Charge carrier decay and diffusion in organic–inorganic CH3NH3PbI3–xClx perovskite based solar cell

In recent years, organic–inorganic lead halides attracted widespread interest, mainly due to their impressive photoconversion properties and low‐cost solution processing. In this study, we employed small amplitude transient photovoltage and photocurrent spectroscopy to investigate charge transport and recombination properties of perovskite CH₃NH₃PbI_3–xCl_x solar cell under realistic light harvesting conditions (<1 sun). Cell structure resembles outlay commonly found in organic photovoltaics, with perovskite absorber being sandwiched between two thin layers of organic polymers. Tested device displayed high power conversion efficiency (10.3%), good fill factor and negligible hysteresis effect. Fundamental device parameters were characterized at various open‐circuit voltages (V_oc) by examination of small voltage and current perturbations created by the low intensity pulsed laser excitations. The obtained results exhibit long charge carrier lifetimes and fast charge transport over the full range of applied optical bias, as well as remarkable diffusion lengths exceeding 1 μm. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Nongeminate recombination in organic bulk heterojunction solar cells: Contribution of exciton–polaron interaction

A new model to explain nongeminate recombination in organic bulk heterojunction solar cells is presented. We suggest that the annihilation of excitons on charge carriers at the interface between donor and acceptor phases competes with the bimolecular recombination of Coulombically bound electron–hole pairs. The exciton–polaron interaction gives visible contribution to the reduction of Langevin recombination. An analytical formula, which describes the reduction prefactor, has been derived. We demonstrate that exciton–charge carrier interactions cause an increase of the recombination order. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of Ga/(Ga + In) grading on deep‐defect states of Cu(In,Ga)Se2 solar cells

The benefits of gallium (Ga) grading on Cu(In,Ga)Se₂ (CIGS) solar cell performance are demonstrated by comparing with ungraded CIGS cells. Using drive‐level capacitance profiling (DLCP) and admittance spectroscopy (AS) analyses, we show the influence of Ga grading on the spatial variation of deep defects, free‐carrier densities in the CIGS absorber, and their impact on the cell's open‐circuit voltage V_oc. The parameter most constraining the cell's V_oc is found to be the deep‐defect density close to the space charge region (SCR). In ungraded devices, high deep‐defect concentrations (4.2 × 10¹⁶cm^–3) were observed near the SCR, offering a source for Shockley–Read–Hall recombination, reducing the cell's V_oc. In graded devices, the deep‐defect densities near the SCR decreased by one order of magnitude (2.5 × 10¹⁵ cm^–3) for back surface graded devices, and almost two orders of magnitude (8.6 × 10¹⁴ cm^–3) for double surface graded devices, enhancing the cell's V_oc. In compositionally graded devices, the free‐carrier density in the absorber's bulk decreased in tandem with the ratio of gallium to gallium plus indium ratio GGI = Ga/(Ga + In), increasing the activation energy, hindering the ionization of the defect states at room temperature and enhancing their role as recombination centers within the energy band. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Assessment of the illumination dependency of Al2O3 and SiO2 rear‐passivated p‐type silicon solar cells

This Letter discusses an important difference between positively charged SiO₂ and negatively charged Al₂O₃ rear‐passivated p‐type Si solar cells: their illumination level dependency. For positively charged SiO₂ rear‐passivated p‐type Si solar cells, a loss in short circuit current (J_SC) and open circuit voltage (V_OC) as a function of illumination level is mainly caused by parasitic shunting and a decrease in surface recombination, respectively. Hence, the relative loss in cell conversion efficiency, J_SC, and V_OC as a function of the illumination level for SiO₂ compared to Al₂O₃ rear‐passivated p‐type Si solar cells has been measured and discussed. Subsequently, an exponential decay fit of the loss in cell efficiency is applied in order to estimate the difference in the energy output for both cell types in three different territories: Belgium (EU), Seattle and Austin (US). The observed trends in the difference in energy output between both cells, as a function of time of the year and region, are as expected and discussed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect removal after low temperature annealing of boron implantations by emitter etch‐back for silicon solar cells

