Hot-wire CVD deposited n-type μc-Si films for μc-Si/c-Si heterojunction solar cell applications

Phosphorous-doped microcrystalline silicon (μc-Si) films were prepared using hot-wire chemical vapor deposition (HWCVD). Structural, electrical and optical properties of these thin films were systematically studied as a function of PH₃ gas mixture ratio. We report recent results for p-type crystalline silicon-based heterojunction (HJ) solar cells using the HWCVD n-μc-Si film to form an n-p junction. The surface morphology of the crystalline Si substrate after hydrogen treatment was examined using atomic force microscopy. A transfer length method was used to modify the indium-tin-oxide (ITO) deposition parameters in order to reduce front ITO/n-μc-Si contact resistance. In our best solar cell sample (1 cm²) without any buffer layer, the conversion efficiency of 15.1% has been achieved with an open circuit voltage of 0.615 V, fill factor of 0.71 and short circuit current density of 34.6 mA/cm² under 100 mW/cm² condition. The spectral response of this cell will also be discussed.     

High efficiency a-Si:H/a-Si:H solar cell with a tunnel recombination junction and a n-type μc-Si:H layer

In this paper, a-Si:H/a-Si:H tandem solar cells have been fabricated using a plasma enhanced chemical vapor deposition. The solar cell has a structure of glass/textured-SnO₂/p-a-SiC:H/i-a-Si:H/n-μc-Si:H/p-μc-Si:H/p-a-SiC:H/i-a-Si:H/n-μc-Si:H/gallium-doped zinc oxide/Ag. Higher efficiency in a-Si:H/a-Si:H tandem solar cells can be achieved by use of a good tunnel recombination junction (TRJ) and current matching. Accordingly, solar cells with a n-μc-Si:H/p-μc-Si:H TRJ are investigated. This paper studies the influence of the thickness of the top intrinsic amorphous silicon (i-a-Si:H) layer with regard to short circuit current density and current matching between the top and the bottom cells. Experimental results with lab-fabricated samples show that the optimal thickness of the i-a-Si:H layer in the top and bottom cells is 60 and 250 nm, respectively. An initial conversion efficiency of 10.29% is achieved for the optimized a-Si:H/a-Si:H tandem solar cell. Light-induced degradation of the solar cells is about 17%.     

Extremely low recombination velocity on crystalline silicon surfaces realized by low-temperature impurity doping in Cat-CVD technology

To reduce surface recombination velocity (SRV) at the interface between amorphous Si (a-Si) and crystalline silicon (c-Si), we particularly investigated the treatment of c-Si surface prior to a-Si deposition using decomposed radicals of hydrogen (H₂) and phosphine (PH₃). The SRV can be reduced dramatically to 1.6 cm/s only for n-type c-Si, while no such reduction is observed in p-type c-Si. Secondary ion mass spectrometry (SIMS) and the Hall effect measurement actually reveal the existence of phosphorus (P) atoms in c-Si near the surface.     

Development of a hot-wire chemical vapor deposition n-type emitter on p-type crystalline Si-based solar cells

We have developed a p-type, crystalline Si-based solar cell using hot-wire chemical vapor deposition (HWCVD) n-type microcrystalline Si to form an n-p junction (emitter). The CVD process was rapid and a low substrate temperature was used. The p-type Czochralski (CZ) c-Si wafer has a thickness of 400 μm and has a thermally diffused Al back-field contact. Before forming the n-p junction, the front surface of the p-type c-Si was cleaned using a diluted HF solution to remove the native oxides. The n-type emitter was formed at 220 °C by depositing 50 Å a-Si:H and then a 100 Å μc-Si n-layer. The total deposition time to form the emitter was less than 1 min. The top contact of the device is a lithograph defined and isolated 1×1 cm² and 780 Å indium tin oxides (ITO) with metal fingers on top. Our best solar cell conversion efficiency is 13.3% with V_oc of 0.58 V, FF of 0.773, and J_sc of 29.86 mA cm⁻² under one-sun condition. Quantum efficiency (QE) measurement on this solar cell shows over 90% in the region between 540 and 780 nm, but poor response in the blue and deep red. We find that the ITO top contact that acts as an antireflection layer increases the QE in the middle region. To improve the device efficiency further, J_sc needs to be increased. Better emitter and light trapping will be developed in future work. The cell shows no degradation after 1000 h of standard light soaking.     

