Sub-bandgap Absorption Research Articles

Defects in 6 MeV H+ irradiated hydrothermal ZnO single crystal

The effect of 6 MeV H+ irradiation on hydrothermally grown ZnO single crystal has been investigated using high resolution x-ray diffraction (HRXRD) and optical absorption (ultraviolet–visible) spectroscopy. The increase of the diffuse scattering in the reciprocal space maps measured using HRXRD indicates an increase of the point defect density upon irradiation. Within the penetration depth of x-rays of several micrometres, the defect density increased with increasing distance from the sample surface. On the other hand, the near band gap optical absorption became sharper for the irradiated crystal. This reflects enhanced band to band absorption and reduced sub-band gap absorption due to defects. Temperature dependent photoluminescence spectra of the pristine sample show negative thermal quenching (NTQ) of the luminescence which is due to the presence of two or more donor related defects. Upon irradiation, a single dominant donor bound transition can be found without any temperature induced NTQ. Enhancement of the band edge luminescence and reduction of the defect related luminescence is observed at 10 K. Such changes have been discussed in the light of the hydrogen present in the as-grown state of hydrothermal ZnO.

Ruling out the impact of defects on the below band gap photoconductivity of Ti supersaturated Si

In this study, we present a structural and optoelectronic characterization of high dose Ti implanted Si subsequently pulsed-laser melted (Ti supersaturated Si). Time-of-flight secondary ion mass spectrometry analysis reveals that the theoretical Mott limit has been surpassed after the laser process and transmission electron microscopy images show a good lattice reconstruction. Optical characterization shows strong sub-band gap absorption related to the high Ti concentration. Photoconductivity measurements show that Ti supersaturated Si presents spectral response orders of magnitude higher than unimplanted Si at energies below the band gap. We conclude that the observed below band gap photoconductivity cannot be attributed to structural defects produced by the fabrication processes and suggest that both absorption coefficient of the new material and lifetime of photoexcited carriers have been enhanced due to the presence of a high Ti concentration. This remarkable result proves that Ti supersaturated Si is a promising material for both infrared detectors and high efficiency photovoltaic devices.

Defects in 700 keV oxygen ion irradiated ZnO

It is well known that energetic oxygen ions induce heavy crystalline disorder in ZnO, however, systematic study on this regard is very much limited. Here, we present photoluminescence (PL), optical absorption and sheet resistance measurements on poly and single crystalline ZnO samples irradiated with 700keV O ions. Results have been compared with the effects of 1.2MeV Ar irradiation on similar ZnO target. Colour change of the samples with increasing O irradiation fluence has also been noted. Non-monotonic variation of room temperature sheet resistance with the increase of fluence has been observed for polycrystalline ZnO. Such an outcome has been understood as point defects transforming to bigger size clusters. Near band edge (NBE) PL emission is largely reduced due to O ion irradiation. However, at 10K NBE emission can be observed for irradiated polycrystalline samples. Irradiated ZnO single crystal does not show any band to band transition even at 10K. It is evident that dynamic recovery of defects is more effective in polycrystalline samples. Ultraviolet–visible absorption spectrum of the irradiated ZnO crystal show pronounced sub-band gap absorption. Oxygen irradiation generated new absorption band in ZnO is at 3.05eV. In the light of earlier reports, this particular band can be ascribed to absorption by neutral oxygen vacancy defects.

Interband absorption of photons by extended states in intermediate band solar cells

This paper considers sub-bandgap photon absorption in an InAs/GaAs quantum dot matrix. Absorption coefficients are calculated for transitions from the extended states in the valence band to confined states in the conduction band. This completes a previous body of work in which transitions between bound states were calculated. The calculations are based on the empirical k·p Hamiltonian considering the quantum dots as parallelepipeds. The extended states may be only partially extended—in one or two dimensions—or extended in all three dimensions. It is found that extended-to-bound transitions are, in general, weaker than bound-to-bound transitions, and that the former are weaker when the initial state is extended in more coordinates. This study is of direct application to the research of intermediate band solar cells and other semiconductor devices based on light absorption in semiconductors nanostructured with quantum dots.

Investigation on optical absorption properties of electrochemically formed porous InP using photoelectric conversion devices

We investigated the optical absorption properties of InP porous structures formed by the electrochemical process using photoelectric conversion (PC) devices formed on p–n junction substrates. The photocurrent measurements revealed that the current from PC devices changed in response to the incident light power and the thickness of the top layer on the p–n interface. Since the photocarriers contributing to the observed photocurrents are excited by the photons reaching the p–n interface through the top layer, the photocurrents give us information on the optical absorption properties of the top layer. The photocurrents observed on a porous device with a porous structure in the top layer were lower than that of a non-porous device, indicating that the absorption properties of InP were enhanced after the formation of porous structures. This phenomenon can be explained in terms of absorption coefficient, α, increased by the light scattering and the sub-bandgap absorption in the porous layer.

