Saturated Photocurrent Research Articles

Steady-state characteristics and transient response of MgZnO-based metal-semiconductor-metal solar-blind ultraviolet photodetector with three types of electrode structures

Detailed studies of MgZnO-based metal-semiconductor-metal (MSM) solar-blind ultraviolet photodetector with different electrode structures are performed. A two-dimensional physical model is established based on the Poisson's equation and time-dependent continuity equations, which is verified by our experimental data of conventional electrode MSM detector. The steady-state characteristics and transient response of semicircular and triangular electrode MSM detectors are also investigated by this model. Compared with the conventional electrode, semicircular and triangular electrode devices exhibit a substantial improvement on the photocurrent. At a bias of 10 V, the steady-state saturated photocurrents for semicircular and triangular electrode devices are 14.69 nA and 24.37 nA respectively, corresponding to a 20.5% and 100% increase over the conventional electrode detector. Meanwhile, the transient peak photocurrents reach 31.38 nA and 52.09 nA respectively, both of which are notably larger than that of conventional device.

Photoconductivity and transient response of Al:ZnO:Al planar structures fabricated via a thermal oxidation process

We have investigated the photoconductivity and transient response of polycrystalline ZnO films grown using a thermal oxidation technique. Zinc-metal films were grown on c-plane sapphire substrates via non-reactive dc sputter deposition at room temperature with subsequent thermal annealing at 300°C, 600°C, 900°C, and 1200°C. Metal–semiconductor–metal Al:ZnO:Al planar ultraviolet (UV) photodetectors were fabricated via sputter deposition of aluminum contacts. Decreasing photoconductivity is seen for increasing annealing temperature, which is consistent with photoluminescence studies showing a similar decrease in the green-to-UV emission ratio. As-grown photodetectors annealed at low temperature (300°C) over 9h demonstrated a responsivity of ~100mA/W. We also present a phenomenological model of photoconductivity transients in which transient recoveries are fitted with a linear combination of two exponential decays. Although annealing temperature did have a significant effect on photocurrent saturation, there was no such relationship for post-illumination recovery time constants.

Photocurrent saturation and negative differential photoconductivity in Mn4Si7-Si〈Mn〉-Mn4Si7 and Mn4Si7-Si〈Mn〉-M heterojunctions

A mechanism behind the saturation of the photocurrent and occurrence of negative differential photoconductivity in Mn4Si7-Si〈Mn〉-Mn4Si7 and Mn4Si7-Si〈Mn〉-M heterojunctions is found. Mn4Si7-Si〈Mn〉-Mn4Si7 and Mn4Si7-Si〈Mn〉-M structures are studied with a model of back-to-back diodes. Photocurrent-voltage characteristics are taken at high constant and pulsed applied biases. It is found that the nonlinearity of the photocurrent-voltage characteristics and photoconductivity kinetics are due to the quenching of photoconductivity by Joule self-heating.

Surface Morphology-Dependent Photoelectrochemical Properties of One-Dimensional Si Nanostructure Arrays Prepared by Chemical Etching

Maximizing the optical absorption of one-dimensional Si nanostructure arrays (1DSiNSAs) is desirable for excellent performance of 1DSiNSA-based optoelectronic devices. However, a quite large surface-to-volume ratio and enhanced surface roughness are usually produced by modulation of the morphology of the 1DSiNSAs prepared in a top-down method to improve their optical absorption. Surface recombination is mainly determined by the surface characteristics and significantly affects the photogenerated carrier collection. In this paper, we systematically investigated the photoelectrochemical characteristics of 1DSiNSAs with various morphologies prepared by the metal-assisted chemical etching of Si wafers. Our results show that the saturation photocurrent density and photoresponsivity of 1DSiNSAs first increased and then gradually decreased with an increasing etching time, while the reflection spectrum was gradually suppressed to the measurable minimum. To identify the behaviors of the photoresponsivity and optical absorption of the various 1DSiNSAs, we analyzed the morphology, structure, and minority-carrier lifetime. Additionally, device physics simulations were used to confirm the significance of surface recombination. We proposed that future directions for the design of nanostructure-based optoelectronic devices should include not only strong optical absorption but also low surface carrier recombination. High-performance devices could be obtained only by balancing the requirements for light absorption and photogenerated carrier collection.

