Polycrystalline Si thin-film solar cell prepared by solid phase crystallization (SPC) method

The solid phase crystallization (SPC) method has been studied for fabricating polycrystalline (poly) Si thin films for solar cells. The approach was to optimize the “partial doping structure” (nondoped a-Si/phosphorus(P)-doped a-Si) which we proposed as a starting structure before SPC. A conversion efficiency of 6.3% was obtained by using nondoped a-Si with a large structural disorder. This cell showed a collection efficiency of 51% at a wavelength of 900 nm. In order to significantly reduce the incubation time which is the important factor for the enlargement of the grain size, P doping of more than 10²⁰ cm⁻³ was required for the P-doped layer.     

Analysis of thin silicon solar cells for high efficiency

A comprehensive theoretical analysis taking into account the contribution from both the emitter and base regions having finite surface recombination velocity has been developed for computing short-circuit current, open-circuit voltage, and efficiency of thin AR coated thin silicon solar cells with textured front surface. The dependence of efficiency on the front surface and back surface recombination velocities and on the cell parameters have been investigated in details for varying cell thickness considering the effects of bandgap narrowing and Auger recombination in the material. It is shown that efficiency exceeding 24% can be attained with silicon solar cells having thickness as low as 25 μm provided both front and back surfaces are well passivated (S < 10³cm/s) and the doping concentration in the base and emitter are in the range of 5 × 10¹⁶ to 10¹⁷cm⁻³ and 10¹⁸ to 5 × 10¹⁸cm⁻³, respectively. It is also shown that an efficiency of about 23% can be obtained for thin cells of 25 μm thickness with a much inferior quality materials having diffusion length of about 40 μm.     

Photoelectrochemical parameters of In-doped thin CdSe layers

Photoanodes of polycrystalline CdSe layers, doped with different concentration of In are investigated. SEM microphotographs show that during the recrystallization process dense and homogenous layers with 50 μm sized crystallites are obtained. In order to obtain maximum performance the effect of In concentration on the photocurrent is analyzed and the optimal value of donor concentration (5×10¹⁶cm⁻³) is established. Applying Gartner-Butler's model for a semiconductor-electrolyte junction, the minority carrier diffusion length L (5.6 × 10⁻⁶ cm) and the donor concentration in the depletion layer N_d are determined for samples with optimal donor concentration. Direct preparation of well crystallized and suitably doped layers removes the necessity of sample posttreatment usually performed to increase their efficiency.     

2D-numerical analysis and optimum design of thin film silicon solar cells

Device modeling for p–i–n junction μc-Si basis thin film polycrystalline Si solar cells has been examined with a simple model of columnar grain structure and its boundary condition utilizing two-dimensional device simulator. As the simulation results of solar cell characteristics show, open-circuit voltage (V_oc) and curve fill factor (FF) considerably depend on those structural parameters, while short-circuit current density (J_sc) is comparatively stable by courtesy of homogeneous built-in electric field in the i layer. It has also been found that conversion efficiency over 12% could be expected with 1 μm grain size and well-passivated condition with 3 μm thick i-layer.     

Crystallographic analysis of high quality poly-Si thin films deposited by atmospheric pressure chemical vapor deposition

Crystallinity of thin film polycrystalline silicon (poly-Si) grown by atmospheric pressure chemical vapor deposition has been investigated by X-ray diffraction measurement and Raman spectroscopy. Poly-Si films deposited at high temperatures of 850–1050°C preferred to 2 2 0 direction. By Raman spectroscopy, the broad peak of around 480–500 cm⁻¹ belonged to microcrystalline Si (μc-Si) phase was observed even for the poly-Si deposited at 950°C. After high-temperature annealing (1050°C) 3 3 1 direction of poly-Si increased. This result indicates that the μc-Si phase at grain boundary became poly-Si phase preferred to 3 3 1 direction by high-temperature annealing. Effective diffusion length of poly-Si films deposited at 1000°C was estimated to be 11.9–13.5 μm and 10.2–12.9 μm before and after annealing, respectively.     