Physical aspects of a-Si:H/c-Si hetero-junction solar cells

We report on the basic properties of amorphous/crystalline hetero-junctions (a-Si:H/c-Si), their effects on the recombination of excess carriers and its influence on the a-Si:H/c-Si hetero-junction solar cells. For that purpose we measured the gap state density distribution of thin a-Si:H layers and determined its dependence on deposition temperature and doping by an improved version of near-UV-photoelectron spectroscopy. Furthermore, the Fermi level position in the a-Si:H and the valence band offset were directly measured. In combination with interface sensitive methods such as surface photovoltage analysis and our numerical simulation program AFORS-HET, we found an optimum in wafer pretreatment, doping and deposition temperature for efficient a-Si:H/c-Si solar cells without an i-type a-Si:H buffer layer. We reached at maximum 19.8% certified efficiency by a deposition at 210 °C with an emitter doping of 2000 ppm of B₂H₆ on a well cleaned pyramidally structured c-Si(n) wafer.     

Poly-silicon thin films by aluminium induced crystallisation of microcrystalline silicon

Al-induced crystallisation of microcrystalline Si thin films prepared by electron cyclotron resonance plasma-enhanced chemical vapour deposition (ECR-PECVD) on glass and SiO₂ coated Si wafers has been studied. The starting structure was substrate/μc-Si/Al. Annealing this structure in the temperature range 370-520 °C, immediately following deposition of the Al layer, resulted in successful layer exchange and the formation of a substrate/Al+Si layer/poly-Si geometry. The top poly-Si layer exhibited grain sizes generally in the range ∼2-6 μm, although larger grains were also sparsely present. The films did not exhibit any appreciable degree of preferred orientation. The surface roughness was relatively high with a R_a value of ∼20 nm.     

Improvement of the efficiency of triple junction n-i-p solar cells with hot-wire CVD proto- and microcrystalline silicon absorber layers

Hot-wire chemical vapour deposition (HWCVD) was applied for the deposition of intrinsic protocrystalline (proto-Si:H) and microcrystalline silicon (μc-Si:H) absorber layers in thin film solar cells. For a single junction μc-Si:H n-i-p cell on a Ag/ZnO textured back reflector (TBR) with a 2.0 μm i-layer, an 8.5% efficiency was obtained, which showed to be stable after 750 h of light-soaking. The short-circuit current density (J_sc) of this cell was 23.4 mA/cm², with a high open-circuit voltage (V_oc) and fill factor (FF) of 0.545 V and 0.67.Triple junction n-i-p cells were deposited using proto-Si:H, plasma-deposited proto-SiGe:H and μc-Si:H as top, middle and bottom cell absorber layers. With Ag/ZnO TBR's from our lab and United Solar Ovonic LLC, respective initial efficiencies of 10.45% (2.030 V, 7.8 mA/cm², 0.66) and 10.50% (2.113 V, 7.4 mA/cm², 0.67) were achieved.     

Process control of high rate microcrystalline silicon based solar cell deposition by optical emission spectroscopy

Silicon thin-film solar cells based on microcrystalline silicon (μc-Si:H) were prepared in a 30 × 30 cm² plasma-enhanced chemical vapor deposition reactor using 13.56 or 40.68 MHz plasma excitation frequency. Plasma emission was recorded by optical emission spectroscopy during μc-Si:H absorber layer deposition at deposition rates between 0.5 and 2.5 nm/s. The time course of SiH^? and H_β emission indicated strong drifts in the process conditions particularly at low total gas flows. By actively controlling the SiH₄ gas flow, the observed process drifts were successfully suppressed resulting in a more homogeneous i-layer crystallinity along the growth direction. In a deposition regime with efficient usage of the process gas, the μc-Si:H solar cell efficiency was enhanced from 7.9 % up to 8.8 % by applying process control.     

