Thermal activation and deactivation of grown‐in defects limiting the lifetime of float‐zone silicon

By studying the minority carrier lifetime in recently manufactured commercially available n‐ and p‐type float‐zone (FZ) silicon from five leading suppliers, we observe a very large reduction in the bulk lifetime when FZ silicon is heat‐treated in the range 450–700 °C. Photoluminescence imaging of these samples at the wafer scale revealed concentric circular patterns, with higher recombination occurring in the centre, and far less around the periphery. Deep level transient spectroscopy measurements indicate the presence of recombination active defects, including a dominant center with an energy level at ～E_v + 0.5 eV. Upon annealing FZ silicon at temperatures >1000 °C in oxygen, the lifetime is completely recovered, whereby the defects vanish and do not reappear upon subsequent annealing at 500 °C. We conclude that the heat‐treatments at >1000 °C result in total annihilation of the recombination active defects. Without such high temperature treatments, the minority carrier lifetime in FZ silicon is unstable and will affect the development of high efficiency (>24%) solar cells and surface passivation studies.     

The electrical properties of zinc in silicon

Electrically active deep levels related to zinc in silicon are investigated in n- and p-type silicon using Deep-Level Transient Fourier Spectroscopy (DLTFS) measurements. While in n-type silicon a level at E _C–0.49 eV is observed, the main zinc-related levels in p-type silicon are determined to be E _V+0.27 eV and E _V+0.60 eV. The latter are associated with zinc situated on regular silicon lattice sites. The emission rate of these centers exhibits a field dependence which cannot be quantitatively explained with the Poole-Frenkel model. On the other hand, a shallow level at E _V+0.09 eV is observed only in boron-doped silicon which may be related to a zinc-boron complex. Other zinc-related levels are found at E _V+0.23 eV and E _V+0.33 eV, their concentration depending on that of zinc on substitutional sites. In addition, the evaluation of depth profiles and the analysis of the field dependence of the emission rate based on the DLTFS method is presented.     

The effect of a weak magnetic field on the mobility of dislocations in silicon

The magnetoplastic effect in dislocation silicon is discovered. It is shown that in the presence of tensile stresses (up to 20 MPa), the mechanically activated path of surface dislocation half-loops is limited mainly by the dynamics of defects in various slip systems relative to the applied load. The activation barriers for the motion of dislocations controlled by various conditions in the temperature range T=850–950 K are E _aF=2.1±0.1 eV and E _aS=1.8±0.1 eV. An increase in the path of surface dislocation half-loops and a change in the activation barriers are detected (E _aF=1.4±0.1 eV and E _aS=1.6±0.1 eV) after subjecting silicon to a magnetic field (B=0.7 T) for 30 min. Possible reasons behind the observed effects are discussed.     

Electrical properties and diffusion behavior of hafnium in single crystal silicon

Electrical properties and diffusivity of Hf in single crystal Si have been studied. Several deep level defects were found for Hf in both the upper and lower half of the silicon band gap, and their parameters were measured. Energy levels, concentrations, and capture cross sections were determined for all Hf defects. The DLTS spectra depend on the cooling rate. Analysis of electrical properties yielded a dominant deep level defect at E_C -0.27 eV, which showed field enhanced emission due to Poole–Frenkel effect, confirming its donor nature. This agreed with results obtained using CV and TSCAP. In the lower half of the bandgap, a defect level at E_V +0.24 eV was found to have a capture barrier of 0.04 eV. Diffusivity of Hf was studied using two methods for Hf incorporation in Si – ion implantation and sputtering. Analysis of broadening of the Hf profile in implanted samples, which were annealed for 168 h, allowed us to estimate the diffusivity of Hf as 1.7×10^-15 cm²/s at 1250 °C: the spreading of implanted profiles at lower temperatures was too small. Analysis of Hf depth profiles in the sputtered and annealed samples reveals that Hf appears to have a fast and slow component to its diffusivity whose migration energy was determined to be 3.5±0.3 eV and 4.1±0.3 eV respectively. The fast and slow component are ascribed to interstitial and substitutional Hf with an energy level of E_C -0.27 eV and E_V +0.43 eV respectively. The mechanism for the fast component seems to indicate a direct interstitial diffusion mechanism whereas the diffusion of the substitutional Hf seems most consistent with the concerted exchange diffusion mechanism. In addition, estimates of solubility for both, interstitial and substitutional Hf, are included. PACS 61.72.Tt; 66.30.Jt; 71.55.Cn     

