Control of μc-Si/c-Si interface layer structure for surface passivation of Si solar cells

Outstanding passivation properties for p-type crystalline silicon surfaces were obtained by using very thin n-type microcrystalline silicon (μc-Si) layers with a controlled interface structure. The n-type μc-Si layers were deposited by the RF PE-CVD method with an insertion of an ultra-thin oxide (UTO) layer or an n-type amorphous silicon (a-Si : H) interface layer. The effective surface recombination velocity (SRV) obtained was very small and comparable to that obtained using thermal oxides prepared at 1000°C. The structural studies by HRTEM and Raman measurements suggest that the presence of UTO produces a very thin a-Si : H layer under the μc-Si. A crystal lattice discontinuity caused by these interface layers is the key to a small SRV.     

Single-crystalline silicon solar cell with pp heterojunction of c-Si substrate and μc-Si : H film

Annealing effects of the single-crystalline silicon solar cells with hydrogenated microcrystaline silicon (μc-Si : H) film were studied to improve the conversion efficiency. Boron-doped (p⁺) μc-Si : H film was deposited in a RF plasma enhanced chemical vapor deposition system (RF plasma CVD) on the rear surface of the cell. With the optimized annealing conditions for the substrate, the conversion efficiency of 21.4% (AM1.5, 25°C, 100 mW/cm²) was obtained for 5 × 5 cm² area single crystalline-solar cell.     

Doping of a-SiCX:H films including μc-Si:H by hot-wire CVD and their application as a wide gap window for heterojunction solar cells

Impurity doping using B₂H₆ gas using hot-wire CVD has been tried for hydrogenated amorphous silicon-carbon (a-SiC_X:H) alloy films including hydrogenated microcrystalline silicon (μc-Si:H) with carbon content, C/(Si+C), of about 28%. The dark- and photoconductivities of B-doped samples are larger than those of undoped samples. The activation energy for dark conductivity of the B-doped sample with the doping gas ratio, B₂H₆/(SiH₄+CH₄), of about 0.054% is 0.17 eV. This value is smaller than that of the undoped sample. The P-doped samples also show larger dark- and photoconductivities and smaller activation energy than the undoped samples.     

Low temperature μc-Si film growth using a CaF2 seed layer

This paper describes low temperature thin film Si growth by remote plasma chemical vapor deposition system for photovoltaic device applications. Using CaF₂/glass substrate, we were able to achieve an improved μc-Si film at a low process temperature of 300°C. The μc-Si film on CaF₂/glass substrate shows that a crystalline volume fraction of 65% and dark conductivity of 1.65×10⁻⁸ S/cm with the growth conditions of 50 W, 300°C, 88 mTorr, and SiH₄/H₂=1.2%. XRD analysis on μc-Si/CaF₂/glass showed crystalline film growth in (1 1 1) and (2 2 0) planes. Grain size was enlarged as large as 700 Å for a μc-Si/CaF₂/glass structure. Activation energy of μc-Si film was given as 0.49 eV. The μc-Si films exhibited dark- and photo-conductivity ratio of 124.     

Microcrystalline silicon thin-film solar cells prepared at low temperature using PECVD

The low-temperature deposition of μc-Si:H has been found to be effective to suppress the formation of oxygen-related donors that cause a reduction in open-circuit voltage (V_oc) due to shunt leakage. We demonstrate the improvement of V_oc by lowering the deposition temperature down to 140°C. A high efficiency of 8.9% was obtained using an Aasahi-U substrate. Furthermore, by optimizing textured structures on ZnO transparent conductive oxide substrates, an efficiency of 9.4% was obtained. In addition, relatively high efficiency of 8.1% was achieved using VHF (60 MHz) plasma at a deposition rate of 12 Å s⁻¹. Thus, this low-temperature deposition technique for μc-Si:H is promising for obtaining both high efficiency and high-rate deposition technique for μc-Si:H solar cells.     

Heat transfer and pressure drop in serpentine μDMFC flow channels

In this paper, a 3-D mathematical model incorporated with Fluent computer code is described to investigate the flow and heat transfer for developing laminar flow in the micro direct methanol fuel cell (μDMFC) with serpentine flow fields. The continuity, momentum, and energy equations are simultaneously solved by a general computational fluid dynamics code. Local, channel-mean, bended region-mean, and overall channel mean friction factors and Nusselt numbers were thus calculated and discussed. Finally, overall channel mean friction factor and Nusselt number were correlated in terms of the relevant parameters.     