Synthesis and photoelectrochemical response of CdS quantum dot-sensitized TiO2 nanorod array photoelectrodes

A continuous and compact CdS quantum dot-sensitive layer was synthesized on TiO2 nanorods by successive ionic layer adsorption and reaction (SILAR) and subsequent thermal annealing. The thickness of the CdS quantum dot layer was tuned by SILAR cycles, which was found to be closely related to light absorption and carrier transformation. The CdS quantum dot-sensitized TiO2 nanorod array photoelectrodes were characterized by scanning electron microscopy, X-ray diffraction, ultraviolet–visible absorption spectroscopy, and photoelectrochemical property measurement. The optimum sample was fabricated by SILAR in 70 cycles and then annealed at 400°C for 1 h in air atmosphere. A TiO2/CdS core-shell structure was formed with a diameter of 35 nm, which presented an improvement in light harvesting. Finally, a saturated photocurrent of 3.6 mA/cm2 was produced under the irradiation of AM1.5G simulated sunlight at 100 mW/cm2. In particular, the saturated current density maintained a fixed value of approximately 3 mA/cm2 without decadence as time passed under the light conditions, indicating the steady photoelectronic property of the photoanode.

Studies of photoconductivity and field effect transistor behavior in examining drift mobility, surface depletion, and transient effects in Si-doped GaN nanowires in vacuum and air

Variable intensity photoconductivity (PC) performed under vacuum at 325 nm was used to estimate drift mobility (μ) and density (σs) of negative surface charge for c-axis oriented Si-doped GaN nanowires (NWs). In this approach, we assumed that σs was responsible for the equilibrium surface band bending (∅) and surface depletion in the absence of illumination. The NWs were grown by molecular beam epitaxy to a length of approximately 10 μm and exhibited negligible taper. The free carrier concentration (N) was separately measured using Raman scattering which yielded N = (2.5 ± 0.3) × 1017 cm−3 for the growth batch studied under 325 nm excitation. Saturation of the PC was interpreted as a flatband condition whereby ∅ was eliminated via the injection of photogenerated holes. Measurements of dark and saturated photocurrents, N, NW dimensions, and dimensional uncertainties, were used as input to a temperature-dependent cylindrical Poisson equation based model, yielding σs in the range of (3.5 to 7.5) × 1011 cm−2 and μ in the range of (850 to 2100) cm2/(V s) across the (75 to 194) nm span of individual NW diameters examined. Data illustrating the spectral dependence and polarization dependence of the PC are also presented. Back-gating these devices, and devices from other growth batches, as field effect transistors (FETs) was found to not be a reliable means to estimate transport parameters (e.g., μ and σs) due to long-term current drift. The current drift was ascribed to screening of the FET back gate by injected positive charge. We describe how these gate charging effects can be exploited as a means to hasten the otherwise long recovery time of NW devices used as photoconductive detectors. Additionally, we present data illustrating comparative drift effects under vacuum, room air, and dry air for both back-gated NW FETs and top-gated NW MESFETs.

Codoping titanium dioxide nanowires with tungsten and carbon for enhanced photoelectrochemical performance

Recent density-functional theory calculations suggest that codoping TiO2 with donor-acceptor pairs is more effective than monodoping for improving photoelectrochemical water-splitting performance because codoping can reduce charge recombination, improve material quality, enhance light absorption and increase solubility limits of dopants. Here we report a novel ex-situ method to codope TiO2 with tungsten and carbon (W, C) by sequentially annealing W-precursor-coated TiO2 nanowires in flame and carbon monoxide gas. The unique advantages of flame annealing are that the high temperature (>1,000 °C) and fast heating rate of flame enable rapid diffusion of W into TiO2 without damaging the nanowire morphology and crystallinity. This is the first experimental demonstration that codoped TiO2:(W, C) nanowires outperform monodoped TiO2:W and TiO2:C and double the saturation photocurrent of undoped TiO2 for photoelectrochemical water splitting. Such significant performance enhancement originates from a greatly improved electrical conductivity and activity for oxygen-evolution reaction due to the synergistic effects of codoping.

Dual Roles of ZnS Thin Layers in Significant Photocurrent Enhancement of ZnO/CdTe Nanocable Arrays Photoanode

The effect of a ZnS thin layer on the photoelectrochemical property of ZnO/CdTe nanocable arrays-on-indium tin oxide was systematically studied by the successive ion layer absorption and reaction (SILAR) of ZnS. The thickness of CdTe on bare ZnO/CdTe nanocable arrays was optimized to approximately 10 nm to achieve a saturated photocurrent density of 6.5 mA/cm(2). Significant photocurrent enhancement was achieved by gradually increasing the ZnS SILAR cycle number from 0 to 10. A "type I" band alignment with conduction and valence band offsets of 0.58 and 1.52 eV, respectively, was deduced for the CdTe/ZnS interface. The detailed microstructure of the CdTe/ZnS interface and the relationship between the photocurrent and the ZnS thickness indicated that ZnS not only serves as a barrier layer that prevents electron injection from CdTe to the electrolyte but also provides an effective tunneling channel for hole transfers to the electrolyte. A ZnO/CdTe/ZnS nanocable photoanode yielded a saturated photocurrent density of 13.8 mA/cm(2) when the thickness of ZnS was controlled to approximately 2 nm.