Interface engineering of Ge using thulium oxide: Band line-up study

Thulium oxide layers on germanium were investigated.The valence band offset was found to be 2.95eV.The band gap of thulium oxide was found to be 5.3eV from the Tauc method.A sub-band gap absorption at 3.2eV points to a bulk thulium oxide defect.A permittivity of 14 was derived from electrical measurements. This paper investigates the band line-up and optical properties (dielectric function) of Tm2O3/Ge gate stacks deposited by atomic layer deposition. X-ray photoelectron spectroscopy has been performed to ascertain the shallow core levels (Ge3d and Tm4d) in ultra-thin and bulk Tm2O3/Ge stacks as well as valence band maxima in Ge and bulk Tm2O3. The valence band offset of Tm2O3/Ge has been found to be 2.95?0.08eV. Vacuum ultra violet variable angle spectroscopic ellipsometry studies reveal the indirect band gap nature of Tm2O3, with the value extracted from the Tauc method of 5.3?0.1eV. A distinct absorption feature is observed at ~3.2eV below the band gap of Tm2O3, and clearly distinguished from the Si and Ge critical points. A dielectric constant of 14 to 15 has been derived from the electrical measurements on 5nm Tm2O3/epi Ge/Si gate stacks. The band line-up study of Tm2O3/Ge implies an acceptable barrier for holes (2.95eV) and electrons (greater than 1.7eV) for Ge MOSFET engineering.

Obtaining an intermediate band photovoltaic material through the Bi insertion in CdTe

Defect interaction can take place in CdTe under Te and Bi rich conditions. We demonstrate in this work through first principles calculations, that this phenomenon allows a Jahn Teller distortion to form an isolated half-filled intermediate band in the host semiconductor band-gap. This delocalized energy band supports the experimental deep level reported in the host band-gap of CdTe at a low bismuth concentration. Furthermore, the calculated optical absorption of CdTe:Bi in this work shows a significant subband-gap absorption that also supports the enhancement of the optical absorption found in the previous experimental results.

Mid-infrared absorptance of silicon hyperdoped with chalcogen via fs-laser irradiation

Silicon hyperdoped with heavy chalcogen atoms via femtosecond-laser irradiation exhibits strong broadband, sub-bandgap light absorption. Understanding the origin of this absorption could enable applications for hyperdoped-silicon based optoelectronic devices. In this work, we measure absorption to wavelengths up to 14 μm using Fourier transform infrared spectroscopy and study sulfur-, selenium-, and tellurium-hyperdoped Si before and after annealing. We find that absorption in the samples extends to wavelengths as far as 6 μm. After annealing, the absorption spectrum exhibits features that are consistent with free-carrier absorption. Although the surface morphology influences the shape of the absorption curves, the data permit us to place an upper bound on the position of the chalcogen dopant energy levels.

Thermally and optically induced effects on sub-band gap absorption in nanocrystalline CdSe (nc-CdSe) thin films

Nanocrystalline cadmium selenide (nc-CdSe) thin films have been prepared by thermal evaporation using the inert gas condensation (IGC) technique. Transmission electron microscopy (TEM) studies show that the CdSe nanocrystals (NCs) are spherical in shape. Constant photocurrent method (CPM) is used to determine the value of absorption coefficient in low absorption region of as-deposited, annealed and light soaked nc-CdSe thin films. Values of optical band gap (Eg) have been determined by using Tauc's relation for as-deposited, annealed and light soaked nc-CdSe thin films from the α values evaluated from reflection and transmission measurements. We have used a derivative procedure to sub-gap absorption spectra in order to get information on the energetic distribution of the occupied density of states below Fermi level. Constants such as optical gap Eg, Urbach edge Eu have been obtained from CPM spectra in as-deposited, annealed and light soaked nc-CdSe thin films. Concentration of defect states has also been calculated in as-deposited, annealed and light soaked nc-CdSe thin films.

A numerical study into the influence of quantum dot size on the sub-bandgap interband photocurrent in intermediate band solar cells

A numerical study is presented of the sub-bandgap interband photon absorption in quantum dot intermediate band solar cells. Absorption coefficients and photocurrent densities are calculated for the valence band to intermediate band transitions using a four-band k·p method. It is found that reducing the quantum dot width in the plane perpendicular to the growth direction increases the photocurrent from the valence band to the intermediate-band ground state if the fractional surface coverage of quantum dots is conserved. This provides a path to increase the sub-bandgap photocurrent in intermediate band solar cells.