Band alignment at sputtered ZnSx O1–x/Cu(In,Ga)(Se,S)2 heterojunctions

Valence band offsets ΔE_VBM at ZnS_x O_1–x/Cu(In,Ga)(Se,S)₂ (CIGSSe) heterojunctions have been studied by photoemission spectroscopy (XPS, UPS) as a function of composition x in sputtered ZnS_x O_1–x films. In the composition range from ZnO to ZnS we found ΔE_VBM between –(2.1 ± 0.3) eV and –(0.8 ± 0.4) eV, respectively. Considering the optical band gaps, the conduction band offsets ΔE_CBM range from –(0.1 ± 0.3) eV to +(1.4 ± 0.4) eV. These results suggest that sputtered ZnS_x O_1–x is suitable as substitution for the CdS buffer and ZnO window layers in standard chalcopyrite‐based solar cells. Current–voltage characteristics of the solar cells have been investigated as a function of the composition x. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Concentrations of radiation defects with almost isoenergetical levels in silicon

Isochronous annealing of radiation defects with almost isoenergetical levels (indistinguishable from each other by means of temperature dependence of the majority charge carriers concentration) in silicon is studied. The concentrations of G- and A-centres with a level E _c?0.17 eV in n-Si and some (unidentified) vacancy-type and V₂+B complexes with a level E _v+0.22 eV in p-Si are determined.     

Synthesis and characterization of a family of layered trichalcogenides for assisted hydrogen photogeneration

Three layered trisulfides (TiS₃, ZrS₃, HfS₃) have been synthesized by solid–gas reaction between metal and sulfur in a vacuum sealed ampoule at 550 °C during 60 h. The samples used in this work were prepared from a colloidal suspension of powder of each one of the metal trisulfides (MS₃, M = Ti, Zr, Hf) in ethanol and deposited on titanium disks and quartz substrates by ”drop coating” technique. These samples have been characterized by X‐ray diffraction, energy dispersive analysis of X‐ray and scanning electron microscopy. The obtained direct optical band gaps are 1.0 ± 0.1 eV, 2.0 ± 0.1 eV and 2.2 ± 0.1 eV for TiS₃, ZrS₃ and HfS₃, respectively. Photoelectrochemical measurements in 0.5 M Na₂SO₃ have been carried out to characterize the MS₃/electrolyte interface. The flat‐band potentials (V_fb) vs. Ag/AgCl measured by electrochemical impedance spectroscopy (EIS) are –0.84 ± 0.02 V (TiS₃), –0.93 ± 0.02 V (ZrS₃) and –0.92 ± 0.02 V (HfS₃). Hydrogen generation was investigated in a photoelectrochemical cell (PEC) with MS₃ as photoanodes under white light illumination of 200 ± 20 mW/cm² at external bias potentials of 0.3 V vs. Ag/AgCl. Hydrogen evolution flows have been quantified by quadrupole mass spectrometry (QMS) reaching instantaneous values up to 19 ± 2 nmol H₂/min cm² with TiS₃ as photoanode.     

Investigation of the electrophysical properties and structures of impurity-defective complexes in silicon doped with palladium

Electric and structural methods are used to investigate formation of impurity-defective complexes in silicon doped with palladium. It is demonstrated that acceptor levels E _C – 0.18 and E _v + 0.34 eV detected in silicon during incorporation of palladium are caused by singly and doubly negatively charged states of [Pd–V] complexes, and the donor level E _v + 0.32 eV is a product of chemical compound of palladium with hydrogen forming the [Pd–H] complex. It is assumed that the palladium impurity in the doped silicon samples causes the elastic crystal energy to change and impurity clouds to be formed around microdefects. An increase in the temperature of palladium diffusion in silicon causes the impurity clouds to decay and the microdefect core sizes to decrease with their subsequent chaining into a needle.     

Infrared modulated reflectance spectra of n and p type gallium antimonide and n type indium antimonide

We have observed the modulated reflectance spectra of n and p type GaSb at 300, 80, and 5 K from 0.56 to 2 eV. The modulated reflectance of intrinsic n type InSb was measured at 80 K from 0.2 to 2 eV. The “dry sandwich” vapor deposition technique was used to make the electroreflectance (ER) samples. The low-temperature spectrum of the undoped p type GaSb sample shows three peaks at the band edge that could be associated with transitions from the top of the valence band, the light (0.903 eV) and heavy (1.014eV) hole state Fermi levels to the conduction band. The energies of the observed peaks are in agreement with the Fermi level determination from Hall effect and Faraday rotation measurements. This modulation mechanism is based on band population effects. The ER signal of InSb under flatband condition at 80 K has five half oscillations at the direct band gap. The contribution of piezoelectric strain to ER is present since the dc bias required to achieve flatband condition is different at the band gap than at E₁. The ER signal corresponding to the direct gap energy E₀ and to the spin-orbit energy E₀ + Δ₀ was determined in the n and p type samples of GaSb at different temperatures. We have measured the intrinsic energy gap in GaSb at room temperature. E_g = 0.74 eV. The corresponding spin-orbit splitting was found to be Δ₀ = 0.733 ± 0.002 eV.     

