Microcrystalline silicon carbide thin films grown by HWCVD at different filament temperatures and their application in n-i-p microcrystalline silicon solar cells

To optimize the performance of microcrystalline silicon carbide (µc-SiC:H) window layers in n-i-p type microcrystalline silicon (µc-Si:H) solar cells, the influence of the rhenium filament temperature in the hot wire chemical vapor deposition process on the properties of µc-SiC:H films and corresponding solar cells were studied. The filament temperature T_F has a strong effect on the structure and optical properties of µc-SiC:H films. Using these µc-SiC:H films prepared in the range of T_F = 1800-2000 °C as window layers in n-side illuminated µc-Si:H solar cells, cell efficiencies of above 8.0% were achieved with 1 µm thick µc-Si:H absorber layer and Ag back reflector.     

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.     

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.     

Analysis of single junction a-Si:H solar cells grown on different TCO’s

In consequence of previous investigation of individual transparent conductive oxide (TCO) and absorber layers a study was carried out on hydrogenated amorphous silicon (a-Si:H) solar cells with diluted intrinsic a-Si:H absorber layers deposited on glass substrates covered with different TCO films. The TCO film forms the front contact of the super-strata solar cell and has to exhibit good electrical (high conductivity) and optical (high transmittance) properties. In this paper we focused our attention on the influence of using different TCO’s as a front contact in solar cells with structure as follows: Corning glass substrate/TCO (800, 950 nm)/p-type μc-Si:H (∼5 nm)/p-type a-Si:H (10 nm)/a-SiC:H buffer layer (∼5 nm)/intrinsic a-Si:H absorber layer with dilution R = [H₂]/[SiH₄] = 20 (300 nm)/n-type a-Si:H layer (20 nm)/Ag + Al back contact (100 + 200 nm). Diode sputtered ZnO:Ga, textured and non-textured ZnO:Al [3] and commercially fabricated ASAHI (SnO₂:F) U-type TCO’s have been used. The morphology and structure of ZnO films were altered by reactive ion etching (RIE) and post-deposition annealing.It can be concluded that the single junction a-Si:H solar cells with ZnO:Al films achieved comparable parameters as those prepared with commercially fabricated ASAHI U-type TCO’s.     

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.     

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.     

Improvement of μc-Si:H n-i-p cell efficiency with an i-layer made by hot-wire CVD by reverse H2-profiling

The technique of maintaining a proper crystalline ratio in microcrystalline silicon (μc-Si:H) layers along the thickness direction by decreasing the H₂ dilution ratio during deposition (H₂ profiling) was introduced by several laboratories while optimizing either n-i-p or p-i-n μc-Si:H cells made by PECVD. With this technique a great increase in the energy conversion efficiency was obtained. Compared to the PECVD technique, the unique characteristics of HWCVD, such as the catalytic reactions, the absence of ion bombardment, the substrate heating by the filaments and filament aging effects, necessitate a different strategy for device optimization. We report in this paper the result of our method of using a reverse H₂ profiling technique, i.e. increasing the H₂ dilution ratio instead of decreasing it, to improve the performance of μc-Si:H n-i-p cells with an i-layer made by HWCVD. The principle behind this technique is thought to be a compensation effect for the influence of progressing silicidation of the filaments during the growth of μc-Si:H, if the filament current is held constant during growth. The dependence of the material crystallinity on thickness with and without H₂ profiling is discussed and solar cell J-V parameters are presented. Thus far, the best efficiency of μc-Si:H n-i-p cells made on a stainless steel substrate with an Ag/ZnO textured back reflector made in house has been improved to 8.5%, which is the highest known efficiency obtained for n-i-p cells with a hot-wire μc-Si:H i-layer.     

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.     

Aluminum-induced in situ crystallization of HWCVD a-Si:H films

Aluminum-induced in situ crystallization (AIC) of amorphous silicon films deposited by hot wire chemical vapor deposition (HWCVD) on glass is demonstrated. Aluminum was deposited at temperatures varying from room temperature to 300 °C on HWCVD a-Si:H films. The AIC was observed to take place in situ during the deposition of Al films, when the glass/a-Si:H temperature is kept 300 °C. A 20-nm Al film was effective in inducing crystallization of about 63% in the a-Si:H film. Thus, separate post-deposition annealing step can be avoided. For an Al film thickness comparable to the amorphous silicon film deposited at an optimum deposition rate, crystallization at temperature as low as 200 °C is observed. It was also observed that the growth pattern of c-Si in case of AIC without post-deposition annealing was identical to AIC with annealing step.     