Determination of free-carrier and phonon-assisted absorptions for Si-doped GaSb thin layers

Photothermal deflection spectroscopy is used in order to investigate near- and sub-band gap absorption of Si-doped GaSb epilayers deposited by MBE on a semi-insulating GaAs substrate. The optical absorption spectra show an extra absorption on the transparency region below the bandgap due to free-carrier absorption. However, for energies above the gap, we notice a linear behavior of the square root of the absorption coefficient versus the heating beam energy, which is attributed to phonon-assisted absorption. From interpolation of the phonon absorption to low energies we have determined the free-carrier absorption that is found to follow the Drude law.

Sub-bandgap absorption in organic solar cells: experiment and theory

Most high-performance organic solar cells involve bulk-heterojunctions in order to increase the active donor-acceptor interface area. The power conversion efficiency depends critically on the nano-morphology of the blend and the interface. Spectroscopy of the sub-bandgap region, i.e., below the bulk absorption of the individual components, provides unique opportunities to study interface-related properties. We present absorption measurements in the sub-bandgap region of bulk heterojunctions made of poly(3-hexylthiophene-2,5-diyl) as an electron donor and [6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) as an electron acceptor and compare them with quantum-chemical calculations and recently published data on the external quantum efficiency (EQE). The very weak absorption of the deep sub-bandgap region measured by the ultra-sensitive Photothermal Deflection Spectroscopy (PDS) features Urbach tails, polaronic transitions, conventional excitons, and possibly charge-transfer states. The quantum-chemical calculations allow characterizing some of the unsettled spectral features.

Double Ion Implantation and Pulsed Laser Melting Processes for Third Generation Solar Cells

In the framework of the third generation of photovoltaic devices, the intermediate band solar cell is one of the possible candidates to reach higher efficiencies with a lower processing cost. In this work, we introduce a novel processing method based on a double ion implantation and, subsequently, a pulsed laser melting (PLM) process to obtain thicker layers of Ti supersaturated Si. We perform ab initio theoretical calculations of Si impurified with Ti showing that Ti in Si is a good candidate to theoretically form an intermediate band material in the Ti supersaturated Si. From time-of-flight secondary ion mass spectroscopy measurements, we confirm that we have obtained a Ti implanted and PLM thicker layer of 135 nm. Transmission electron microscopy reveals a single crystalline structure whilst the electrical characterization confirms the transport properties of an intermediate band material/Si substrate junction. High subbandgap absorption has been measured, obtaining an approximate value of 104 cm−1in the photons energy range from 1.1 to 0.6 eV.

Optimization of Idealized Quantum Dot Intermediate Band Solar Cells Considering Spatial Variation of Generation Rates

The influences of the intermediate band (IB) filling, the absorption coefficient constants, and the IB position on the efficiency of a quantum dot intermediate band solar cell (QD-IBSC) are investigated considering the spatial variation of subbandgap generation rates. A new definition of optimal intermediate band filling is proposed. A mathematical model is developed to optimize the intermediate band solar cell (IBSC) structure under idealized conditions, which calculates the optimal ratio of the subbandgap absorption coefficient constants and the optimal position of IB.

Using carrier-depletion silicon modulators for optical power monitoring

Defect-mediated subbandgap absorption is observed in ion-implanted silicon-on-oxide waveguides that experience a rapid thermal annealing at 1075°C. With this effect, general carrier-depletion silicon modulators exhibit the capability of optical power monitoring. Responsivity is measured to be 22 mA/W for a 3 mm long Mach-Zehnder modulator of 2×10(18) cm(-3) doping concentration at -7.1 V bias voltage and 5.9 mA/W for a ring modulator of 1×10(18) cm(-3) doping concentration at -10 V bias voltage. The former is used to demonstrate data detection of up to 35 Gbits/s.

Bias Dependence of Sub-Bandgap Light Detection for Core–Shell Silicon Nanowires

We experimentally demonstrate a vertically arrayed silicon nanowire-based device that exhibits voltage dependence of photoresponse to infrared sub-bandgap optical radiation. The device is fabricated using a proximity solid-state phosphorus diffusion method to convert the surface areas of highly boron-doped silicon nanowires into n-type, thus forming a radial core-shell p-n junction structure. Prominent photoresponse from such core-shell Si nanowires is observed under sub-bandgap illumination at 1310 nm. The strong bias dependence of the photoresponse and other device characteristics indicates that the sub-bandgap absorption is attributed to the intrinsic properties of core-shell Si nanowires rather than the surface states. The attractive characteristics are based on three physical mechanisms: the Franz-Keldysh effect, quasi-quantum confinement effect, and the impurity-state assisted photon absorption. The first two effects enhance carrier tunneling probability, rendering a stronger wave function overlap to facilitate sub-bandgap absorption. The last effect relaxes the k-selection rule by involving the localized impurity states, thus removing the limit imposed by the indirect bandgap nature of Si. The presented device uses single-crystal silicon and holds promise of fabricating nanophotonic systems in a fully complementary metal-oxide-semiconductor (CMOS) compatible process. The concept and approach can be applied to silicon and other materials to significantly extend the operable wavelength regime beyond the constraint of energy bandgap.