Organic–inorganic hybrid composites for photovoltaics: Organic guest molecules embedded in μc-Si and ZnSe host matrices

The concept of organic–inorganic hybrid composites for bulk sensitization of inorganic semiconductors by organic dye molecules is introduced. The idea is either to increase the absorptivity of e.g. indirect semiconductors as μc-Si or to expand in a two-step process the absorption spectrum of wide gap semiconductors to photons of energy smaller than the band gap. The composites are prepared by vacuum-based codeposition. Raman and optical spectroscopy, and photoemission have been used to prove the stability of the organic molecules ZnPc and F₁₆ZnPc for the applied growth conditions. Enhancement of photoconductivity has been shown for ZnPc–Si bilayer. As a crucial parameter for the transfer of excited charges, the alignment of dye HOMO–LUMO states versus semiconductor band edges has been determined using photoelectron spectroscopy.     

Amorphous and microcrystalline silicon solar cells prepared at high deposition rates using RF (13.56 MHz) plasma excitation frequencies

This paper presents a-Si:H and μc-Si:H p–i–n solar cells prepared at high deposition rates using RF (13.56 MHz) excitation frequency. A high deposition pressure was found as the key parameter to achieve high efficiencies at high growth rates for both cell types. Initial efficiencies of 7.1% and 11.1% were achieved for a μc-Si:H cell and an a-Si:H/μc-Si:H tandem cell, respectively, at a deposition rate of 6 Å/s for the μc-Si i-layers. A μc-Si:H cell prepared at 9 Å/s exhibited an efficiency of 6.2%.     

New materials and deposition techniques for highly efficient silicon thin film solar cells

This paper reviews recent efforts to provide the scientific and technological basis for cost-effective and highly efficient thin film solar modules based on amorphous (a-Si:H) and microcrystalline (μc-Si:H) silicon. Textured ZnO:Al films prepared by sputtering and wet chemical etching were applied to design optimised light-trapping schemes. Necessary prerequisite was the detailed knowledge of the relationship between film growth, structural properties and surface morphology obtained after etching. High rate deposition using plasma enhanced chemical vapour deposition at 13.56 MHz plasma excitation frequency was developed for μc-Si:H solar cells yielding efficiencies of 8.1% and 7.5% at deposition rates of 5 and 9 Å/s, respectively. These μc-Si:H solar cells were successfully up-scaled to a substrate area of 30×30 cm² and applied in a-Si:H/μc-Si:H tandem cells showing initial test cell efficiencies up to 11.9%.     

Photovoltaic cells based on cadmium sulphide–phthalocyanine heterojunction

Hybrid photovoltaic (PV) cells based on cadmium sulphide (CdS) single crystal and phthalocyanine (Pc) films have been developed and their PV performance was measured. Five different Pcs have been selected as candidates for the PV cell, PcCu, PcMn, PcZn, PcMg, and PcVO. It was found that all the chosen Pcs are capable of forming a hybrid heterojunction with the CdS surface, and that illumination results in charge separation at the interface. However, the performance of the In/CdS/Pc/Au device was dependent on the Pc used. PV cells with PcMg and PcZn showed the best results. An unoptimized cell with the PcZn film showed an open-circuit voltage V_oc=0.595 V, a short-circuit current density J_sc=1.88 μA/cm², a fill factor FF=0.265, and a power conversion efficiency PCE=3.0×10⁻⁴% under the AM1.5 conditions.     

Investigation of non-aqueous electrodeposited CdS/Cd1−xZnxTe heterojunction solar cells

Polycrystalline Cd_1−xZn_xTe solar cells with efficiency of 8.3% were grown by cathodic electrodeposition on glass/ITO/CdS substrates using non-aqueous ethylene glycol bath. The deposit is characterised versus the process conditions by XRD and found to possess a preferred (1 1 1) orientation on Sb doping in the electroplating bath. The surface morphology of the deposit is studied using atomic force microscope. The average RMS roughness for the ternary film was higher than that for the binary CdTe. Optical properties of the films were carried out to study the band gap and calculation of molar concentration ‘x’. The effects of Sb doping in CdS/Cd_1−xZn_xTe heterojunctions have been studied. The short circuit current density (c) was found to improve and series resistance (R_s) reduced drastically upon Sb doping. This improvement in J_sc is attributed to an increase in quantum efficiency. The evaluation of solar cell parameters was also carried out using the current–voltage characteristics in dark and illumination. The best results were obtained when 2×10⁻³ M ZnCl₂ along with antimony were present in the deposition bath. Under AM 1.5 conditions the open circuit voltage, short circuit current density, and fill factor of our best cell were V_oc=600 mV, J_sc=26.66 mA/cm², FF=0.42 and efficiency, η=8.3%. The carrier concentration and built-in potential of Cd_1−xZn_xTe calculated from Mott–Schottky plot was 2.72×10¹⁷ cm⁻³ and 1.02 eV.     