Interface characterisation of ZnSe/CuGaSe2 heterojunction

The ZnSe/CuGaSe₂ heterojunctions were fabricated by flash evaporation technique of CuGaSe₂ onto the (110) surface of ZnSe crystals. CuGaSe₂ layers had thickness 2–4 μm and showed a hole concentration up to (1.5–18.0)×10¹⁸ cm⁻³ and mobility μ4–24 cm² V⁻¹ s⁻¹ at 300 K. The charge carrier concentration in ZnSe crystals at 300 K was n=5.6×10¹⁶ cm⁻³ and their mobility μ=300 cm² V⁻¹ s⁻¹. The investigated ZnSe/CuGaSe₂ heterojunctions have at the interface an intermediate layer with a thickness of 450–750 Å and a linear graded band gap as well as an i-ZnSe compensated layer with a thickness of 1–2 μm and resistivity ρ10⁸–10⁹ Ω cm. The i-ZnSe layer is highly compensated due to the presence of Cu acceptor impurities. In this layer the Fermi level position E_c−F₀690 meV and a trap level position E_t−F₀17 meV were determined. The total trap concentration in the i-ZnSe layer is N_t5×10¹⁴ cm⁻³. The mean free path of excited charge carriers in the graded band gap region was calculated as λ55 Å. On the basis of experimental data analysis of electrophysical properties of both ZnSe/CuGaSe₂ heterojunctions and constituent materials the energetic band diagram of the investigated heterostructures is proposed. The current transport mechanism through ZnSe/CuGaSe₂ heterojunctions is consequently elucidated.     

A preliminary study of the electro-oxidation of l-ascorbic acid on polycrystalline silver in alkaline solution

Electrochemical oxidation of l-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at −500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10⁻⁵ cm² s⁻¹. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm⁻² and 4 mF cm⁻² as well as the adsorption and decomposition resistances (rates).     

Preparation and characterisation of electrodeposited n-CdS/p-CdTe thin film solar cells

Cadmium sulphide and cadmium telluride films have been electrodeposited for n-CdS/p-CdTe solar cells. Cell efficiency varied considerably from 9.5% to 11.5% for each deposition set. The reverse saturation currents of 9.5% and 11.5% cells at 298 K were 25 and 6.7 nA cm⁻², respectively. The cells with higher efficiency has a lower number of interface states than the less efficient cells. The 11.5% cell had interface states (N_IS) of 3× 10¹⁰ cm⁻² eV⁻¹ at zero volt bias in dark and when it was illuminated with 35 mW cm⁻² light at zero volt bias N_IS increased by two orders to 1.2×10¹² cm⁻² eV⁻¹. At higher frequency the large voltage intercept of the Mott-Schottky plot indicates the existence of the near intrinsic layer of the polycrystalline heterojunction.     

Effects of grain boundaries on cell performance of poly-silicon thin film solar cells by 2-D simulation

The effect of grain boundaries on the performance of poly-Si thin film solar cells was studied theoretically using a 2-D simulation assuming the presence of either rectangular-shaped or graded width grain boundaries in the i-layer of p/i/n structure of solar cells. The grain boundary had an adverse effect mainly on V_oc. J_sc gradually increased and saturated with increasing solar cell thickness in cells without grain boundaries, whereas it reached a maximum for an i-layer thickness of 5 μm in polycrystalline silicon cells. The calculation using the graded width model showed that the efficiency of the p⁺/p⁻/n⁺ structure was better than that of the p⁺/n⁻/n⁺ structure. A slight p-type doping of the i-layer was found to be effective in improving cell performance.     

Low-temperature deposition of polycrystalline silicon thin films by hot-wire CVD

Polycrystalline silicon films have been prepared by hot-wire chemical vapor deposition (HWCVD) at a relatively low substrate temperature of 430°C. The material properties have been optimized for photovoltaic applications by varying the hydrogen dilution of the silane feedstock gas, the gas pressure and the wire temperature. The optimized material has 95% crystalline volume fraction and an average grain size of 70 nm. The grains have a preferential orientation along the (2 2 0) direction. The optical band gap calculated from optical absorption by photothermal deflection spectroscopy (PDS) showed a value of 1.1 eV, equal to crystalline silicon. An activation energy of 0.54 eV for the electrical transport confirmed the intrinsic nature of the films. The material has a low dangling bond-defect density of 10¹⁷ cm³. A photo conductivity of 1.9 × 10⁻⁵ Ω⁻¹cm⁻¹ and a photoresponse (σ_ph/σ_d) of 1.4 × 10² were achieved. A high minority-carrier diffusion length of 334 nm as measured by the steady-state photocarrier grating technique (SSPG) and a large majority-carrier mobility-lifetime (μτ) product of 7.1 × 10⁻⁷cm²V⁻¹ from steady-state photoconductivity measurement ensure that the poly-Si : H films possess device quality. A single junction n---i---p cell made in the configuration n⁺-c-Si/i-poly-Si: H/p-μc-Si : H/ITO yielded 3.15% efficiency under 100 mW/cm² AM 1.5 illumination.     

