Large-area SnO2: F thin films by offline APCVD

In this paper, we reported the successful preparation of fluorine-doped tin oxide (FTO) thin films on large-area glass substrates (1245 mm × 635 mm × 3 mm) by self-designed offline atmospheric pressure chemical vapor deposition (APCVD) process. The FTO thin films were achieved through a combinatorial chemistry approach using tin tetrachloride, water and oxygen as precursors and Freon (F-152, C2H4F2) as dopant. The deposited films were characterized for crystallinity, morphology (roughness) and sheet resistance to aid optimization of materials suitable for solar cells. We got the FTO thin films with sheet resistance 8-11 Ω/□ and direct transmittance more than 83%. X-ray diffraction (XRD) characterization suggested that the as-prepared FTO films were composed of multicrystal, with the average crystal size 200-300 nm and good crystallinity. Further more, the field emission scanning electron microscope (FESEM) images showed that the films were produced with good surface morphology (haze). Selected samples were used for manufacturing tandem amorphous silicon (a-Si:H) thin film solar cells and modules by plasma enhanced chemical vapor deposition (PECVD). Compared with commercially available FTO thin films coated by online chemical vapor deposition, our FTO coatings show excellent performance resulting in a high quantum efficiency yield for a-Si:H solar cells and ideal open voltage and short circuit current for a-Si:H solar modules.     

Textured surface boron-doped ZnO transparent conductive oxides on polyethylene terephthalate substrates for Si-based thin film solar cells

Textured surface boron-doped zinc oxide (ZnO:B) thin films were directly grown via low pressure metal organic chemical vapor deposition (LP-MOCVD) on polyethylene terephthalate (PET) flexible substrates at low temperatures and high-efficiency flexible polymer silicon (Si) based thin film solar cells were obtained. High purity diethylzinc and water vapors were used as source materials, and diborane was used as an n-type dopant gas. P-i-n silicon layers were fabricated at ~ 398 K by plasma enhanced chemical vapor deposition. These textured surface ZnO:B thin films on PET substrates (PET/ZnO:B) exhibit rough pyramid-like morphology with high transparencies (T ~ 80%) and excellent electrical properties (Rs ~ 10 Ω at d ~ 1500 nm). Finally, the PET/ZnO:B thin films were applied in flexible p-i-n type silicon thin film solar cells (device structure: PET/ZnO:B/p-i-n a-Si:H/Al) with a high conversion efficiency of 6.32% (short-circuit current density J_SC = 10.62 mA/cm², open-circuit voltage V_OC = 0.93 V and fill factor = 64%).     

Characterization of pulsed laser deposited hydrogenated amorphous silicon films by spectroscopic ellipsometry

The wide absorption band of hydrogenated amorphous silicon (a-Si:H) is being realized as a key component of solar cells on glass. In this study, a-Si:H films were prepared by reactive pulsed laser deposition onto silicon and glass substrates. Ellipsometry showed that the optical properties of the films are effectively independent on the choice of substrate. According to the optical properties, the character of the films changes from amorphous silicon to dielectric as the hydrogen background pressure increases from 0 to 25 Pa. This observation was attributed to oxygen incorporation indicated by Rutherford Backscattering Spectrometry. Furthermore, a refractive index gradient in depth was revealed, which was attributed to the oxygen concentration gradient.     

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.     

Spectroscopic ellipsometry studies on hydrogenated amorphous silicon thin films deposited using DC saddle field plasma enhanced chemical vapor deposition system

Hydrogenated amorphous silicon (a-Si H) films deposited on crystalline silicon substrates using the DC saddle field (DCSF) plasma enhanced chemical vapor deposition (PECVD) system have been investigated. We have determined the complex dielectric function, ε(E) = ε₁(E) + iε₂(E) for hydrogenated amorphous silicon (a-Si:H) thin films by spectroscopic ellipsometry (SE) in the 1.5-4.5 eV energy range at room temperature. The results indicate that there is a change in the structure of the a-Si:H films as the thickness is increased above 4 nm. This is attributed to either an increase in the bonded hydrogen content and, or a decrease of voids during the growth of a-Si:H films. The film thickness and deposition temperature are two important parameters that lead to both hydrogen content variation and silicon bonding change as well as significant variations in the optical band gap. The influence of substrate temperature during deposition on film and interface properties is also included.     