Preparation of (n) a-Si: H/(p) c-Si heterojunction solar cells

Heterojunction solar cells have been manufactured by depositing n-type a-Si: H on p-type 1–2Ω cm CZ single crystalline silicon substrates. Although our cell structure is very simple - neither a BSF nor a surface texturing is used - a conversion efficiency of 13.1% has been achieved on an area of 1 cm². In this paper the technology is described and the dependence of the solar cell parameters on the properties of the n-type a-Si: H layer is discussed. It is shown that this cell type exhibits no degradation under light exposure.     

Poly‐3‐hexylthiophene doped with iron disulfide nanoparticles for hybrid solar cells

In this work, the pyrite crystalline phase of iron disulfide nanoparticles (FeS₂) about 20 to 30 nm was obtained by a two‐pot thermal method at 220°C. Subsequently, different concentrations of these nanoparticles were used as a doping agent for the conjugated poly‐3‐hexylthiophene (P3HT). The electrical resistivity of P3HT was decreased almost three orders of magnitude while adding FeS₂ nanoparticles as doping, and dichlorobenzene solvent was a determinant factor for the dispersion of polymer with nanoparticles. Doped‐P3HT dichlorobenzene solution was spin coated onto the FTO/TiO₂ substrate to fabricate the FTO/TiO₂/P3HT:FeS₂/C‐Au hybrid solar cells. Moreover, the power conversion efficiency (PCE) of hybrid devices was studied as a function of pyrite FeS₂ nanoparticle concentration. The highest efficiency of 0.83% was obtained at 1% concentration of FeS₂ nanoparticles. Hence, the results revealed that the FeS₂ nanoparticles could be considered as an alternative charge carrier to develop the bulk hybrid solar cells.     

A new route for fabricating CdO/c-Si heterojunction solar cells

CdO/c-Si solar cells have been made by depositing CdO thin films on p-type monocrystalline silicon substrate by means of the rapid thermal oxidation (RTO) technique using a halogen lamp at 350 °C/45 s in static air. Results on structural, optical, and electrical properties of grown CdO films are reported. The electrical and photovoltaic properties of CdO/Si solar cells are examined. Under AM1 illumination condition, the cell shows an open circuit voltage (V_OC) of 500 mV, a short circuit current density (J_SC) of 27.5 mA/cm², a fill factor (FF) of 60%, and a conversion efficiency (η) of 8.84% without using frontal grid contacts and/or post-deposition annealing. Furthermore, the stability of solar cells characteristics is tested.     

p-doped μc-Si:H window layers prepared by hot-wire CVD for amorphous solar cell application

We report on boron-doped μc-Si:H films prepared by hot-wire chemical vapor deposition (HWCVD) using silane as a source gas and trimethylboron (TMB) as a dopant gas and their incorporation into all-HW amorphous silicon solar cells. The dark conductivity of these films was in the range of 1–10 (Ω cm)⁻¹. The open circuit voltage V_oc of the solar cells was found to decrease from 840 mV at low hydrogen dilution H-dil=91% to 770 mV at high H-dil =97% during p-layer deposition which can be attributed to the increased crystallinity at higher H-dil and to subsequent band edge discontinuity between μc-Si:H p- and amorphous i-layer. The short circuit current density J_sc and the fill factor FF show an optimum at an intermediate H-dil and decrease for the highest H-dil. To improve the conversion efficiency and the reproducibility of the solar cells, an amorphous-like seed layer was incorporated between TCO and the bulk p-layer. The results obtained until now for amorphous solar cells with and without the seed layer are presented. The I–V parameters for the best p–i–n solar cell obtained so far are J_sc=13.95 mA/cm², V_oc=834 mV, FF=65% and η=7.6%, where the p-layers were prepared with 2% TMB. High open circuit voltages up to 847 mV could be achieved at higher TMB concentrations.     

Cell structures with low-high heterojunction of c-Si and μc-Si: H under rear contact for improvement of efficiencies

For a remarkable improvement of conversion efficiencies of single-crystalline silicon (c-Si) solar cells, we have been investigating rear surface structures. The structure has a highly conductive boron (B) doped hydrogenated microcrystalline silicon (μc-Si:H) film with a wide optical bandgap between a p-type c-Si substrate and a rear contact instead of a heavily diffused layer. The conditions of depositing the μc-Si:H film were investigated. Both short-circuit current density (J_sc) and open-circuit voltage (V_oc) of the cell with the μc-Si:H film are much higher than those without the film. The V_oc obtained was higher than 650 mV and the efficiency was 19.6% for a 5 cm × 5 cm cell. It is confirmed that a low-high heterojunction of the c-Si substrate and the μc-Si:H film is very effective in preventing minority carriers near the rear contact from recombining.     

