Structural and optical properties of textured ZnO:Al films on glass substrates prepared by in-line rf magnetron sputtering

Textured ZnO:Al films with excellent light scattering properties as a front electrode of silicon thin film solar cells were prepared on glass substrates by an in-line rf magnetron sputtering, followed by a wet-etching process to modify the surface morphologies of the films. Deposition parameters and wet etching conditions of the films were controlled precisely to obtain the optimized surface features. All as-deposited films show a strong preferred orientation in the [0 0 1] direction under our experimental conditions. The microstructure of the films was significantly affected by working pressure and film compactness was reduced with increasing working pressure, while the effect of a substrate temperature on the microstructure is less pronounced. A low resistivity of 4.25×10⁻⁴ Ω cm and high optical transmittance of above 80% in a visible range were obtained in the films deposited at 1.5 mTorr and 100 °C. After wet etching process, the surface morphologies of the films were changed dramatically depending on the microstructure and film compactness of the initial films. By controlling the surface feature, the haze factor and angular resolved distribution of the textured ZnO:Al films were improved remarkably when compared with commercial SnO₂:F films. The textured ZnO:Al and SnO₂:F films were applied as substrates for a silicon thin film solar cells with tandem structure of a-Si:H/μc-Si:H. Compared with the solar cells with the SnO₂:F films, a significant enhancement in the short-circuit current density of the μc-Si:H bottom cell was achieved, which is due to the improved light scattering on the highly textured ZnO:Al film surfaces in the long wavelength above 600 nm.     

Development of thin film amorphous silicon oxide/microcrystalline silicon double-junction solar cells and their temperature dependence

We have developed thin film silicon double-junction solar cells by using micromorph structure. Wide bandgap hydrogenated amorphous silicon oxide (a-SiO:H) film was used as an absorber layer of top cell in order to obtain solar cells with high open circuit voltage (V_oc), which are attractive for the use in high temperature environment. All p, i and n layers were deposited on transparent conductive oxide (TCO) coated glass substrate by a 60 MHz-very-high-frequency plasma enhanced chemical vapor deposition (VHF-PECVD) technique. The p-i-n-p-i-n double-junction solar cells were fabricated by varying the CO₂ and H₂ flow rate of i top layer in order to obtain the wide bandgap with good quality material, which deposited near the phase boundary between a-SiO:H and hydrogenated microcrystalline silicon oxide (μc-SiO:H), where the high V_oc can be expected. The typical a-SiO:H/μc-Si:H solar cell showed the highest initial cell efficiency of 10.5%. The temperature coefficient (TC) of solar cells indicated that the values of TC for conversion efficiency (η) of the double-junction solar cells were inversely proportional to the initial V_oc, which corresponds to the bandgap of the top cells. The TC for η of typical a-SiO:H/μc-Si:H was −0.32%/ °C, lower than the value of conventional a-Si:H/μc-Si:H solar cell. Both the a-SiO:H/μc-Si:H solar cell and the conventional solar cell showed the same light induced degradation ratio of about 20%. We concluded that the solar cells using wide bandgap a-SiO:H film in the top cells are promising for the use in high temperature regions.     

Deposition of μc-Si and μc-SiC thin films by remote plasma-enhanced chemical-vapor deposition

This paper describes properties of microcrystalline silicon (μc-Si), and microcrystalline silicon-carbon (μc-SiC) thin films formed by the process of remote plasma-enhanced chemical-vapor deposition (PECVD). We discuss: (i) the way that the remote PECVD deposition process is applied to the deposition of μc-Si and μc-SiC thin films; (ii) the characterization and properties of the intrinsic and doped μc-Si thin film materials; (iii) the characterization and properties of the intrinsic and doped μc-SiC thin film materials; and (iv) the application of remote PECVD μc-Si and μc-SiC thin films in device structures.     

Wet-etch texturing of ZnO:Ga back layer on superstrate-type microcrystalline silicon solar cells

Surface wet etching is applied to the ZnO:Ga (GZO) back contact in μc-Si thin film solar cells. GZO transparency increases with increasing deposition substrate temperature. Texturing enhances reflective scattering, with etching around 5-6 s producing the best scattering, whereas etching around 5 s produces the best fabricated solar cells. Etching beyond these times produces suboptimal performance related to excessive erosion of the GZO. The best μc-Si solar cell achieves FF=68%, V_OC=471 mV and J_SC=21.48 mA/cm² (η=6.88%). Improvement is attributed to enhanced texture-induced scattering of light reflected back into the solar cell, increasing the efficiency of our lab-made single μc-Si solar cells from 6.54% to 6.88%. Improved external quantum efficiency is seen primarily in the longer wavelengths, i.e. 600-1100 nm. However, variation of the fabrication conditions offers opportunity for significant tuning of the optical absorption spectrum.     