Using TiO2 as a Conductive Protective Layer for Photocathodic H2 Evolution

Surface passivation is a general issue for Si-based photoelectrodes because it progressively hinders electron conduction at the semiconductor/electrolyte interface. In this work, we show that a sputtered 100 nm TiO(2) layer on top of a thin Ti metal layer may be used to protect an n(+)p Si photocathode during photocatalytic H(2) evolution. Although TiO(2) is a semiconductor, we show that it behaves like a metallic conductor would under photocathodic H(2) evolution conditions. This behavior is due to the fortunate alignment of the TiO(2) conduction band with respect to the hydrogen evolution potential, which allows it to conduct electrons from the Si while simultaneously protecting the Si from surface passivation. By using a Pt catalyst the electrode achieves an H(2) evolution onset of 520 mV vs NHE and a Tafel slope of 30 mV when illuminated by the red part (λ > 635 nm) of the AM 1.5 spectrum. The saturation photocurrent (H(2) evolution) was also significantly enhanced by the antireflective properties of the TiO(2) layer. It was shown that with proper annealing conditions these electrodes could run 72 h without significant degradation. An Fe(2+)/Fe(3+) redox couple was used to help elucidate details of the band diagram.

Chemical bath deposition of vertically aligned TiO2 nanoplatelet arrays for solar energy conversion applications

We report a facile, scalable, and low cost chemical bath deposition of vertically aligned TiO2 nanoplatelet arrays on various substrates including fluorine-doped tin oxide coated glass substrates and their applications for photoelectrochemical (PEC) water splitting and dye sensitized solar cells. The TiO2 arrays consisting of single crystal rutile nanoplatelets with heights (film thicknesses) of up to 1 μm, lengths of up to 130 nm, and widths of ∼5 nm were grown via controlling oxidation and hydrolysis of TiCl3 at low pH (0.71–0.85) and low TiCl3 concentration (8–40 mM). As a photoanode for water oxidation in a PEC water splitting cell, the TiO2 nanoplatelets show excellent charge separation characteristics with a saturated photocurrent in 1 M KOH electrolyte under AM 1.5 G illumination of ∼0.4 mA cm−2 reached at an exceptionally low bias of −0.6 V vs. Ag/AgCl (0.4 V vs. reversible hydrogen electrode). Dye sensitized solar cells assembled using N719 dye sensitized-TiO2 nanoplatelet arrays also show promising performance with photoconversion efficiencies of 1.28% for as-synthesized (no thermal post-treatment) and 3.7% for annealed TiO2 nanoplatelets.

Electrochemical fabrication of ZnO–CdSe core–shell nanorod arrays for efficient photoelectrochemical water splitting

Efficient hydrogen production from photoelectrochemical (PEC) water splitting is a promising route to solve the approaching energy crisis. Herein, we report a facile all-electrochemical approach to fabricate well-aligned ZnO-CdSe core-shell nanorod arrays with excellent uniformity on transparent indium tin oxide (ITO) substrates. The shell thickness of the core-shell nanorods can be tuned precisely by adjusting the charge density passing through the working electrode during the deposition of CdSe quantum dots (QDs). The optimized ZnO-CdSe nanorod arrays showed excellent PEC performance with a significant saturated photocurrent density of 14.9 mA cm(-2) at 0.8 V (vs. RHE) under AM 1.5 illumination, which is, to the best of our knowledge, the highest value ever reported for similar nanostructures, owing to the favourable band alignment and good distribution of CdSe QDs on ZnO nanorods. Our results demonstrate that the electrochemically deposited ZnO-CdSe nanorod arrays can be utilized as efficient photoanodes in PEC water splitting cells.