Potential of thin-film silicon solar cells by using high haze TCO superstrates

Potential improvements in the performance of tandem amorphous silicon/microcrystalline silicon (a-Si:H/μc-Si:H) solar cells, related to the TCO superstrates with enhanced scattering properties are studied. In particular, optical effects of a high haze double textured (W-textured) SnO₂:F TCO superstrate are analyzed and compared to the properties of the pyramidal type SnO₂:F TCO superstrate. Solar cell with W-textured superstrate exhibits higher long-wavelength external quantum efficiency of the bottom μc-Si:H cell than the one with pyramidal type TCO superstrate. Optical simulations are employed to study the potential improvements of the solar cell performance if ideal haze parameter (H = 1) and/or a broad angular distribution function (Lambertian) of scattered light are applied to textured interfaces in the solar cell structure. Simulations reveal significant improvements in long-wavelength quantum efficiencies if a broad angular distribution function of scattered light is applied. Optical losses in the cells with enhanced scattering properties are analysed and evaluated in terms of short-circuit current losses in the supporting layers and losses due to reflected light.     

Hot Wire CVD for thin film triple junction cells and for ultrafast deposition of the SiN passivation layer on polycrystalline Si solar cells

We present recent progress on hot-wire deposited thin film solar cells and applications of silicon nitride. The cell efficiency reached for μc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.5%, in line with the state-of-the-art level for μc-Si:H n-i-p's for any method of deposition. Such cells, used in triple junction cells together with hot-wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.5% efficiency. The single junction μc-Si:H n-i-p cell is entirely stable under prolonged light soaking. The triple junction cell, including protocrystalline i-layers, is within 3% stable, due to the limited thicknesses of the two top cells. The application of SiN_x:H at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency. We have also achieved record high deposition rates of 7.3 nm/s for transparent and dense SiN_x;H. Hot-wire SiN_x:H is likely to be the first large commercial application of the Hot Wire CVD (Cat-CVD) technology.     

Texturing of the back reflector for light trapping enhancement in micromorph thin film solar cells

The effects of textured back reflectors on light trapping in a-Si:H/μc-Si:H tandem cells are investigated with textured ZnO:Ga (GZO) back contacts obtained by surface wet etching. It is observed that rough back reflectors in fabricated tandem solar cells increase the short circuit current density of the bottom cells by 8%, which is attributed to light-trapping improvement. It is shown that enhanced longer wavelength light trapping is mainly attributable to improved light scattering at the back side by comparing identical a-Si:H/μc-Si:H tandem solar cells, both with a GZO back reflector but only one with a textured back reflector. The effectiveness of the textured GZO back reflector is also demonstrated in a textured a-Si:H/μc-Si:H tandem cell with a bottom cell thickness of 2 μm, which showed higher conversion efficiency than the reference cell.     

Synthesis and characterization of AgInSe2 for application in thin film solar cells

AgInSe₂ (AIS) films were grown on n-type Si substrates by the ultra-high-vacuum pulsed laser deposition technique from the AIS target synthesized from high-purity materials. The X-ray diffraction and microscopic studies of the films show that films are textured having terrace-like surface morphology. The optical studies of the films show that the optical band gap is about 1.24 eV. The electrical conductivity of AgInSe₂/Si films shows excellent diode characteristics. The photoconductivity of the AgInSe₂/Si device shows photocurrent of 2.8 mA at a bias-voltage of − 1 V with an open circuit voltage of 0.15 V. This shows that AIS films are very good absorber material for solar cell technology.     

Electrical properties/Doping efficiency of doped microcrystalline silicon layers prepared by hot-wire chemical vapor deposition

Microcrystalline silicon (μc-Si) doped films were prepared by hot-wire chemical vapor deposition (HWCVD) to investigate the doping efficiency. The incorporation probability of different dopant atoms into the solid-phase is always increasing with the doping gas concentrations, but very different for the doping gases used: trimethylboron (TMB), boron trifluoride (BF₃) and phosphine (PH₃). At the same doping gas concentration in the process gas the incorporation of phosphorus atoms into the solid μc-Si phase is much larger than that of boron atoms with respect to the dissociation probability of the doping gases. The electron and hole concentrations, estimated from Hall measurements, are directly related to the solid phase concentration of the doping atoms and independent of the type of dopant and the doping gas used. This results in an equal doping efficiency of about 20 % for the incorporated B and P atoms in doped HWCVD μc-Si films. For the dopant atom concentration regime investigated the doping efficiency of B atoms is in good agreement with corresponding PECVD doping efficiencies however, the doping efficiency of P atoms is considerably lower for our n-doped films.     