Microcrystalline silicon films and solar cells deposited by PECVD and HWCVD

The application of microcrystalline silicon (μc-Si:H) in thin-film solar cells is addressed in the present paper. Results of different technologies for the preparation of μc-Si:H are presented, including plasma enhanced chemical vapour deposition (PECVD) using 13.56 MHz (radio frequency, rf) and 94.7 MHz (very high frequency, vhf) and hot-wire chemical vapour deposition (HWCVD). The influence of the silane concentration (SC) on the material and solar cell parameters is studied for the different techniques as the variation of SC allows to optimise the solar cell performance in each deposition regime. The best performance of μc-Si:H solar cells is always observed near the transition to amorphous growth. The highest efficiency obtained so far at a deposition rate of 5 Å/s is 9.4%, achieved with rf-PECVD in a deposition regime of using high pressure and high discharge power. High deposition rates and solar cell efficiencies could be also achieved by vhf-PECVD. An alternative approach represents the HWCVD which also demonstrated high deposition rates for μc-Si:H. However, good material quality and solar cell performance could only be achieved at low substrate temperatures and, consequently, low deposition rates. The μc-Si:H solar cells prepared by HWCVD exhibit comparably high efficiencies up to 9.4% and exceptionally high open circuit voltages up to 600 mV but at lower deposition rates (≈1 Å/s). The properties of PECVD and HWCVD solar cells are carefully compared.     

Silicon-organic pigment material hybrids for photovoltaic application

Hybrid materials of silicon and organic dyes have been investigated for possible application as photovoltaic material in thin film solar cells. High conversion efficiency is expected from the combination of the advantages of organic dyes for light absorption and those of silicon for charge carrier separation and transport. Low temperature remote hot wire chemical vapor deposition (HWCVD) was developed for microcrystalline silicon (μc-Si) deposition using SiH₄/H₂ mixtures. As model dyes zinc phthalocyanines have been evaporated from Knudsen type sources. Layers of dye on μc-Si and μc-Si on dye films, and composites of simultaneously and sequentially deposited Si and dye have been prepared and characterized. Raman, absorption, and photoemission spectroscopy prove the stability of the organic molecules against the rough HWCVD-Si process. Transient microwave conductivity (TRMC) indicates good electronic quality of the μc-Si matrix. Energy transfer from dye to Si is indicated indirectly by luminescence and directly by photoconductivity measurements. F_xZnPc pigments with x=0,4,8,16 have been synthesized, purified and adsorbed onto H-terminated Si(1 1 1) for electronic state line up determination by photoelectron spectroscopy. For x=4 and 8 the dye frontier orbitals line up symmetrically versus the Si energy gap offering similar energetic driving forces for electron and hole injection, which is considered optimum for bulk sensitization and indicates a direction to improve the optoelectronic coupling of the organic dyes to silicon.     

Plasma enhanced chemical vapor deposition of excellent a-Si:H passivation layers for a-Si:H/c-Si heterojunction solar cells at high pressure and high power

The intrinsic a-Si:H passivation layer inserted between the doped a-Si:H layer and the c-Si substrate is very crucial for improving the performance of the a-Si:H/c-Si heterojunction (SHJ) solar cell. The passivation performance of the a-Si:H layer is strongly dependent on its microstructure. Usually, the compact a-Si:H deposited near the transition from the amorphous phase to the nanocrystalline phase by plasma enhanced chemical vapor deposition (PECVD) can provide excellent passivation. However, at the low deposition pressure and low deposition power, such an a-Si:H layer can be only prepared in a narrow region. The deposition condition must be controlled very carefully. In this paper, intrinsic a-Si:H layers were prepared on n-type Cz c-Si substrates by 27.12 MHz PECVD at a high deposition pressure and high deposition power. The corresponding passivation performance on c-Si was investigated by minority carrier lifetime measurement. It was found that an excellent a-Si:H passivation layer could be obtained in a very wide deposition pressure and power region. Such wide process window would be very beneficial for improving the uniformity and the yield for the solar cell fabrication. The a-Si:H layer microstructure was further investigated by Raman and Fourier transform infrared (FTIR) spectroscopy characterization. The correlation between the microstructure and the passivation performance was revealed. According to the above findings, the a-Si:H passivation performance was optimized more elaborately. Finally, a large-area SHJ solar cell with an efficiency of 22.25% was fabricated on the commercial 156 mm pseudo-square n-type Cz c-Si substrate with the opencircuit voltage (V_oc) of up to 0.732 V.     