Amorphous hydrogenated silicon-nitride films for applications in solar cells

The application of anti-reflective coatings (ARC) is a good method to improve the solar cell construction. The authors developed the RF plasma enhanced chemical vapour deposition method for preparation of amorphous silicon-nitrogen (a-Si:N:H) films for potential optoelectronic applications. The films have been obtained on borosilicate glass and monocrystalline silicon (1 0 0) (Cz-Si) in a process with optimised technological parameters such as a content of gaseous mixture of silane (SiH₄) and ammonia (NH₃). The properties of samples have been investigated by optical spectroscopy (PERKIN-ELMER Lambda 19) and scanning electron microscopy (SEM). The correlation between film properties and process parameters has been found. The results of optical investigations show that these materials are characterised by a variable optical gap dependent on the nitrogen content. After deposition of a-Si:N:H, a decrease in the total reflectivity, as compared to that of monocrystalline Si, was observed. The simulation of multicrystalline silicon solar cells performance with and without the ARC was done with the use of PC1D programme. The influence of the ARC on solar cell efficiency was observed. The obtained results indicate that a-Si:N:H films are suitable for application as antireflective and protective coatings for solar cells.     

Multi-phase structured silicon carbon nitride thin films prepared by hot-wire chemical vapour deposition

In this work, Silicon Carbon Nitride (Si-C-N) thin films were deposited by Hot Wire Chemical Vapour Deposition (HWCVD) technique from a gas mixture of silane (SiH₄), methane (CH₄) and nitrogen (N₂). Six sets of Si-C-N thin films were produced and studied. The component gas flow rate ratio (SiH₄:CH₄:N₂) was kept constant for all film samples. The total gas flow-rate (SiH₄ + CH₄ + N₂) was changed for each set of films resulting in different total gas pressure which represented the deposition pressure for each of these films ranging from 40 to 100 Pa. The effects of deposition pressure on the chemical bonding, elemental composition and optical properties of the Si-C-N were studied using Fourier transform infrared (FTIR) spectroscopy, Auger Electron Spectroscopy (AES) and optical transmission spectroscopy respectively. This work shows that the films are silicon rich and multi-phase in structure showing significant presence of hydrogenated amorphous silicon (a-Si:H) phase, amorphous silicon carbide (a-SiC), and amorphous silicon nitride (a-SiN) phases with Si-C being the most dominant. Below 85 Pa, carbon content is low, and the films are more a-Si:H like. At 85 Pa and above, the films become more Si-C like as carbon content is much higher and carbon incorporation influences the optical properties of the films. The properties clearly indicated that the films underwent a transition between two dominant phases and were dependent on pressure.     

Optimization of indium tin oxide by pulsed DC power on single junction amorphous silicon solar cells

We investigated the optimal deposition conditions of a thin indium tin oxide (ITO) film on an amorphous silicon (a-Si) single-junction solar cell using pulsed DC magnetron sputtering. Thin ITO films were deposited while power, deposition time, pressure, gas flow and temperature were varied to find such conditions. The efficiency of a-Si solar cells with ITO films was 6.65% at the optimal conditions — a pulsed DC power of 40 W, a deposition time of 460 s, a pressure of 0.53 Pa, gas flow of 16 sccm and 151 °C. On the other hand, an a-SiGe tandem solar cell with the ITO films made at the optimal conditions yields an efficiency of 7.20%. We have also examined the surface morphology of ITO coated a-Si solar cells, using atomic force microscopy. Interestingly, a change in power does not alter the surface morphology at small length scales, whereas at large scales, the lower power sample had a lower surface roughness than the samples made with higher powers. We also find that for the range of deposition conditions examined, the value of the roughness exponent does not change with α ? 2/3 and a thin layer of ITO does not modify the surface morphology significantly.     

Effect of thermal coupling on the electronic properties of hydrogenated amorphous silicon thin films deposited by electron cyclotron resonance

In photovoltaic devices, rather thin intrinsic layers of good quality materials are required and high deposition rates are a key point for a cost-effective mass production. In a previous study we have shown that good quality amorphous silicon (a-Si:H) films can be deposited by matrix distributed electron cyclotron resonance (MDECR) plasma CVD at very high deposition rates (∼ 2.5 nm/s). However, only thick films (> 1 μm) exhibited good transport properties. A very poor thermal coupling between the substrate holder and the substrate is the main reason for such a behaviour. We present here experimental data which support this conclusion as well as the improved transport and defect-related properties of new very thin a-Si:H samples (thickness around 0.3 μm) deposited at a higher temperature than the previous ones.     

Thin-film polycrystalline silicon solar cells formed by flash lamp annealing of a-Si films

We have fabricated thin-film solar cells using polycrystalline silicon (poly-Si) films formed by flash lamp annealing (FLA) of 4.5-µm-thick amorphous Si (a-Si) films deposited on Cr-coated glass substrates. High-pressure water-vapor annealing (HPWVA) is effective to improve the minority carrier lifetime of poly-Si films up to 10 µs long. Diode and solar cell characteristics can be seen only in the solar cells formed using poly-Si films after HPWVA, indicating the need for defect termination. The actual solar cell operation demonstrated indicates feasibility of using poly-Si films formed through FLA on glass substrates as a thin-film solar cell material.     