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%.     

Enhancement of microcrystalline n-i-p solar cell performance via use of pre-covering layers and H2 treatment

We study the effects of a-Si:H and μc-Si:H covering layers and an H₂ treatment on the characteristics of μc-Si:H thin film solar cells deposited in open single chamber very high frequency plasma enhanced chemical vapor deposition systems. Secondary ion mass spectrometry is used to evaluate the phosphor concentration in the μc-Si:H material. Compared to use of an a-Si:H covering layer, use of a μc-Si:H covering layer reduces dopant contamination by a relative 50%, and improves efficiency by a relative 6%, and use of an H₂ treatment reduces dopant contamination by a relative 64%, and improves efficiency by a relative 17%.     

Thin-film silicon solar cells applying optically decoupled back reflectors

Thin-film silicon solar cells often apply a metal back reflector (BR) separated from the silicon layers by a thin rear dielectric of thickness around 80 nm or a white paint combined with a thick rear dielectric of several micrometers. In this work, we investigate the optical performance of microcrystalline silicon (μc-Si:H) solar cells applying BRs of various topographies. In contrast to a standard 80 nm-ZnO/Ag BR design, for which the BR nearly strictly follows the texture of the underlying μc-Si:H layers, placing the Ag BR far from the μc-Si:H layers allows for a variation of the BR topography. Irrespective of the investigated BR topographies and also for a conventional white paint BR, long distances (of several micrometers) between the BR and the μc-Si:H layers are found to be detrimental for the light trapping. Optical simulations based on both rigorous and scalar scattering theory have been performed to understand the impact of the diverse BR designs on the optical cell performance.     

Nano-structural properties of ZnO films for Si based heterojunction solar cells

Properties and structure of ZnO and ZnO:Al films deposited on c-Si, a-Si:H/Si and glass substrates are studied by various methods. The transmittance of the ZnO:Al was found to be higher when compared to ZnO, and the refractive index lower. X-ray photoelectron spectroscopy (XPS) shows that the screening efficiency in the presence of core holes is enhanced in the Al doped ZnO. The roughness of the ZnO:Al surfaces is strongly substrate dependent. With transmission electron microscopy (TEM) a 2-3 nm thick amorphous interfacial layer was observed independently of substrate and doping. Deposition of ZnO on a-Si:H substrate results in crystallization of the a-Si:H layer independently of Al doping.     

Characterization of SiNx/a-Si:H crystalline silicon surface passivation under UV light exposure

One of the most promising solution for crystalline silicon surface passivation in solar cell fabrication consists in a low temperature (< 400 °C) Plasma Enhanced Chemical Vapor Deposition of a double layer composed by intrinsic hydrogenated amorphous silicon (a-Si:H) and hydrogenated amorphous silicon nitride (SiN_x). Due to the high amount of hydrogen in the gas mixture during the double layer deposition, the passivation process results particularly useful in case of multi-crystalline silicon substrates in which hydrogenation of grain boundaries is very needed. In turn the presence of hydrogen inside both amorphous layers can induce metastability effects. To evaluate these effects we have investigated the stability of the silicon surface passivation obtained by the double layer under ultraviolet light exposure. In particular we have verified that this double layer is effective to passivate both p- and n-type crystalline silicon surface by measuring minority carrier high lifetime, via photoconductance-decay. To get better inside the passivation mechanisms, strongly connected to the charge laying inside the SiN_x layer, we have collected the Infrared spectra of the SiN_x/a-Si:H/c-Si structures and we have monitored the capacitance-voltage profiles of Al/SiN_x/a-Si:H/c-Si Metal Insulator Semiconductor structures at different stages of UltraViolet (UV) light exposure. Finally we have verified the stability of the double passivation layer applied to the front side of solar cell devices by measuring their photovoltaic parameters during the UV light exposure.     