Intrinsic microcrystalline silicon: A new material for photovoltaics

Microcrystalline silicon (μc-Si:H) prepared by plasma-enhanced chemical vapor deposition (PECVD) has been investigated as material for absorber layers in solar cells. The deposition process has been adjusted to achieve high deposition rates and optimized solar cell performance. In particular, already moderate variations of the crystalline vs. amorphous volume fractions were found to effect the electronic material – and solar cell properties. Such variation is readily achieved by changing the process gas mixture of silane to hydrogen. Best cell performance was found for material near the transition to the amorphous growth regime. With this optimized material efficiencies of 7.5% for a 2 μm thick μc-Si:H single solar cell and 12% for an a-Si:H/μc-Si:H stacked solar cell have been achieved.     

The effects of the band gap and defects in silicon nitride on the carrier lifetime and the transmittance in c-Si solar cells

In this paper, silicon nitride thin films with different silane and ammonia gas ratios were deposited and characterized for the antireflection and passivation layer of high efficiency single crystalline silicon solar cells. An increase in the transmittance and a recombination decrease using an effective antireflection and passivation layer can be enhanced by an optimized SiN_x film in order to attain higher solar cell efficiencies. As the flow rate of the ammonia gas increased, the refractive index decreased and the band gap increased. Consequently, the transmittance increased due to the higher band gap and the decrease of the defect states, which existed for the 1.68 and 1.80 eV in the SiN_x films. The interface trap density found in silicon can be reduced down to 1.0×10¹⁰ cm⁻² eV⁻¹ for the SiN_x layer deposited under the optimized silane to ammonia gas ratio. Reduction in the carrier lifetime of the SiN_x films deposited using a higher NH₃/SiH₄ flow ratio was caused by the increase of the interface traps and the defect states in/on the interface between the SiN_x and the silicon wafer. Silicon and nitrogen rich films are not suitable for generating both higher carrier lifetimes and transmittance. An improvement in the single c-Si solar cell parameters was observed for the cells with an optimal SiN_x layer, as compared to those with non-optimal SiN_x layers. These results indicate that the band gap and the defect states of the SiN_x films should be carefully controlled in order to obtain the maximum efficiency for c-Si solar cells.     

I-V characteristics of a-Si-c-Si hetero-junction diodes made by hot wire CVD

p-Type hydrogenated amorphous silicon (a-Si:H) was deposited on n-type crystalline silicon (c-Si) substrates to obtain hetero-junction diodes. Additionally, a thin intrinsic a-Si:H layer was inserted between both the p-type film and the n-type substrate to study its passivation effect on the c-Si surface. The amorphous films were obtained by the hot wire chemical vapor deposition (HWCVD) technique, using a tungsten filament and silane (SiH₄), hydrogen (H₂) and diborane (B₂H₆) gases, where the deposition parameters such as gas flow, substrate temperature and filament temperature were varied. Optical band gap, deposition rate and conductivity were measured for all the films. We studied the influence of the quality of the amorphous films upon the performance of the hetero-junction diodes. In particular, the diode ideality factor (n) and the saturation current density (J₀) were determined by measuring the current-voltage characteristics in dark conditions. It is shown that the presence of the intrinsic layer is fundamental for making good diodes, since devices made without this film cause the diodes to have high saturation current density and ideality factor (J₀>10×10⁻⁶ A/cm², n>4) as compared to diodes with a good intrinsic layer (J₀=5×10⁻⁹ A/cm², n=1.39). The results obtained are encouraging, but the quality of the intrinsic films still should be improved for applying them to HIT solar cells.     

A pre-hydrogen glow method to improve the reproducibility of intrinsic microcrystalline silicon thin film depositions in a single-chamber system

Material property differences are observed in hydrogenated microcrystalline silicon (μc-Si:H) thin films deposited under the same nominal conditions in a single-chamber plasma enhanced chemical vapor deposition system but at different stages of chamber history during prolonged usage. This phenomenon is called system shift, which results from the increase of powder coverage on the surface of the cathode and the coatings on other areas in the chamber. We propose a pre-hydrogen glow method to suppress the system shifting. Experimental results show that this method is very effective to reduce the non-reproducibility in μc-Si:H depositions for prolonged usage of the deposition system. In addition, the μc-Si:H films deposited with the pre-hydrogen glow have an improved structural homogeneity along the film thickness.     