Fabrication of poly-crystalline silicon films using plasma spray method

We have developed a new fabrication technique of poly-crystalline silicon (poly-Si) sheet for solar cells, namely the DC-RF hybrid plasma spray method. It has some advantages such as high deposition rate of more than 10 μm/s and large grain size of the obtained poly-Si films. Poly-Si films with a grain size of more than 20 μm and a defect density of 10⁶–10⁷ cm⁻² have been obtained at the initial stage trial. The solar cell conversion efficiency of 4.3% has been obtained using the plasma sprayed poly-Si. It is considered that the reasons for the low conversion efficiency are metallic impurity contamination, regions of micro grain due to rapid nucleation, and many defects in the films due to thermal stress.     

Investigation of the damage as induced by 1.7 MeV protons in an amorphous/crystalline silicon heterojunction solar cell

Current–voltage under illumination and quantum yield characteristics of an amorphous silicon/crystalline silicon hetero solar cell have been measured before and after exposure to high-energy (1.7 MeV) protons. A comparison of the measured wavelength-dependent quantum yield with calculated values enabled to determine the effective electron diffusion length of the crystalline silicon, that dropped from a value of 434 μm before to a value of 4 μm after irradiation with 5×10¹² cm⁻² protons. Good agreement has been obtained between measured and simulated data using DIFFIN,¹ a finite-element simulation program for a-Si:H/c-Si heterojunction solar cells, enabling us to extract the depth profile of the recombination rate and the density of states distribution in the semiconductor layers before and after irradiation.     

Radiation resistant AlGaAs/GaAs concentrator solar cells with internal Bragg reflector

The problem of increasing efficiency, reliability and radiation resistance of solar cells based on AlGaAs/GaAs heterostructures can be solved by using an internal Bragg reflector. The Bragg reflector as a back surface reflector and as a back surface potential barrier which allows to conserve the high photosensitivity in the long- and middle-wavelength parts of the spectrum after electron and proton irradiation. The effect of base doping and base thickness on the radiation resistance of AlGaAs/GaAs solar cells with the internal Bragg reflector has been investigated. Concentrator solar cells efficiency and related parameters before and after 3 MeV electron irradiation at the fluence up to 3×10¹⁵ cm⁻² are represented. A base doping level of 1×10¹⁵ cm⁻³ and base thickness in the range 1.1–1.6 μm give an EOL AM0 efficiency of 15.8% (BOL–22%) at 30 Suns concentration after exposure to 1×10¹⁵ cm⁻² electron fluence. This EOL efficiency is among the highest reported for GaAs single-junction concentrator cells under AM0 conditions. Making the base doping level lower and the base thinner allows retaining a j_EOL/j_BOL ratio of 0.96 upon exposure up to 3×10¹⁵e/cm² 3 MeV electron fluence. These results are additionally supported by the modeling calculations of the relative damage coefficient.     

Calculations of light trapping, responsivity, and internal quantum efficiency of In-doped silicon (n) structure

This research intends to investigate a mathematical model for In-doped silicon (n) structure, and calculate the absorbance of the simulated cell, then study the effect of impurity photovoltaic effect on the responsivity and internal quantum efficiency using the Shockley–Read–Hall model. It is found that the internal flux inside the simulated Lambertian cell could be enhanced as much as 25 times as a result of light trapping. Maximum responsivity and internal quantum efficiency of the simulated cell was obtained at a wavelength around 1 μm and 10¹⁷ cm⁻³ indium concentration. Near infrared response of the simulated cell is improved due to the enhancements of sub-band gap response by indium doping. To compare the mathematical model with the practical results, few samples of In-doped n-type silicon structures have been fabricated using the thermal vacuum resistive technique. Maximum responsivity and maximum internal quantum efficiency are obtained at wavelength 0.9–1 μm and 3.96×10¹⁷ cm⁻³ indium concentration. The results of the simulated and practical cells agree.     

Towards high-efficiency thin-film silicon solar cells with the “micromorph” concept

Tandem solar cells with a microcrystalline silicon bottom cell (1 eV gap) and an amorphous-silicon top cell (1.7 eV gap) have recently been introduced by the authors; they were designated as “micromorph” tandem cells. As of now, stabilised efficiencies of 11.2% have been achieved for micromorph tandem cells, whereas a 10.7% cell is confirmed by ISE Freiburg. Micromorph cells show a rather low relative temperature coefficient of 0.27%/K. Applying the grain-boundary trapping model so far developed for CVD polysilicon to hydrogenated microcrystalline silicon deposited by VHF plasma, an upper limit for the average defect density of around 2 × 10¹⁶/cm³ could be deduced; this fact suggests a rather effective hydrogen passivation of the grain-boundaries. First TEM investigations on μc-Si : H p-i-n cells support earlier findings of a pronounced columnar grain structure. Using Ar dilution, deposition rates of up to 9 Å/s for microcrystalline silicon could be achieved.     