Ion implantation offers new possibilities for silicon solar cell production, e.g. single side doping that can be structured in‐situ with shadow masks. While phosphorus implantations can easily be annealed at low temperature, the annealing of boron implantations is challenging. In this study, we use low energy implantations of boron (1 keV and 5 keV) with a projected range of 5.6 nm and 21.2 nm that form defects causing charge carrier recombination after a low temperature anneal (950 °C, 30 min). An ozone‐based wet chemical etching step is applied to remove this near surface damage. With increasing chemical etch‐back the electrical quality (i.e. emitter saturation current density, J_0e) improves continuously. The calculated limit for J_0e was reached with an abrasion of 35 nm for 1 keV and 85 nm for 5 keV implantations, showing that the relevant defects causing charge carrier recombination are located very close to the surface, corresponding to the as‐implanted profile depth. This emitter etch‐back allows for the fabrication of defect free boron doping profiles with good sheet resistance uniformity (standard deviation <2%). With the resulting characteristics (sheet resistance <100 Ω/sq, surface doping concentration >5 × 10¹⁹ cm^–3, J_0e < 30 fA/cm²), these boron profiles are well suited for silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Laser illumination for manipulation of hydrogen charge states in silicon solar cells

This Letter investigates the important parameters of illumination for control of hydrogen charge states in p‐type silicon solar cells. Through variations in the wavelength and intensity of illumination, evidence is provided for the importance of the neutral charge state of interstitial hydrogen, H⁰, for the passivation of defects in upgraded metallurgical grade (UMG) silicon. It is shown that through this approach minority carrier lifetimes may be achieved in excess of those realised through previous techniques, resulting in open‐circuit voltages (iV_OC) over 710 mV. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Internal cooling efficiency of a junction diode

The three thermal rate equations were built newly up at both ends and at the junction of a p–n diode, in order to derive analytically the temperature difference ΔT (between a junction and both ends) and the internal cooling efficiency η defined newly for a homojunction diode. The maxima ΔT and η of a diode were derived analytically as a function of V _j within the short-length approximation and calculated numerically as a function of V _j or V _bi, where V _j is a voltage across the junction and V _bi is a built-in voltage at the junction. As a result, ΔT increases abruptly with an increase of V _j below V _j=0.050 V or of V _bi below V _bi=0.10 V, while above their values, it increases slowly with an increase of V _j or V _bi to saturate a certain value. For example, ΔT was estimated as 14.6 K for Hg_0.8Cd_0.2Te diode with V _bi=0.36 V. η has a local maximum of 63% at V _j≈0.01 V or at V _bi≈0.03 V, while above their respective values, it decreases abruptly with an increase of V _j or V _bi and falls to 4.4% at V _bi=0.80 V which is equivalent to that of a diode emitting a laser for fiber optical communication. However, the greater enhancements in ΔT and η of a diode are required to apply the internal cooling system to a laser-emitting diode which needs the exact control of temperature. These results should be useful for the application of the internal cooling system to the double heterojunction diode used in the optical communication.     

Direct detection of carrier traps in Si solar cells after light‐induced degradation

In solar cells fabricated from boron‐doped Cz‐Si wafers minority and majority carrier traps were detected by deep level transient spectroscopy (DLTS) after so‐called “light‐induced degradation” (LID). The DLTS signals were detected from mesa‐diodes with the full structure of the solar cells preserved. Preliminary results indicate metastable traps with energy levels positioned at E_V + 0.37 eV and E_C – 0.41 eV and apparent carrier capture cross‐sections in the 10^–17–10^–18 cm² range. The concentration of the traps was in the range of 10¹²–10¹³ cm^–3. The traps were eliminated by annealing of the mesa‐diodes at 200 °C. No traps were detected in Ga‐doped solar cells after the LID procedure or below the light protected bus bar locations in B‐doped cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Comparative charge transfer studies in nonmetallated and metallated porphyrin fullerene dyads

Single material organic solar cells become an interesting area of research to overcome the challenges with efficient charge separation efficiencies in conventional organic solar cells. In this article, we have synthesized nonmetallated and metallated porphyrin‐fullerene dyad materials (H2P‐C60 and ZnP‐C60, respectively) with simple structure, comprehensively studied their charge transfer mechanism, and established a proof of concept that nonmetallated porphyrin‐fullerene dyads are better candidates to be used in organic solar cells compared with metallated dyads. Absorption and electrochemical analysis revealed the ground state electronic interactions between donor‐acceptor moieties in both types of dyads. Driving force (?ΔG^o_ET) for intramolecular electron transfer process was calculated by first oxidation and reduction potentials of dyads. The excited state electronic interactions were characterized by time‐resolved fluorescence and pump‐probe transient absorption experiments. Strong fluorescence quenching of porphyrin along with reduced lifetimes in dyads due to deactivation of singlet excited states by photoinduced charge transfer process between porphyrin/Zn‐porphyrin core and fullerene in different polarity solvents was observed. Transient absorption spectroscopy was also applied to identify the transient spectral features, ie, cationic (H2P⁺/ZnP⁺) and anionic (C₆₀^?) radicals formed because of the charge separation in both types of dyads. Finally, organic solar cell device was also fabricated using the dyads. We obtained higher V_oc, J_sc, and fill factor in single material organic solar cell using H2P‐C60 compared to previous reports.     