Optical absorption dependence on composition and thickness of InxGa1 − xN (0.05 < × < 0.22) grown on GaN/sapphire

We report the change in optical absorption properties of InGaN epilayers around the critical layer thickness determined from X-ray diffraction. Detrimental sub-band gap absorption is observed in InGaN thin films grown beyond the critical layer thicknesses, and is caused by localized electric fields around extended crystalline defects and aided by V-defects through light channeling. The photoluminescence response from InGaN thin films, grown beyond the critical layer thickness, is reduced owing to absorption of the incident laser light by non-radiative recombination extended crystalline defects. The formation of V-defects is observed to occur beyond the critical layer thickness and continues to grow in areal coverage aiding in sub-band gap absorption. This optical behavior sets constraints to be incorporated in the design of InGaN solar cell and requirement for improvement in epitaxial growth techniques to reduce V-defects.

Sub-bandgap absorption in polymer-fullerene solar cells studied by temperature-dependent external quantum efficiency and absorption spectroscopy

We study the sub-bandgap (SBG) absorption in solar cells made of poly(3-hexylthiophene-2,5-diyl) and [6,6]-phenylC61-butyric-acid-methyl-ester by photothermal deflection absorption spectroscopy and measurement of temperature-dependent external-quantum-efficiency (EQE) spectra. Several models for SBG absorption are critically reviewed in view of the EQE results. The latter suggest polaron-related transitions as origin of the Gaussian SBG peak near 1.6eV. Intermolecular charge transfer (CT) excitations as an explanation cannot completely be ruled out. However, the assumption of CT excitons with large binding energies is difficult to reconcile with the rapid loss of weight of the Gaussian SBG-peak seen in EQE above room temperature.

Enhancement of optical absorption by modulation of the oxygen flow of TiO2 films deposited by reactive sputtering

Oxygen-deficient TiO2 films with enhanced visible and near-infrared optical absorption have been deposited by reactive sputtering using a planar diode radio frequency magnetron configuration. It is observed that the increase in the absorption coefficient is more effective when the O2 gas supply is periodically interrupted rather than by a decrease of the partial O2 gas pressure in the deposition plasma. The optical absorption coefficient at 1.5 eV increases from about 1 × 102 cm−1 to more than 4 × 103 cm−1 as a result of the gas flow discontinuity. A red-shift of ∼0.24 eV in the optical absorption edge is also observed. High resolution transmission electron microscopy with composition analysis shows that the films present a dense columnar morphology, with estimated mean column width of 40 nm. Moreover, the interruptions of the O2 gas flow do not produce detectable variations in the film composition along its growing direction. X-ray diffraction and micro-Raman experiments indicate the presence of the TiO2 anatase, rutile, and brookite phases. The anatase phase is dominant, with a slight increment of the rutile and brookite phases in films deposited under discontinued O2 gas flow. The increase of optical absorption in the visible and near-infrared regions has been attributed to a high density of defects in the TiO2 films, which is consistent with density functional theory calculations that place oxygen-related vacancy states in the upper third of the optical bandgap. The electronic structure calculation results, along with the adopted deposition method and experimental data, have been used to propose a mechanism to explain the formation of the observed oxygen-related defects in TiO2 thin films. The observed increase in sub-bandgap absorption and the modeling of the corresponding changes in the electronic structure are potentially useful concerning the optimization of efficiency of the photocatalytic activity and the magnetic doping of TiO2 films.

Correlation between near infrared-visible absorption, intrinsic local and global sheet resistance of poly(3,4-ethylenedioxy-thiophene) poly(styrene sulfonate) thin films

The ordinary dielectric function of poly(3,4-ethylenedioxy-thiophene) poly(styrene sulfonate) (PEDOT:PSS) thin films was measured using a combination of spectroscopic ellipsometry and photothermal deflection spectroscopy. This method combination allows for a highly sensitive optical characterization of thin films. Hence, even the detection of weak sub-bandgap and intra-band absorptions is enabled. These intraband transitions of free charge carriers were modeled using a Drude-type oscillator to derive an intrinsic resistances for PEDOT:PSS. These optically derived resistances were compared with those determined by a 4-probe measurement setup for two different types of PEDOT:PSS and for varied annealing temperatures. Good agreement between optical and electrical measurements could be obtained for annealing temperatures smaller than 180∘C. Therefore, we conclude that the proposed combination of our two optical methods is well suited to determine electrical resistances of organic layers.