Electrodeposition of ZnO thin films on n-Si(1 0 0)

In this study, ZnO thin films have been deposited onto monocrystalline n-type Si(1 0 0) by electrodeposition at different applied potentials. XRD shows a preferential orientation (0 0 0 2) that increases when the applied cathodic potential increases. The XPS analysis presents a Zn/O composition close to stoichiometric. SEM micrographs show a compact structure with localized platelets with a grain size of about 10 μm. However, crystallite size determined by the Scherrer method shows a size close to 2.50×10⁻² μm, then the grains can be considered as clusters of crystallites. Optical measurements were made on samples deposited on ITO/glass through the same procedures giving a band gap of 3.3 eV in agreement with the reported values for ZnO at room temperature.     

Thermogalvanic conversion of heat to electricity

A thermogalvanic (nonisothermal) cell was constructed for carrying out power conversion efficiency measurements. The design departed from that of traditional thermogalvanic cells which have largely been used only for studies of open-circuit voltage. The cell was used to obtain temperature coefficients, ∂E/∂T, of the open circuit voltage and power conversion efficiencies, Φ, for an interelectrode temperature difference, ΔT, of 20 K, using various redox couples. The values obtained were the following: Cu²⁺/Cu (1.0 mol dm⁻³), ∂E/∂T = 785 μV K⁻¹; Zn²⁺/Zn (1.0 mol dm⁻³), ∂E/∂T = 790 μV K⁻¹; Fe phen(CN)₄⁻/Fe phen(CN)₄²⁻ (10⁻³ mol dm⁻³), ∂E/∂T = 1046 μV K⁻¹, Φ = 4.17 × 10⁻⁵%; Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ (0.07 mol dm⁻³), ∂E/∂T = 1600 μV K⁻¹, Φ = 1.4 × 10⁻²%. More detailed studies of the latter system when [Fe(CN)₆³⁻] = [Fe(CN)₆⁴⁻] = 0.26 mol dm⁻³ and [KCl] = 0.80 mol dm⁻³, using platinum electrodes, with ΔT = 20 K, gave a current density of 1.45 mA cm⁻² and a power conversion efficiency, Φ, of 2.8 × 10⁻²%. This approaches 0.5% of the maximum theoretical efficiency of a Carnot engine operating across the same temperature difference.     

Extension of the a-Si:H electronic transport model to μc-Si:H: use of the μτ product to correlate electronic transport properties and solar cell performances

The aim of this communication is to show that it is possible to extend the model of the electronic transport developed for amorphous silicon (a-Si:H) to microcrystalline silicon (μc-Si:H). By describing the electronic transport with the μ⁰τ^R products (mobility×recombination time) as a function of the Fermi level, we observed the same behaviour for both materials, indicating a similar type of recombination. Moreover, applying the normalised μ⁰τ⁰ product (mobility×life-time) obtained by combining the photoconductivity (σ_photo) and the ambipolar diffusion length (L_amb) measured in individual layers, we are able, as in the case of a-Si:H, to predict the quality of the solar cells incorporating these layers as the active i layer.     

Device simulation and modeling of microcrystalline silicon solar cells

Device modeling for p–i–n junction basis thin film microcrystalline Si solar cells has been examined with a simple model of columnar grain structure utilizing two-dimensional device simulator. The simulation results of solar cell characteristics show that open-circuit voltage (V_oc) and fill factor considerably depend on structural parameters such as grain size and acceptor doping in intrinsic layer, while short-circuit current density (J_sc) is comparatively stable by built-in electric field in the i-layer. It is also found that conversion efficiency of more than 16% could be expected with 1 μm grain size and well-passivated condition with 10 μm thick i-layer and optical confinement.     

Polycrystalline silicon solar cells on mullite substrates

Polycrystalline silicon layers have been grown on various alumino-silicate substrates in a rapid thermal chemical vapor deposition (RTCVD) system at high temperatures (>1000°C). Structural analysis shows a columnar growth with grain sizes up to 15 μm and growth rates up to 5 μm/min. Solar cell devices on this fine-grained Si material result in a short-circuit current of about 13 mA/cm² but a poor open-circuit voltage (<0.4 V). Larger grains obtained by the zone melting recrystallization (ZMR) technique boosted the current up to 26.1 mA/cm², thanks to the light-trapping by the mullite substrate. Best efficiency is 8.2% on a 1 cm² cell made on a 20 μm thick poly-Si layer.