Photovoltaic properties and technological aspects of In1−xGaxN/Si, Ge (0<x<0.6) heterojunction solar cells

Photovoltaic properties of n-In_1−xGa_xN/p-Si, Ge (IGN) heterostructures, covering the compositional range 0<x<0.6, have been evaluated by 1d device simulation, and are compared with the performance of c-Si homojunction thin film cells. Film morphology and physical properties were characterized by high-resolution transmission electron microscopy (TEM), secondary ion mass spectrometry (SIMS) and photoluminescence (PL). Best achievable cell performances under AM1.5 illumination conditions were 18% for p-Ge, and up to 27% for n-IGN/p-Si contacts, achievable under optimum cell design, materials and operation parameters. Pure InN bottom layers, exhibiting an intrinsic band gap of 0.7 eV, reveal a reduced efficiency of 2.5%. The cell efficiency is strongly affected by film quality, accounted for by variation of electron affinity, majority carrier mobility, minority carrier lifetime, film thickness and doping levels. The morphology of thin IGN and InN films deposited onto silicon and sapphire substrate material revealed granular growth, along with a high density of grain boundaries. TEM resolved the formation of a very thin homogeneous silicon nitride interlayer on silicon substrates. The electrically isolating layer almost completely suppresses the photovoltaic effect. Depth profiling of InN films deposited onto sapphire substrates by SIMS analysis indicated oxygen as the dominant material contamination. It accounts, among other effects, for a gradually increasing band gap throughout the film structure. Observed large photoluminescence broadening effects, and related short minority carrier lifetimes are most likely related to high levels of oxygen contamination and concentration of grain boundaries. Possible routes to overcome these problems are discussed.     

Total SiH4/H2 pressure effect on microcrystalline silicon thin films growth and structure

The effect of the total SiH₄/H₂ gas pressure (1–10 Torr) on the growth rate, the film crystallinity and the nature of hydrogen bonding of microcrystalline silicon thin films deposited by 13.56 MHz plasma-enhanced chemical vapour deposition (PECVD) was investigated under well-controlled discharge conditions. The deposition rate presents an optimum for 2.5 Torr, which does not follow the trend of silane consumption that increases with pressure and is attributed to an increase in plasma density. The film crystallinity increases with pressure from 1–2.5 Torr and then remains almost the same, whereas the films deposited at 1 Torr are highly stressed. On the other hand, hydrogen bonding is also drastically affected.     

Microcrystalline silicon solar cells fabricated by VHF plasma CVD method

A series of systematic investigations on microcrystalline silicon (μc-Si:H) solar cells at high deposition rates has been studied. The effect of high deposition pressure and narrow cathode-substrate (CS) distance on the deposition rate and quality of microcrystalline silicon is discussed. The microcrystalline silicon solar cell is adopted as middle cell and bottom cell in a three-stacked junction solar cell. The characteristics of large area three-stacked junction solar cells, whose area is 801.6 cm² including grid electrode areas, are studied in various deposition rates from 1 to 3 nm/s of microcrystalline silicon. An initial efficiency of 13.1% is demonstrated in the three-stacked junction solar cell with microcrystalline silicon deposited at 3 nm/s.     

MoOx/Ag/MoOx multilayers as hole transport transparent conductive electrodes for n-type crystalline silicon solar cells

Substitution of highly doped layers with conventional transparent conductive electrodes as carrier collecting and selective contacts in conventional crystalline silicon (c-Si) solar cell configurations is crucial in increasing affordability of solar cells by lowering material costs. In this study, oxide/metal/oxide (OMO) multilayers featuring molybdenum oxide (MoO_x) and silver (Ag) thin films are developed by thermal evaporation technique, as dopant-free hole transport transparent conductive electrodes (HTTCEs) for n-type c-Si solar cells. Semidopant-free asymmetric heterocontact (semi-DASH) solar cells on n-type c-Si utilizing OMO multilayers are fabricated. The effect of outer MoO_x layer thickness and Ag deposition rate on the photovoltaic characteristics of the fabricated semi-DASH solar cells are investigated. A comparison of front side pyramid textured and flat surface solar cells is performed to optimize the optical and electrical properties. Highest efficiency of 9.3% ± 0.2% is achieved in a pyramid textured semi-DASH c-Si solar cell with 15/10/30 nm of HTTCE structure.     