Silicon-based thin-film solar cells fabricated near the phase boundary by VHF PECVD technique

The light-soaked and annealing behaviors for silicon (Si)-based thin-film single-junction solar cells fabricated near the phase boundary using a very-high-frequency plasma-enhanced chemical vapor deposition (VHF PECVD) technique are investigated. The hydrogen dilution ratio is changed in order to achieve wide band gap hydrogenated amorphous Si (a-Si:H) and narrow band gap hydrogenated microcrystalline Si (μc-Si:H) absorbers. Just below the a-Si:H-to-μc-Si:H transition, highly hydrogen-diluted a-Si:H solar cells with a good stability against light-soaking and fast annealing behavior are obtained. In contrast, the solar cell fabricated at the onset of the μc-Si:H growth is very unstable and its annealing behavior is slow. In the case of μc-Si:H solar cells with the crystal volume fraction of 43–53%, they show the lowest light-induced degradation among the fabricated solar cells. However, it is very difficult to recover the degraded μc-Si:H solar cells via thermal annealing.     

Long-lived bulk heterojunction solar cells fabricated with photo-oxidation resistant polymer

We report the fabrication of long-lived polymer solar cells using a new donor-acceptor type alternating copolymer, poly(5,5,10,10-tetrakis(2-ethylhexyl)-5,10-dihydroindeno[2,1-α]indene-2,7-diyl)-co-4,7-di-2-thienyl-2,1,3-benzothiadiazole (PININE-DTBT) in bulk heterojunction composites with the fullerene derivative [6,6]-phenyl C₇₀-butyricacidmethyl ester (PC₇₀BM). The PININE-DTBT:PC₇₀BM solar cells exhibit an extended device lifetime (as compared with other polymer systems) with a reasonable power conversion efficiency of ∼2.7% under air mass 1.5 global (AM 1.5 G) irradiation of 100 mW/cm². The long-lived feature of the devices originates from the photo-oxidation resistant backbone unit and the deep HOMO (highest occupied molecular orbital) level of PININE-DTBT.     

Electronic transport properties of the μc-(Si,Ge) alloys prepared by ECR

Some μc-(Si,Ge):H alloys have been grown using low-pressure, reactive ECR plasma deposition with high H dilution and subtle (sub ppm) B-doping. Incorporating these high-quality materials into devices leads to low-gap μc-(Si,Ge) solar cells with acceptable performance. This justifies a detailed investigation of the electronic transport properties of μc-(Si,Ge):H alloys by employing the microwave photomixing technique.From the measurements of the electric field dependence of the drift mobility and lifetime, we have found strong evidence for the existence of long-range potential fluctuations in μc-(Si,Ge):H alloys. We determine the depth and range of the potential fluctuations, and subsequently the charged defect density, as a function of the deposition rate. It was found that the film transport properties do not degrade or enhance monotonically with increasing deposition rate; there exists a valley point where the strongest potential fluctuations occur as a result of a significant increase in the charged defect density. Beyond this point, the film quality increases again. The evidence indicates that it is the long-range potential fluctuations that result in the deterioration of the transport properties of μc-(Si,Ge):H alloys. Specifically, it is the increase in the depth, and a decrease in the length of the potential fluctuations, which lead to a decrease in the mobility, and consequently in the photoconductivity. Our present results demonstrate that aside from the increase of charged scattering centers, compositional disorder in the alloys play an important role with the build-up of the potential fluctuations.     

Low-temperature a-Si:H/ZnO/Al back contacts for high-efficiency silicon solar cells

The paper analyses the electronic transport of high-efficiency silicon solar cells with high-quality back contacts that use a sequence of amorphous (a-Si) and microcrystalline (μc-Si) silicon layers prepared at a maximum temperature of 220 °C. Our best solar cells having diffused emitters with random texture and full-area a-Si/μc-Si contacts have an independently confirmed efficiency of 21.0%. An alternative concept uses a simplified a-Si layer sequence combined with Al-point contacts and yields a confirmed efficiency of 19.3%. Analysis of the internal quantum efficiency (IQE) shows that both types of back contacts lead to effective diffusion lengths L_eff exceeding the wafer thickness considerably. Fill factor limitations for the full area contacts result from non-ideal diode behavior, possibly due to the injection dependence of the interface recombination velocity.