Gradient etching of silicon-based thin films for depth-resolved measurements: The example of Raman crystallinity

An etching procedure was applied to microcrystalline silicon (μc-Si:H) thin films in order to obtain a wedge-shaped profile for depth-resolved characterization. A microfluidic flow cell that merges deionized water with a potassium hydroxide solution (KOH_aq) was utilized. The samples consisted of texture-etched ZnO:Al on a Corning Glass substrate, a microcrystalline p-doped layer serving as seed layer and the investigated intrinsic microcrystalline or amorphous silicon (a-Si:H). Along the etched profiles, microscopic Raman spectroscopy was used to estimate the crystalline volume fraction X_c for samples deposited with intentionally varied silane concentration to investigate the a-Si:H/μc-Si:H and μc-Si:H/a-Si:H transition.     

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%.     

Improvement of the short-circuit current density and efficiency in micromorph tandem solar cells by an anti-reflection layer

An anti-reflection layer has been fabricated and applied in micromorph tandem (a-Si:H/μc-Si:H) solar cells. In this work, the porous anti-reflection layers are produced on glass substrates by plasma enhanced chemical vapor deposition using a CF₄ and O₂ gas mixture. The process is simple and easily controlled. The tandem solar cells with the anti-reflection layer show the increased short-circuit current density of the solar cells due to increased light transmittance from air/glass interface. With the anti-reflection layer, the short-circuit current density of the tandem cell increases by 0.29 mA/cm². Meanwhile, the solar cell efficiency increases from 11.15% to 11.55% (3.5% in relative) which allows us to develop more efficient a-Si based solar cells.     

Nanocrystalline silicon thin films on PEN substrates

We study the structural and electrical properties of intrinsic layer growth close to the transition between amorphous silicon (a-Si:H) and nanocrystalline silicon (nc-Si:H), deposited on glass and PEN without intentional heating. These samples showed different behaviour in Raman shift and XRD spectra when compared with that of samples deposited at 200 °C. Electrical properties of these films also reflect the transition between a-Si:H and nc-Si:H, and put in evidence some differences between the microstructure of the films grown on PEN and on glass.P- and n-doped layers were deposited onto glass substrate without intentional heating and at 100 °C with thicknesses ranging from 1000 nm to 35 nm. Conductivity measurements indicate the capability of doping this material, but, for very thin layers, substrate heating was found to be essential.     

Defect analysis of thin film Si-based alloys deposited by hot-wire CVD using junction capacitance methods

We evaluate and compare the electronic properties of hot-wire CVD deposited a-Si:H and a-Si,Ge:H films with those produced by the glow discharge (PECVD) method. A good indicator of film quality with respect to solar cell applications is the narrowness of the band tail widths determined by transient photocapacitance (TPC) spectroscopy. We focus on the excellent electronic properties of hot-wire CVD a-Si,Ge:H alloys that have recently been produced by a 1800  °C filament temperature process. These alloy samples were compared to a-Si,Ge:H films of the same optical gaps deposited by PECVD. Light-induced degradation was examined in a few samples and compared to the behavior PECVD a-Si,Ge:H alloys of similar optical gap. The effects of intentional oxygen contamination were also studied on a series of HWCVD a-Si,Ge:H samples containing 29at.% Ge.     

Ultrafast deposition of silicon nitride and semiconductor silicon thin films by hot wire chemical vapor deposition

The technology of Hot Wire Chemical Vapor Deposition (HWCVD) or Catalytic Chemical Vapor Deposition (Cat-CVD) has made great progress during the last couple of years. This review discusses examples of significant progress. Specifically, silicon nitride deposition by HWCVD (HW-SiN_x) is highlighted, as well as thin film silicon single junction and multijunction junction solar cells. The application of HW-SiN_x at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency and preliminary tests of our transparent and dense material obtained at record high deposition rates of 7.3 nm/s yielded 14.9% efficiency. We also present recent progress on Hot-Wire deposited thin film solar cells. The cell efficiency reached for (nanocrystalline) nc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.6%. Such cells, used in triple junction cells together with Hot-Wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.9% efficiency. Further, in our research on utilizing the HWCVD technology for roll-to-roll production of flexible thin film solar cells we recently achieved experimental laboratory scale tandem modules with HWCVD active layers with initial efficiencies of 7.4% at an aperture area of 25 cm².