Nanocrystalline silicon thin films deposited by high-frequency sputtering at low temperature

Intrinsic and n-type hydrogenated nanocrystalline silicon thin films (nc-Si:H) were deposited at a temperature as low as 95 °C by high-frequency (HF) sputtering, with hydrogen dilution percentage varying from 31% to 73%. In order to study the properties of the films prepared by this method, the samples were examined by infrared absorption spectroscopy (IR), X-ray diffraction (XRD), SEM, spectroscopic ellipsometry (SE), laser Raman spectrometry and atomic force microscopy (AFM). XRD measurements showed that this film has a new microstructure, which is different from the films deposited by other methods. In addition, an n-type nc-Si:H/p-type c-Si heterojunction solar cell, which has an open circuit voltage (V_oc) of 370 MV and a short-circuit current intensity (J_sc) of 6.5 mA/cm², was produced on the nanocrystalline silicon thin film. After 10 h light exposure under AM1.5 (100 MW/cm²) light intensity at room temperature, radiation degradation has not been found for the device.     

Development of CZTS thin films solar cells by pulsed laser deposition: Influence of pulse repetition rate

High-quality Cu₂ZnSnS₄ (CZTS) thin films were synthesized by pulsed laser deposition as a function of pulse repetition rate onto the SLG substrates. Influence of pulse repetition rate onto the structural, morphological, compositional and optical properties have been investigated for as-deposited and annealed thin films. X-ray diffraction study shows transformation of amorphous to crystalline phase after tuning pulse repetition rate and annealing of samples. FESEM images of thin films show increase in grain size upon annealing. Films are nearly stoichiometric deposited at 10 Hz repetition rate has been confirmed with the help of EDAX and XPS analysis. The direct band gap energy of the deposited CZTS thin films are in the solar energy range. The performance of solar cell based on CZTS absorber layer has been tested and the efficiency is about 2%.     

Fabrication of microcrystalline silicon solar cells on a SnO2 coated substrate using seed layer insertion

We fabricated hydrogenated microcrystalline silicon (μc-Si:H) solar cells on SnO₂ coated glass using a seed layer insertion technique. Since rich hydrogen atoms from the μc-Si:H deposition process degrade the SnO₂ layer, we applied p-type hydrogenated amorphous silicon (p-a-Si:H) as a window layer. To grow the μc-Si:H layer on the p-a-Si:H window layer, we developed a seed layer insertion method. We inserted the seed layer between the p-a-Si:H layer and intrinsic bulk μc-Si:H. This seed layer consists of a thin hydrogen diluted silicon buffer layer and a naturally hydrogen profiled layer. We compared the characteristics of solar cells with and without the seed layer. When the seed layer was not applied, the fabricated cell showed the characteristics of a-Si:H solar cell whose spectral response was in a range of 400-800 nm. Using the seed layer, we achieved a μc-Si:H solar cell with performance of V_oc=0.535 V, J_sc=16.0 mA/cm², FF=0.667, and conversion efficiency=5.7% without any back reflector. The spectral response was in the range of 400-1100 nm. Also, the fabricated device has little substrate dependence, because a-Si:H has weaker substrate selectivity than μc-Si:H.     

氮化硅薄膜的性能研究以及在多晶硅太阳电池上的应用

利用椭圆偏振仪、准稳态光电导衰减法(QSSPCD)、X射线光电子能谱(XPS)、红外吸收光谱(IR)、反射谱等手段，研究了不同硅烷和氨气配比条件以及沉积温度对在多晶硅太阳电池上所沉积的氮化硅薄膜性能的影响，优化了沉积条件。通过比较沉积前后电池的各项性能，确认经氮化硅钝化后电池效率提高了40％以上，电池的短路电流也提高了30％以上，对于电池的开路电压提高也很大.     

Microcrystalline silicon thin film solar modules on glass

We developed microcrystalline silicon (μc-Si:H) thin film solar modules on textured ZnO-coated glass. The single junction (p–i–n) cell structure was prepared by plasma-enhanced chemical vapour deposition (PECVD) at substrate temperatures below 250 °C. Front ZnO and back contacts were prepared by sputtering. A process for the monolithic series connection of μc-Si:H cells by laser scribing was developed. These microcrystalline p–i–n modules showed aperture area efficiencies up to 8.3% and 7.3% on aperture areas of 64 and 676 cm², respectively. The temperature coefficient of the efficiency was −0.4%/K.