Electrochemical reduction induced self-doping of Ti3+ for efficient water splitting performance on TiO2 based photoelectrodes

Hetero-element doping (e.g., N, F, C) of TiO2 is inevitably accompanied by significantly increased structural defects due to the dopants' nature being foreign impurities. Very recently, in situ self-doping with homo-species (e.g., Ti(3+)) has been emerging as a rational solution to enhance TiO2 photoactivity within both UV and visible light regions. Herein we demonstrate that conventional electrochemical reduction is indeed a facile and effective strategy to induce in situ self-doping of Ti(3+) into TiO2 and the self-doped TiO2 photoelectrodes showed remarkably improved and very stable water splitting performance. In this study, hierarchical TiO2 nanotube arrays (TiO2 NTs) were chosen as TiO2 substrates and then electrochemically reduced under varying conditions to produce Ti(3+) self-doped TiO2 NTs (ECR-TiO2 NTs). The optimized saturation photocurrent density and photoconversion efficiency on the ECR-TiO2 NTs under simulated AM 1.5G illumination were identified to be 2.8 mA cm(-2) at 1.23 V vs. RHE and 1.27% respectively, which are the highest values ever reported for TiO2 based photoelectrodes. The electrochemical impedance spectra measurement confirms that the electrochemical induced Ti(3+) self-doping improved the electrical conductivity of the ECR-TiO2 NTs. The versatility and effectiveness of the electrochemical reduction method for Ti(3+) self-doping in P25 based TiO2 was also examined and confirmed.

Nanostructured ZnO Thin Films for Optical, Electrical, and Photoelectrochemical Applications from a New Zn Complex

New hexanuclear zinc complex, Zn6(OAc)8(μ-O)2(dmae)4 (1) (OAc = acetato, dmae = N,N-dimethyl aminoethanolato) has been synthesized and characterized by its melting point, elemental analysis, Fourier transform infrared spectroscopy, atmospheric-pressure chemical-ionization mass spectrometry, thermal gravimetric analysis, and single crystal X-ray analysis. The complex (1) crystallizes in the monoclinic space group C2/c. The high solubility of complex (1) in organic solvents such as alcohol, THF, and toluene and low decomposition temperature as compared to Zn(OAc)2 make it a promising single source candidate for the deposition of nanostructured ZnO thin films by aerosol-assisted chemical vapor deposition. Films with various nanostructures, morphology, and crystallographic orientation have been deposited by controlling the deposition temperature. The deposited films have been characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. The optical characterization of ZnO films deposited on the FTO substrate show a direct band gap of 3.31 eV, and the photoelectrochemical study revealed that the photocurrent onset is at about −0.32 V, whereas no photocurrent saturation was observed. The I–V measurements designated the deposited films as ohmic semiconductors.

Tuning the dynamic properties of electrons between a quantum well and quantum dots

We present a study of the dynamic properties of electrons tunneling from an InGaAs quantum well to self assembled InAs quantum dots. The experiments were conducted on three highly asymmetric quantum dot infrared photodetectors, where the quantum well and quantum dots were separated by a composite GaAs/AlGaAs/GaAs barrier, which varied from 3.5 nm to 7.0 nm. We performed interband (photoluminescence) and intraband (photocurrent) measurements to characterize the spectral properties of the well and the dots. The photoluminescence measurements revealed that the two nanostructures are decoupled when the device is at zero bias. By intraband pump-probe experiments and photocurrent saturation experiments, we were able to extrapolate a refilling time τ from the well to the dots, which varied from a few μs for the thinnest barrier and hundreds of μs for the thickest one. The extracted values are in good agreement with characteristic tunneling times computed by using a model based on the theoretically predicted transmission coefficient of the electrons through the composite barrier.

Enhanced Water Photolysis with Pt Metal Nanoparticles on Single Crystal TiO2 Surfaces

Two novel deposition methods were used to synthesize Pt-TiO(2) composite photoelectrodes: a tilt-target room temperature sputtering method and aerosol-chemical vapor deposition (ACVD). Pt nanoparticles (NPs) were sequentially deposited by the tilt-target room temperature sputtering method onto the as-synthesized nanostructured columnar TiO(2) films by ACVD. By varying the sputtering time of Pt deposition, the size of deposited Pt NPs on the TiO(2) film could be precisely controlled. The as-synthesized composite photoelectrodes with different sizes of Pt NPs were characterized by various methods, such as SEM, EDS, TEM, XRD, and UV-vis. The photocurrent measurements revealed that the modification of the TiO(2) surface with Pt NPs improved the photoelectrochemical properties of electrodes. Performance of the Pt-TiO(2) composite photoelectrodes with sparsely deposited 1.15 nm Pt NPs was compared to the pristine TiO(2) photoelectrode with higher saturated photocurrents (7.92 mA/cm(2) to 9.49 mA/cm(2)), enhanced photoconversion efficiency (16.2% to 21.2%), and increased fill factor (0.66 to 0.70). For larger size Pt NPs of 3.45 nm, the composite photoelectrode produced a lower photocurrent and reduced conversion efficiency compared to the pristine TiO(2) electrode. However, the surface modification by Pt NPs helped the composite electrode maintain higher fill factor values.