Silicon nanoparticle charge trapping memory cell

A charge trapping memory with 2 nm silicon nanoparticles (Si NPs) is demonstrated. A zinc oxide (ZnO) active layer is deposited by atomic layer deposition (ALD), preceded by Al₂O₃ which acts as the gate, blocking and tunneling oxide. Spin coating technique is used to deposit Si NPs across the sample between Al₂O₃ steps. The Si nanoparticle memory exhibits a threshold voltage (V_t) shift of 2.9 V at a negative programming voltage of –10 V indicating that holes are emitted from channel to charge trapping layer. The negligible measured V_t shift without the nanoparticles and the good re‐ tention of charges (>10 years) with Si NPs confirm that the Si NPs act as deep energy states within the bandgap of the Al₂O₃ layer. In order to determine the mechanism for hole emission, we study the effect of the electric field across the tunnel oxide on the magnitude and trend of the V_t shift. The V_t shift is only achieved at electric fields above 1 MV/cm. This high field indicates that tunneling is the main mechanism. More specifically, phonon‐assisted tunneling (PAT) dominates at electric fields between 1.2 MV/cm < E < 2.1 MV/cm, while Fowler–Nordheim tunneling leads at higher fields (E > 2.1 MV/cm). (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dopant‐free back contact silicon heterojunction solar cells employing transition metal oxide emitters

The present study investigates the electrical properties of transition metal oxide (TMO) emitters in dopant‐free n‐Si back contact solar cells by comparing the properties of solar cells employing three TMOs (WO_x, MoO_x and V₂O_x) with varying electrical properties acting as p‐type contacts. The TMOs are found to induce large band bending in n‐Si, which reduces the injection level dependent interfacial recombination speed S_eff and contact resistivity ρ_c. Among the TMO/n‐Si contacts considered, the V₂O_x/n‐Si contact achieves the lowest S_eff of 138 cm/s and ρ_c of 0.034 Ω cm², providing the significant advantages over heavily doped a‐Si:H(p)/n‐Si contacts. The best device performance was achieved by the V₂O_x/n‐Si solar cell, demonstrating an efficiency of 16.59% and an open‐circuit voltage of 610 mV relative to solar cells based on MoO_x/n‐Si (15.09%, 594 mV) and WO_x/n‐Si (12.44%, 539 mV). Furthermore, the present work is the first to employ WO_x, V₂O_x and Cs₂CO₃ in back contact solar cells. The fabrication process employed offers great potential for the mass production of back contact solar cells owing to simple, metal mask patterning with high alignment quality and dopant‐free steps conducted at a lower temperature.     

Increased open‐circuit voltage of ZnO nanowire/PbS quantum dot bulk heterojunction solar cells with solution‐deposited Mg(OH)2 interlayer

An ultrathin Mg(OH)₂ layer was solution‐deposited onto the ZnO nanowires to solve the problem of interfacial charge recombination, caused by the increase of interfacial area in bulk heterojunction (BHJ) PbS colloidal quantum dot solar cells (CQDSCs). This Mg(OH)₂ interlayer efficiently passivated the surface defects of ZnO nanowires and provided tunnel barrier at ZnO/PbS interface. As a result, the charge recombination at ZnO/PbS interface was largely suppressed, proved by the significantly elongated electron lifetime and the increased open‐circuit voltage of the Mg(OH)₂‐involved BHJ CQDSCs. Careful thickness optimization of Mg(OH)₂ interlayer finally brought a ～33% increase in V_oc and ～25% improvement in power conversion efficiency.     

Micro‐Raman analysis of GaAs Schottky barrier solar cell

Gallium arsenide (GaAs) cells have been in the race with silicon single‐crystal cells for the highest efficiency photovoltaic devices. The annealed, irradiated Schottky barrier (SB) solar cells were characterised using micro‐Raman spectroscopy at three different regions: namely, at the (1) ohmic contact region, (2) unirradiated region and (3) irradiated region. We also present a micro‐Raman study of the damage process in annealed GaAs SB solar cells bombarded by high‐energy ions. A Gaussian line shape was fitted to the Raman spectra of the longitudinal optical phonon A₁(LO), and parameters such as intensity, full width at half maximum (FWHM) and the area under the peak were obtained for the different annealing temperatures. Biaxial stress (σ), carrier concentration (n), depletion length (L_d), dislocation velocity (ν) and life time of the first‐order optical phonon (τ) of the A₁(LO) mode of the irradiated region of the samples annealed at different temperatures were calculated. Copyright © 2010 John Wiley & Sons, Ltd.     