Studies of annealing of point defects and their influence on the electrical degradation and recovery behaviors of heavily neutron irradiated silicon

We have investigated the annealing behaviors of point defects and their influence on the electrical degradation and recovery of heavily neutron irradiated silicon. It is found that high concentrations of divacancy (V₂) and vacancy-oxygen (VO) complexes are introduced in heavily irradiated silicon, which is responsible for the enhanced carrier recombination and therefore the observed drastic decrease of carrier lifetime. While the dopants deactivation from vacancy-phosphorus (VP) complexes and carrier compensation from VO and V₂ complexes result in the remarkable increase of resistivity. After post-irradiation isochronal annealing at 200–400°C the carrier lifetime and resistivity exhibit insignificant changes, which is attributed to the transformation of V₂ and VO complexes into [VO?+?O_i], V₂O, V₃O complexes at 200–300°C and the possible formation of VP-O complexes at 400°C. While the heat treatments at elevated temperatures (>400°C) result in the elimination of the majority of electrically active V_mO_n and the possible VP-O complexes, and therefore the carrier lifetime and resistivity of silicon begin to recover at 500°C and 650°C, respectively. However, the recovery of carrier lifetime is incomplete, which is due to the enhanced carrier-recombination from the survival defects with deep levels at E_C ? 0.24?eV and E_C ? 0.44?eV during annealing.     

Low temperature photoconductivity in electron - irradiated p-type Si

The photoconductivity spectra of p-type silicon irradiated at ～15 °K with 1.2 MeV electrons were studied in the wavelength range from 1.2 to 5.5 μ at temperatures from 23 to 80 °K. The 3.9 μ photoconductivity band appears immediately after irradiation in all crystals already at low temperatures, giving further evidence that it is due to the divacancy formed directly during irradiation by electrons. Three main annealing stages of the photoconductivity have been observed; (a) below 160 °K, (b) 160–250 °K, and (c) 280–360 °K. A radiation-induced deep level at E_v , +(0.12±0.02 eV disappears upon annealing at stage b. The annealing behavior of the spectra depends strongly on the measuring temperature. The dependence of the spectra on chopper speed was also investigated.     

Tuning of the open‐circuit voltage by wide band‐gap absorber and doped layers in thin film silicon solar cells

We present an experimental study combined with computer simulations on the effects of wide band‐gap absorber and window layers on the open‐circuit voltage (V_oc) in single junction thin film silicon solar cells. The quantity ΔE_p, taking as the difference between the band gap and the activation energy in ?p? layer, is treated as a measure of the p‐layer properties and shows a linear relation with V_oc over a range of 100 mV with a positive slope of around 430 mV/eV. Two limiting mechanisms of V_oc are identified: the built‐in potential at lower ΔE_p and the band gap of the absorber layer at higher ΔE_p. The results of the experimental findings are confirmed by computer simulations. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Plasma hydrogenated,reactively sputtered aluminium oxide for silicon surface passivation

The intentional addition of hydrogen during reactive sputtering of AlO_x films has led to a dramatic improvement of the surface passivation of crystalline silicon wafers achieved with this technique. The 5 ms effective minority carrier lifetime measured on 1.5 Ω cm n‐type CZ silicon wafers is close to the 6 ms of a control wafer coated by atomic layer deposition (ALD) of AlO_x. Hydrogen‐sputtered films also provide excellent passivation of 1 Ω cm p‐type silicon, as demonstrated by an effective lifetime of 1.1 ms. It is likely that the improved passivation is related to the formation of an interfacial silicon oxide layer, as indicated by FTIR measurements. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Efficient interdigitated back‐contacted silicon heterojunction solar cells

We present back‐contacted amorphous/crystalline silicon heterojunction solar cells (IBC‐SHJ) on n‐type substrates with fill factors exceeding 78% and high current densities, the latter enabled by a SiN_x /SiO₂ passivated phosphorus‐diffused front surface field. V_oc calculations based on carrier lifetime data of reference samples indicate that for the IBC architecture and the given amorphous silicon layer qualities an emitter buffer layer is crucial to reach a high V_oc, as known for both‐side contacted silicon heterojunction solar cells. A back surface field buffer layer has a minor influence. We observe a boost in solar cell V_oc of 40 mV and a simultaneous fill factor reduction introducing the buffer layer. The aperture‐area efficiency increases from 19.8 ± 0.4% to 20.2 ± 0.4%. Both, efficiencies and fill factors constitute a significant improvement over previously reported values. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fast and slow lifetime degradation in boron‐doped Czochralski silicon described by a single defect

