-conjugated polybenzoxazine system

In this paper, we report the study of a novel p-aminoazobenzene based non-conjugated, benzoxazine polymer, poly([4-(6-tert-butyl-4H-benzo[e][1,3]oxazin-3-yl)phenyl]-phenyldiazene) (AZO-PBZ) synthesized using solvent free, thermally activated cationic ring opening polymerization. The thermal, photophysical, electrochemical, and photoconducting properties of the polymer were investigated. The optical absorption band edges of AZO-PBZ thin film was observed at 555 nm. Photoinduced charge transfer nature of AZO-PBZ was studied by analyzing the fluorescence spectra and performing photoconductivity experiments. Incorporation of [6, 6]-phenyl-C61-butyric acid methyl ester denoted as PCBM into the polymer leads to quenching of the fluorescent intensity and exhibits significant photoconductivity. The photocurrent through the PCBM blend films was measured as a function of electric field to recognize the field dependence on carrier generation. Internal photocurrent efficiency of the polymer:PCBM blend samples was found to be in the order of 10−5 and photoconductive sensitivity was of the order of 10−11 S W−1cm, which is adequate for photorefractivity.

Shallow Heavily Doped n++ Germanium by Organo-Antimony Monolayer Doping.

Functionalization of Ge surfaces with the aim of incorporating specific dopant atoms to form high-quality junctions is of particular importance for the development of solid-state devices. In this study, we report the shallow doping of Ge wafers with a monolayer doping strategy that is based on the controlled grafting of Sb precursors and the subsequent diffusion of Sb into the wafer upon annealing. We also highlight the key role of citric acid in passivating the surface before its reaction with the Sb precursors and the benefit of a protective SiO2 overlayer that enables an efficient incorporation of Sb dopants with a concentration higher than 1020 cm-3. Microscopic four-point probe measurements and photoconductivity experiments show the full electrical activation of the Sb dopants, giving rise to the formation of an n++ Sb-doped layer and an enhanced local field-effect passivation at the surface of the Ge wafer.

The study of flexible emission and photoconductivity in 2D layered InSe toward an applicable 1000-nm light emitter and absorber

Multilayer InSe with a thickness above ~20 nm is a direct semiconductor proposed for solar-energy conversion and to use in flexible optoelectronics. We demonstrate herein a superior 1000-nm light emission and absorption capability of two-dimensional (2D) multilayer InSe studied by photoluminescence (PL) and photoconductivity (PC) experiments. Layered crystals of InSe have been grown by chemical vapor transport method using ICl3 as a transport agent. Polarized Raman measurement confirmed 2 H e crystalline phase of the as-grown crystals. For 2D flexible applications, the bending photoluminescence (BPL) result of InSe (t ≈ 30 nm) showed an enhancement in light intensity with respect to that of the flat PL condition. It might be because the cylinder surface area under bending (convex) is larger than that of the flat surface under the same laser excitation condition. Besides, the luminescence efficiency of BPL is also enhanced owing to the widening of emission solid angle of each Se-In-In-Se unit in the InSe as compared to that of the flat PL condition. The emission wavelength is about 1000 nm at room temperature. Furthermore, for the PC study, photoresponsivity spectrum of a Ag-InSe-Ag multilayer photoconductor demonstrates a prominent peak absorption at 1.1 ~ 1.3 eV, matching well with the direct-free-exciton energy of the multilayer InSe. All the experimental results demonstrate that 2D multilayer InSe is a promising 1000 nm light emitter and absorber available for potential optoelectronics applications.

Structural, optical, thermal, photoconductivity, laser damage threshold and fluorescence analysis of an organic material: β-P-amino benzoic acid single crystal

β-P-amino benzoic acid, an organic single crystal was grown by slow evaporation technique. Single crystal X-ray diffraction studies show that the grown crystal has β-polymorph of P-amino benzoic acid [β-PABA] form and the lattice parameters are a=6.30Å, b=8.61Å, c=12.43Å α=γ=90° and β=100.20°. FTIR analysis confirms that bands at 1588cm−1, 1415cm−1 are assigned to ring skeletal vibrations of title compound. The molecular structure of the grown crystal has been identified by Nuclear Magnetic Resonance spectral study. The optical absorbance spectrum from 200 to 1100nm shows that there is an edge absorbance in UV region. Optical band gap of the crystal has been assessed from the absorbance spectrum. The thermal properties of crystals were evaluated from TG-DTA analysis, it exhibits that there is no weight loss up to 187°C. Laser damage threshold indicates that the grown crystal has no surface damage up to 35mJ. Photoconductivity and fluorescence spectral experiments are also carried out and the results are discussed.

Metal-to-metal charge transfer between dopant and host ions: Photoconductivity of Yb-doped CaF2 and SrF2 crystals.

Dopant-to-host electron transfer is calculated using ab initio wavefunction-based embedded cluster methods for Yb/Ca pairs in CaF2 and Yb/Sr pairs in SrF2 crystals to investigate the mechanism of photoconductivity. The results show that, in these crystals, dopant-to-host electron transfer is a two-photon process mediated by the 4f(N-1)5d excited states of Y b(2+): these are reached by the first photon excitation; then, they absorb the second photon, which provokes the Y b(2+) + Ca(2+) (Sr(2+)) → Y b(3+) + Ca(+) (Sr(+)) electron phototransfer. This mechanism applies to all the observed Y b(2+) 4f-5d absorption bands with the exception of the first one: Electron transfer cannot occur at the first band wavelengths in CaF2:Y b(2+) because the Y b(3+)-Ca(+) states are not reached by the two-photon absorption. In contrast, Yb-to-host electron transfer is possible in SrF2:Y b(2+) at the wavelengths of the first 4f-5d absorption band, but the mechanism is different from that described above: first, the two-photon excitation process occurs within the Y b(2+) active center, then, non-radiative Yb-to-Sr electron transfer can occur. All of these features allow to interpret consistently available photoconductivity experiments in these materials, including the modulation of the photoconductivity by the absorption spectrum, the differences in photoconductivity thresholds observed in both hosts, and the peculiar photosensitivity observed in the SrF2 host, associated with the lowest 4f-5d band.

Electron Tunneling from Colloidal CdSe Quantum Dots to ZnO Nanowires Studied by Time-Resolved Luminescence and Photoconductivity Experiments

CdSe quantum dots (QDs) with different organic linker molecules are attached to ZnO nanowires (NWs) to study the luminescence dynamics and the electron tunneling from the QDs to the NWs in time-resolved photoluminescence (PL) and photoconductivity experiments. The PL transients of the QD luminescence indicate two different recombination channels: the direct recombination inside of the QD core and the recombination via QD surface defect states. After linking the QDs to the ZnO NW surface, photoinduced electron tunneling from an excited state of the QD into the conduction band of the NW becomes visible by a clear decrease of the PL decay time. Efficient electron tunneling is confirmed by a strong enhancement of the photocurrent through the functionalized NWs in which the tunneling rate can be controlled by using different organic linker molecules.