Ion implantation into amorphous Si layers to form carrier‐selective contacts for Si solar cells

This paper reports our findings on the boron and phosphorus doping of very thin amorphous silicon layers by low energy ion implantation. These doped layers are implemented into a so‐called tunnel oxide passivated contact structure for Si solar cells. They act as carrier‐selective contacts and, thereby, lead to a significant reduction of the cell's recombination current. In this paper we address the influence of ion energy and ion dose in conjunction with the obligatory high‐temperature anneal needed for the realization of the passivation quality of the carrier‐selective contacts. The good results on the phosphorus‐doped (implied V_oc = 725 mV) and boron‐doped passivated contacts (iV_oc = 694 mV) open a promising route to a simplified interdigitated back contact (IBC) solar cell featuring passivated contacts. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

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)     

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)     

95 MeV Oxygen Ion Irradiation Effects on N-Channel Mosfets

The N-channel metal oxide semiconductor field effect transistors (MOSFETs) were exposed to 95 MeV oxygen ions in the fluence range of 5 × 10¹⁰ to 5 × 10¹³ ions/cm². The influence of ion irradiation on threshold voltage (V_TH), linear drain current (I_DLin), leakage current (I_L), drain conductance (gD), transconductance (gm), mobility (μ) and drain saturation current (I_DSat) of MOSFETs was studied systematically for various fluence. The V_TH of the irradiated MOSFET was found to decrease significantly after irradiation. The interface (N_it) and oxide trapped charge (N_ot) were estimated from the subthreshold measurements and were found to increase after irradiation. The densities of oxide-trapped (ΔN_it) charge in irradiated MOSFETs were found to be higher than those of the interface trapped charge (ΔN_ot). The I_DLin and I_DSat of MOSFETs were also found to decrease significantly after irradiation. Studies on effects of 95 MeV oxygen ion irradiation on gm, gD and μ show a degradation varying from 70 to 75% after irradiation. The mobility degradation coefficients for N_it(α_it) and N_ot(α_it) were estimated. The results of these studies are presented and discussed.     

Excellent passivation of thin silicon wafers by HF‐free hydrogen plasma etching using an industrial ICPECVD tool

In this work, hydrogen plasma etching of surface oxides was successfully accomplished on thin (～100 µm) planar n‐type Czochralski silicon wafers prior to intrinsic hydrogenated amorphous silicon [a‐Si:H(i)] deposition for heterojunction solar cells, using an industrial inductively coupled plasma‐enhanced chemical vapour deposition (ICPECVD) platform. The plasma etching process is intended as a dry alternative to the conventional wet‐chemical hydrofluoric acid (HF) dip for solar cell processing. After symmetrical deposition of an a‐Si:H(i) passivation layer, high effective carrier lifetimes of up to 3.7 ms are obtained, which are equivalent to effective surface recombination velocities of 1.3 cm s^–1 and an implied open‐circuit voltage (V_oc) of 741 mV. The passivation quality is excellent and comparable to other high quality a‐Si:H(i) passivation. High‐resolution transmission electron microscopy shows evidence of plasma‐silicon interactions and a sub‐nanometre interfacial layer. Using electron energy‐loss spectroscopy, this layer is further investigated and confirmed to be hydrogenated suboxide layers. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Temperature-dependent photovoltaic behavior of CdSe quantum dots/P3HT hybrid thinfilm

An organic–inorganic hybrid solar cell based on CdSe quantum dots (QDs) and poly(3-hexylthiophene) (P3HT) was fabricated. Its temperature-dependent photovoltaic behaviors, such as I–V characteristic curves and open circuit voltage (V_oc) transient response, were measured. The photovoltaic behavior of this hybrid thin film device was similar with that of organic thin film solar cells, according to analysis results based on the equivalent circuit method. The exact carrier lifetime was remarkably different between under low-temperature region and under temperature above 197 K.     

Efficiency enhancement of Cu(In,Ga)Se2 thin‐film solar cells by a post‐deposition treatment with potassium fluoride

Alkali‐free Cu(In,Ga)Se₂(CIGS) absorbers grown on Mo‐coated alumina (Al₂O₃) substrates were doped with potassium (K) after CIGS growth by a potassium fluoride (KF) post‐deposition treatment (PDT). The addition of K to the absorber leads to a strong increase in cell efficiency from 10.0% for the K‐free cell to 14.2% for the K‐doped cell, mainly driven by an increase in the open‐circuit voltage V_oc and the fill factor FF, and to an increase in the net charge carrier density. Hence K doping by KF‐PDT is comparable to doping with Na.