A demonstration that boron–oxygen related degradation in boron‐doped Czochralski silicon could be caused by a single defect with two trap energy levels is presented. In this work, the same two‐level defect can describe the fast and slow lifetime decay with a capture cross‐section ratio of electrons and holes for the donor level of σ_n/σ_p = 19 ± 4. A model is proposed for the multi‐stage degradation involving a single defect, in which the product of the slow reaction is a reactant in the fast reaction. After thermal processing, a population of interstitial oxygen (O_i) exists in a certain state (the precursor state) that can rapidly form defects (fast degradation) and another population of O_i exists in a state that is required to undergo a slow transformation into the precursor state before defect formation can proceed (slow degradation). Kinetic modelling is able to adequately reproduce the multi‐stage degradation for experimental data. Dark annealing is also shown to impact the extent of ‘fast’ degradation. By decreasing the dark annealing time on pre‐degraded wafers, a more severe ‘fast’ degradation of the samples can be enabled during subsequent illumination, consistent with this theory. The paper then discusses possible candidates for the chemical species involved. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

用阻塞效应测量28Si 13.095MeV激发态能级寿命

改进Al单晶样品的处理方法,得到了高质量的样品。进行了Al单晶辐照损伤实验,直接测量了E_p=1565keV时²⁷Al(p,α)²⁴Mg共振所形成的²⁸Si 13.095MeV激发态能级寿命。采用MonteCarlo模拟和“分析”方法计算得到其寿命值τ=16.3±2.4as,对应的能级宽度Γ=40±6eV,与文献报道的共振产额法结果符合得较好。 关键词：     

Monovacancy formation energy in copper,silver, and gold by positron annihilation

Monovacancy formation energies in copper, silver, and gold have been deduced from the temperature variation of the peak counting rate in the angular correlation curve of positron annihilation radiation from these metals. The counting rate was temperature dependent over the entire temperature range, including temperatures so low that no trapping of positrons at vacancies is effective. At these temperatures the increase in counting rate results from thermal expansion of the lattice. By separating this thermal expansion effect from the vacancy trapping effect at higher temperatures, we obtained values for the monovacancy formation energyE _1v for copper, silver, and gold to 1.29±0.02 eV, 1.16±0.02 eV, and 0.97±0.01 eV, respectively.     

Surface passivation schemes for high‐efficiency n‐type Si solar cells

An effective passivation on the front side boron emitter is essential to utilize the full potential of solar cells fabricated on n‐type silicon. However, recent investigations have shown that it is more difficult to achieve a low surface recombination velocity on highly doped p‐type silicon than on n‐type silicon. Thus, the approach presented in this paper is to overcompensate the surface of the deep boron emitter locally by a shallow phosphorus diffusion. This inversion from p‐type to n‐type surface allows the use of standard technologies which are used for passivation of highly doped n‐type surfaces. Emitter saturation current densities (J_0e) of 49 fA/cm² have been reached with this approach on SiO₂ passivated lifetime samples. On solar cells a certified conversion efficiency of 21.7% with an open‐circuit voltage (V_oc) of 676 mV was achieved. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Interstitial iron and iron-acceptor pairs in silicon

Deep levels in iron-dopedp-type silicon are investigated by means of Deep Level Transient Spectroscopy (DLTS) and the Hall effect. Pairs of Fe with the acceptors B, Al, and Ga are observed at 0.1, 0.19, and 0.24 eV above the valence band edgeE _v. For interstitial iron, (Fe _i ), a level energy ofE _v+0.39+-0.02 eV is obtained with DLTS after correction with a measured temperature dependence of the capture cross section. The Hall effect yieldsE _v+0.37 eV for Fe_i. The annealing behavior of levels related to Fe is investigated up to 160 °C. Iron participates in at least four different types of impurity states: Fe _i , Fe-acceptor pairs, precipitations (formed above 120 °C) and an additional electrically inactive state, which is formed at room temperature.     

Transition metal impurities in silicon: New defect reactions

Recent investigations on transition-metal impurities in silicon emphasizing the effect of the combined diffusion of two transition metals are presented and briefly discussed. The electronic properties and basic thermal kinetics are analysed by DLTS. The conversion of a Pd-related multivalent defect atE _c-0.35 eV andE _c-0.57 eV to the Pd-related defect atE _c –0.22 eV is observed, and a Pd-Fe complex level atE _c –0.32 eV is identified. The annealing characteristics of the multivalent Rh levels atE _c-0.33 eV andE _c-0.57 eV are observed, and used to analyse the influence of prior Rh doping on the Au diffusion. A complex formed by the codiffusion of Au and Cu is observed atE _v+0.32eV andE _v+0.42 eV, and shown to exhibit bistable behavior as does a similarly produced Au-Ni complex observed atE _v + 0.35 eV andE _v+0.48 eV.