Hot-wire CVD amorphous Si materials for solar cell application

Hydrogenated amorphous silicon (a-Si:H) thin films and their application to solar cells fabricated using the hot-wire chemical vapor deposition (HWCVD) or (CAT)-CVD will be reviewed. This review will focus on the comparison to the standard plasma enhance (PE) CVD in the terms of deposition technique, film properties, and solar cell performance. The advantages of using HWCVD for a-Si:H solar cell research as well as the criteria for industry's adaptation of this technique for mass production will be addressed.     

Low-temperature preparation of flexible a-Si:H solar cells with hydrogenated nanocrystalline silicon p layer

In this paper we report on flexible a-Si:H solar cells prepared on polyethylene naphthalate (PEN) substrates using p-type hydrogenated nanocrystalline silicon thin films (p-nc-Si:H) as the window layer. The p-nc-Si:H films were prepared at low temperature (150 °C) using trimethylboron (TMB) as a dopant gas. The influence of the silane concentration (SC) on the electrical and structural properties of ultra-thin p-nc-Si:H as well as the performance of solar cells on PEN was investigated. The results show that the crystalline fraction and conductivity of p-nc-Si:H thin films diminished, while the deposition rate and RMS roughness of films increased, when the SC increases from 0.53% to 0.8%. For the a-Si:H solar cells on PEN with the non-textured electrodes, the best efficiency of 6.3% was achieved with the p-nc-Si:H thin films deposited at SC = 0.67%.     

Microstructure characterization of microcrystalline silicon thin films deposited by very high frequency plasma-enhanced chemical vapor deposition by spectroscopic ellipsometry

We applied ex situ spectroscopic ellipsometry (SE) on silicon thin films across the a-Si:H/μc-Si:H transition deposited using different hydrogen dilutions at a high pressure by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD). The optical models were based on effective medium approximation (EMA) and effective to estimate the thickness of the amorphous incubation layer and the volume fractions of amorphous, microcrystalline phase and void in μc-Si:H thin films. We obtained an acceptable data fit and the SE results were consistent with that from Raman spectroscopy and atomic force microscopy (AFM). We found a thick incubation layer in μc-Si:H thin films deposited at a high rate of ~ 5 Å/s and this microstructure strongly affected their conductivity.     

Plasma deposition of n-SiOx nanocrystalline thin film for enhancing the performance of silicon thin film solar cells

In this paper, we firstly optimized the properties of n-SiO_x nanocrystalline thin film through tuning deposition parameters by plasma enhanced chemical vapor deposition, so that we can actively control the properties of materials obtained. Secondly, we proposed using n-SiO_x/Al as back reflector for amorphous silicon (a-Si:H) solar cells. Compared to Al single-layer as back reflector, adding an n-SiO_x layer into the back reflector could improve the solar cell performance, which not only enhances the short circuit current density by an improvement of spectral response in the wavelength range of 550-750 nm, but also improves the open circuit voltage. With an optimized n-SiO_x/Al back reflector, a-Si:H solar cells with an intrinsic layer thickness of 270 nm show 13.1% enhancement in efficiency. In addition, a-Si:H/μc-Si:H tandem solar cells with n-SiO_x as intermediate reflector were also researched. As a result, it evidently balanced the current matching between top and bottom cell.     

Study on the mechanism of rapid solid-phase recrystallization of hydrogenated amorphous silicon film by rapid thermal processing

High-quality hydrogenated amorphous silicon films (a-Si:H) were deposited on quartz glass substrates by radio-frequency plasma-enhanced chemical vapor deposition method. The films were then annealed at 800 °C for 3 min by rapid thermal processing (RTP). As confirmed by X-ray diffractometry and Raman spectrometry, hydrogenated microcrystalline silicon films were obtained after the annealing procedure. The mechanism of the rapid solid-phase recrystallization of a-Si:H film by RTP was theoretically mainly attributed to the interaction between short-wavelength photons and ground-state precursor radicals (silicon, SiH₂ and SiH₃).     

Highly conductive p-type nanocrystalline silicon films deposited by RF-PECVD using silane and trimethylboron mixtures at high pressure

In this paper we present a study of boron-doped nc-Si:H films prepared by PECVD at high deposition pressure (≥4 mbar), high plasma power and low substrate temperature (≤200 °C) using trimethylboron (TMB) as a dopant gas. The influence of deposition parameters on electrical, structural and optical properties is investigated. We determine the deposition conditions that lead to the formation of p-type nanocrystalline silicon thin films with very high crystallinity, high value of dark conductivity (>7 (Ω cm)⁻¹) and high optical band gap (≥1.7 eV). Modeling of ellipsometry spectra reveals that the film growth mechanism should proceed through a sub-surface layer mechanism that leads to silicon crystallization.The obtained films are very good candidates for application in amorphous and nanocrystalline silicon solar cells as a p-type window layer.     