Mechanical properties of amorphous and microcrystalline silicon films

Hydrogen-free amorphous silicon (a-Si) films with thickness of 4.5-6.5 μm were prepared by magnetron sputtering of pure silicon. Mechanical properties (hardness, intrinsic stress, elastic modulus), and film structure (Raman spectra, electron diffraction) were investigated in dependence on the substrate bias and temperature. The increasing negative substrate bias or Ar pressure results in simultaneous reducing compressive stress, the film hardness and elastic modulus. Vacuum annealing or deposition of a-Si films at temperatures up to 600 °C saving amorphous character of the films, results in reducing compressive stress and increasing the hardness and elastic modulus. The latter value was always lower than that for monocrystalline Si(111). The crystalline structure (c-Si) starts to be formed at deposition temperature of ∼ 700 °C. The hardness and elastic modulus of c-Si films were very close to monocrystalline Si(111). Phase transformations observed in the samples at indentation depend not only on the load and loading rate but also on the initial phase of silicon. However, the film hardness is not too sensitive to the presence of phase transformations.     

Enhanced crystal grain size by bromine doping in electrodeposited Cu2O

Extremely large crystal grains are obtained by bromine doping in electrodeposited Cu₂O on indium tin oxide (ITO) substrate through an acetate bath. The grains are as large as 10,000 μm² in area, or ~ 100 μm in linear dimension, while the film is only 1-5 μm thick. The enhanced grain size is explained by the effect of over-potential for the Cu²⁺/Cu⁺ redox couple on nucleation density of Cu₂O on ITO substrate. The over-potential is a function of several deposition conditions including solution pH, deposition potential, deposition temperature, bromine precursor concentration, and copper precursor concentration. In addition, undoped Cu₂O displays a high resistivity of 100 MΩcm. Bromine doping in Cu₂O significantly reduces the resistivity to as low as 42 Ωcm after vacuum annealing. Br-doped Cu₂O shows n-type behavior.     

Sb2S3:C/CdS p-n junction by laser irradiation

In this paper, we report laser irradiated carbon doping of Sb₂S₃ thin films and formation of a p-n junction photovoltaic structure using these films. A very thin carbon layer was evaporated on to chemical bath deposited Sb₂S₃ thin films of approximately 0.5 μm in thickness. Sb₂S₃ thin films were prepared from a solution containing SbCl₃ and Na₂S₂O₃ at 27 °C for 5 h and the films obtained were highly resistive. These C/Sb₂S₃ thin films were irradiated by an expanded laser beam of diameter approximately 0.5 cm (5 W power, 532 nm Verdi laser), for 2 min at ambient atmosphere. Morphology and composition of these films were analyzed. These films showed p-type conductivity due to carbon diffusion (Sb₂ S₃:C) by the thermal energy generated by the absorption of laser radiation. In addition, these thin films were incorporated in a photovoltaic structure Ag/Sb₂S₃:C/CdS/ITO/Glass. For this, CdS thin film of 50 nm in thickness was deposited on a commercially available ITO coated glass substrate from a chemical bath containing CdCl₂, sodium citrate, NH₄OH and thiourea at 70 °C. On the CdS film, Sb₂S₃/C layers were deposited. This multilayer structure was subjected to the laser irradiation, C/Sb₂S₃ side facing the beam. The p-n junction formed by p-Sb₂S₃:C and n-type CdS showed V_oc = 500 mV and J_sc = 0.5 mA/cm² under illumination by a tungsten halogen lamp. This work opens up a new method to produce solar cell structures by laser assisted material processing.     