Preparation of well-aligned WO3 nanoflake arrays vertically grown on tungsten substrate as photoanode for photoelectrochemical water splitting

Well-aligned WO3 nanoflake arrays (WNA) as effective photoanode was vertically fabricated on tungsten sheet through a facile hydrothermal process. Before reaction, the tungsten sheet was pre-annealed to produce a thin-layer WO3 on surface to serve as seeded sites for crystal growth in hydrothermal reaction, which also provided a strong connection between the growing WO3 and substrate. Polyethylene glycol (PEG) was used as the structure-directing agent to confine the crystal growth. This preparation route obviously facilitated the charge transfer and reduced the recombination of photoexcited electron/hole. The saturated photocurrent density and IPCE value were found to be 2.35mAcm−2 at 1.5V and 56% which were much higher than that prepared in the absence of pre-annealed WO3 layer and PEG.

Si/Ge uni-traveling carrier photodetector

We have fabricated and characterized a germanium on silicon uni-traveling carrier photodetector for analog and coherent communications applications. The device has a bandwidth of 20GHz, a large-signal 1dB saturation photocurrent of 20mA at -3V, and a low thermal impedance of 520K/W.

Photovoltaic phenomena in BiFeO3 multiferroic ceramics

Open-circuit photovoltage and short-circuit photocurrent were investigated in BiFeO3 (BFO) ceramics as functions of laser wavelength (λ = 373 and 532 nm), illumination intensity, and sample thickness. BFO ceramics exhibit significant photovoltaic responses under near-ultraviolet illumination of λ = 373 nm. The photovoltaic responses strongly depend on wavelength, light intensity, and sample thickness. The relation between photovoltaic responses and light intensity can be described by exponential equations, EOC = ES[1 – exp(–I/α)] and JSC = JS[1 – exp(−I/β)]. EOC, JSC, ES, and JS are open-circuit photovoltage (V/cm), short-circuit photocurrent density (A/cm2), saturated photovoltage (V/cm), and saturated photocurrent density, respectively. This work suggests that BFO ceramic exhibits stronger photovoltaic responses than the ferroelectric WO3-doped Pb1-xLax(ZryTiz)1-x/4O3 ceramics and Pb(Mg1/3Nb2/3)1-xTixO3 crystals.

Double-shelled ZnO/CdSe/CdTe nanocable arrays for photovoltaic applications: microstructure evolution and interfacial energy alignment

A series of high-density double- and single-shelled ZnO/CdSe/CdTe, ZnO/CdTe/CdSe, ZnO/CdTe and ZnO/CdSe nanocable arrays were synthesized as photoanodes by an electrodeposition method using ZnO nanorod arrays as cores. For ZnO/CdSe/CdTe nanocable arrays, the uniform CdSe and CdTe nanoshells were composed of zinc-blende phase nanocrystals with a respective average size range of 10–20 nm and 7–15 nm, and formed a compact and continuous interface in between. Based on the band offset of the bulk material before contact and the interfacial Fermi level shift after contact, the energy level alignments at the CdSe/CdTe and CdTe/CdSe interface were deduced for the double-shelled nanocable arrays. The CdTe/CdSe interface of the ZnO/CdTe/CdSe nanocables has a negative band offset of −0.16 eV whilst for ZnO/CdSe/CdTe nanocables, the band edge of CdTe lies above CdSe with a conduction band offset of 0.16 eV at the CdSe/CdTe interface. Such a stepwise band alignment, together with the compact interface, fewer grain boundaries along the radial direction, and the fast transfer rate along the axial direction of the nanocables, makes the ZnO/CdSe/CdTe nanocable arrays photoanode have a saturated photocurrent of ∼14.3 mA cm−2. This is under the irradiation of AM1.5G simulated sunlight at 45 mW cm−2, which is greatly higher than ZnO/CdTe/CdSe, ZnO/CdSe or ZnO/CdTe nanocable arrays.

High-power high-linearity flip-chip bonded modified uni-traveling carrier photodiode

We demonstrate a flip-chip bonded modified uni-traveling carrier (MUTC) photodiode with an RF output power of 0.75 W (28.8 dBm) at 15 GHz and OIP3 as high as 59 dBm. The photodiode has a responsivity of 0.7 A/W, 3-dB bandwidth > 15 GHz, and saturation photocurrent > 180 mA at 11 V reverse bias.