Effect of TiO2 nanopatterns on the performance of hydrogenated amorphous silicon thin-film solar cells

We investigate how TiO₂ nanopatterns formed onto ZnO:Al (AZO) films affect the performance of hydrogenated amorphous silicon (a-Si:H) solar cells. Scanning electron microscopy results show that the dome-shaped TiO₂ nanopatterns (300 nm in diameter) having a period of 500 nm are formed onto AZO films and vary from 60 to 180 nm in height. Haze factor increases with an increase in the height of the nanopatterns in the wavelength region below 530 nm. Short circuit current density also increases with an increase in the height of the nanopatterns. As the nanopatterns increases in height, the fill factor of the cells slightly increases, reaches maximum (0.64) at 100 nm, and then decreases. Measurements show that a-Si:H solar cells fabricated with 100 nm-high TiO₂ nanopatterns exhibit the highest conversion efficiency (6.34%) among the solar cells with the nanopatterns and flat AZO sample.     

Amorphous/crystalline silicon heterojunction solar cells with varying i-layer thickness

We study the effect on various properties of varying the intrinsic layer (i-layer) thickness of amorphous/crystalline silicon heterojunction (SHJ) solar cells. Double-side monocrystalline silicon (c-Si) heterojunction solar cells are made using hot-wire chemical vapor deposition on high-lifetime n-type Czochralski wafers. We fabricate a series of SHJ solar cells with the amorphous silicon (a-Si:H) i-layer thickness at the front emitter varying from 3.2 nm (0.8xi) to ~ 96 nm (24xi). Our optimized i-layer thickness is about 4 nm (1xi). Our reference cell (1xi) performance has an efficiency of 17.1% with open-circuit voltage (V_oc) of 684 mV, fill factor (FF) of 76%, and short-circuit current density (J_sc) of 33.1 mA/cm². With an increase of i-layer thickness, V_oc changes little, whereas the FF falls significantly after 12 nm (3xi) of i-layer. Transient capacitance measurements are used to probe the effect of the potential barrier at the n-type c-Si/a-Si interface on minority-carrier collection. We show that hole transport through the i-layer is field-driven transport rather than tunneling.     

Natively textured surface aluminum-doped zinc oxide transparent conductive layers for thin film solar cells via pulsed direct-current reactive magnetron sputtering

Natively textured surface aluminum-doped zinc oxide (ZnO:Al) layers for thin film solar cells were directly deposited without any surface treatments via pulsed direct-current reactive magnetron sputtering on glass substrates. Such an in-situ texturing method for sputtered ZnO:Al thin films has the advantages of efficiently reducing production costs and dramatically saving time in photovoltaic industrial processing. High purity metallic Zn-Al (purity: 99.999%, Al 2.0 wt.%) target and oxygen (purity: 99.999%) were used as source materials. During the reactive sputtering process, the oxygen gas flow rate was controlled using plasma emission monitoring. The performance of the textured surface ZnO:Al transparent conductive oxides (TCOs) thin films can be modified by changing the number of deposition rounds (i.e. thin-film thicknesses). The initially milky ZnO:Al TCO thin films deposited at a substrate temperature of ~ 553 K exhibit rough crater-like surface morphology with high transparencies (T ~ 80-85% in visible range) and excellent electrical properties (ρ ~ 3.4 × 10^− 4 Ω cm). Finally, the textured-surface ZnO:Al TCO thin films were preliminarily applied in pin-type silicon thin film solar cells.     

Impact of the nanorod structure on the tandem thin-film solar cell

The novel thin-film solar cell was investigated with a nanorod structure that could solve the conflict between light absorption and carrier transport in the amorphous silicon (a-Si)/amorphous silicon-germanium (a-SiGe) tandem thin-film solar cell. This structure has an n-type a-Si nanorod array on the substrate, and an a-SiOx p-layer and an a-SiGe i-layer are sequentially grown along the surface of each n-type a-Si nanorod, for the bottom cell. After the above bottom-cell process, a similar process is used to fabricate an amorphous Si p-i-n top cell on the bottom cell. Under sunlight illumination, the light is absorbed along the vertical direction of the nanorod, but as the carrier transport is along the horizontal direction, the nanorod may absorb most of the sunlight. In the meantime, the solar cell is still thin enough for the effective transport of photogenerated carriers.