Analysis on the interfacial properties of transparent conducting oxide and hydrogenated p-type amorphous silicon carbide layers in p-i-n amorphous silicon thin film solar cell structure

Quantitative estimation of the specific contact resistivity and energy barrier at the interface between transparent conducting oxide (TCO) and hydrogenated p-type amorphous silicon carbide (a-Si_1 − xC_x:H(p)) was carried out by inserting an interfacial buffer layer of hydrogenated p-type microcrystalline silicon (μc-Si:H(p)) or hydrogenated p-type amorphous silicon (a-Si:H(p)). In addition, superstrate configuration p-i-n hydrogenated amorphous silicon (a-Si:H) solar cells were fabricated by plasma enhanced chemical vapor deposition to investigate the effect of the inserted buffer layer on the solar cell device. Ultraviolet photoelectron spectroscopy was employed to measure the work functions of the TCO and a-Si_1 − xC_x:H(p) layers and to allow direct calculations of the energy barriers at the interfaces. Especially interface structures were compared with/without a buffer which is either highly doped μc-Si:H(p) layer or low doped a-Si:H(p) layer, to improve the contact properties of aluminum-doped zinc oxide and a-Si_1 − xC_x:H(p). Out of the two buffers, the superior contact properties of μc-Si:H(p) buffer could be expected due to its higher conductivity and slightly lower specific contact resistivity. However, the overall solar cell conversion efficiencies were almost the same for both of the buffered structures and the resultant similar efficiencies were attributed to the difference between the fill factors of the solar cells. The effects of the energy barrier heights of the two buffered structures and their influence on solar cell device performances were intensively investigated and discussed with comparisons.     

High-rate synthesis of microcrystalline silicon films using high-density SiH4/H2 microwave plasma

A high electron density (> 10¹¹ cm^− 3) and low electron temperature (1-2 eV) plasma is produced by using a microwave plasma source utilizing a spoke antenna, and is applied for the high-rate synthesis of high quality microcrystalline silicon (μc-Si) films. A very fast deposition rate of ∼ 65 Å/s is achieved at a substrate temperature of 150 °C with a high Raman crystallinity and a low defect density of (1-2) × 10¹⁶ cm^− 3. Optical emission spectroscopy measurements reveal that emission intensity of SiH and intensity ratio of H_α/SiH are good monitors for film deposition rate and film crystallinity, respectively. A high flux of film deposition precursor and atomic hydrogen under a moderate substrate temperature condition is effective for the fast deposition of highly crystallized μc-Si films without creating additional defects as well as for the improvement of film homogeneity.     

Ion implanted crystalline silicon solar cells with blanket and selective emitter

We present an alternative method to form a blanket and selective emitter using a method that implants ion. This avoids several problems such as losing area by laser isolation and wet process for removing phosphosilicate glass formed on silicon substrate during the conventional thermal POCl₃ diffusion process. It was demonstrated that laser isolation is not necessary after the ion implanted solar cells were fabricated. Furthermore, we also fabricated selective emitter solar cells. After studying their characteristics, it was clear that the solar cells with ion implanted selective emitter improved cell efficiency. This is because their blue response increased and their reverse saturation current density decreased. Using an industrially feasible process, solar cell efficiencies of >18.5% on 156 mm × 156 mm using a shallow 100 Ω/sq. emitter and an ion implanted 65 Ω/sq. selective emitter were achieved.     

Fabrication and characteristics of n-Si/c-Si/p-Si heterojunction solar cells using hot-wire CVD

A double-side (bifacial) heterojunction (HJ) Si solar cell was fabricated using hot-wire chemical vapor deposition. The properties of n-type, intrinsic and p-type Si films were investigated. In these devices, the doped microcrystalline Si layers (n-type Si for emitter and p-type Si for back contact) are combined with and without a thin intrinsic amorphous Si buffer layer. The maximum temperature during the whole fabrication process was kept below 150 °C. The influence of hydrogen pre-treatment and n-Si emitter thickness on performance of solar cells have been studied. The best bifacial Si HJ solar cell (1 cm² sample) with an intrinsic layer yielded an active area conversion efficiency of 16.4% with an open circuit voltage of 0.645 V, short circuit current of 34.8 mA/cm² and fill factor of 0.73.