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Nanocrystalline silicon oxide (nc-SiOx:H) is a multipurpose material with varied applications in solar cells as a transparent front contact, intermediate reflector, back reflector layer, and even tunnel layer for passivating contacts, owing to the easy tailoring of its optical properties. In this work, we systematically investigate the influence of the gas mixture (SiH4, CO2, PH3, and H2), RF power, and process pressure on the optical, structural, and passivation properties of thin n-type nc-SiOx:H films prepared in an industrial, high-throughput, plasma-enhanced chemical vapor deposition (PECVD) reactor. We provide a detailed description of the n-type nc-SiOx:H material development using various structural and optical characterization techniques (scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Raman spectroscopy, and spectroscopic ellipsometry) with a focus on the relationship between the material properties and the passivation they provide to n-type c-Si wafers characterized by their effective carrier lifetime (τeff). Furthermore, we also outline the parameters to be kept in mind while developing different n-type nc-SiOx:H layers for different solar cell applications. We report a tunable optical gap (1.8–2.3 eV) for our n-type nc-SiOx:H films as well as excellent passivation properties with a τeff of up to 4.1 ms (implied open-circuit voltage (iVoc)~715 mV) before annealing. Oxygen content plays an important role in determining the crystallinity and hence passivation quality of the deposited nanocrystalline silicon oxide films.

Boron doping level and boron activation in silicon thin films grown by PECVD under epitaxial (p+ epi‑Si) and microcrystalline (p+ µc-Si) conditions have been investigated as functions of the substrate material and annealing in the range of 200°C – 300°C. Hall effect measurements show that in the as-deposited state, the conductivity is mainly governed by the carrier concentration, while the hole mobility is controlled by the crystalline quality. SIMS measurements reveal that dark conductivity is not directly proportional to the boron doping level, nor to the presence of B-H complexes, suggesting that carbon contamination and the formation of B-O complexes could play an important role in the electrical properties of the material. Annealing in air resulted in an increase in the dark conductivity for all samples. However, the increase was much higher (up to two orders of magnitude) for the samples deposited on silicon-on-insulator (SOI) substrates which have better crystalline quality and displayed the highest increase in hole carrier concentration, related to boron activation. Thus, the substrate material influences both the crystalline quality and the boron incorporation in the p-type material. At high boron incorporation, the mobility limitations are likely to be due to carrier concentration rather than to the crystalline quality, indicating that p+ µc-Si conditions allow a conductivity advantage over p+ epi‑Si conditions due to a higher doping level, which makes them suitable as hole-selective contacts in solar cells.

We report silicon nanowire (SiNW) growth with a novel Cu-In bimetallic catalyst using a plasma-enhanced chemical vapor deposition (PECVD) method. We study the structure of the catalyst nanoparticles (NPs) throughout a two-step process that includes a hydrogen plasma pre-treatment at 200 °C and the SiNW growth itself in a hydrogen-silane plasma at 420 °C. We show that the H2-plasma induces a coalescence of the Cu-rich cores of as-deposited thermally evaporated NPs that does not occur when the same annealing is applied without plasma. The SiNW growth process at 420 °C induces a phase transformation of the catalyst cores to Cu7In3; while a hydrogen plasma treatment at 420 °C without silane can lead to the formation of the Cu11In9 phase. In situ transmission electron microscopy experiments show that the SiNWs synthesis with Cu-In bimetallic catalyst NPs follows an essentially vapor-solid–solid process. By adjusting the catalyst composition, we manage to obtain small-diameter SiNWs—below 10 nm—among which we observe the metastable hexagonal diamond phase of Si, which is predicted to have a direct bandgap.

Modulated photoluminescence (MPL) is a powerful technique for determining the effective minority carrier lifetime (τeff) of semiconductor materials and devices. MPL is based on the measurement of phase shifts between two sinusoidal waves (minimal amplitude excitation; and PL signal). In particular, in situ τeff has been proven to be an effective measurement at showing changes within a plasma-enhanced chemical vapor deposition reactor during fabrication of c-Si solar cells. However, the required time for a single measurement, using the previous method, was 40 s. In this paper a new input signal is proposed, called Dolphin's Wave, providing a method for decreasing the required measurement period to under 2 s, using superposition, frequency sweeps, and wavelets.

Abstract This work focuses on the extraction of the open circuit voltage (V OC) on photovoltaic nanowires by surface photovoltage (SPV) based on Kelvin probe force microscopy (KPFM) measurements. In a first approach, P-I-N radial junction (RJ) silicon nanowire (SiNW) devices were investigated under illumination by KPFM and current-voltage (I-V) analysis. Within 5%, the extracted SPV correlates well with the V OC. In a second approach, local SPV measurements were applied on single isolated radial junction SiNWs pointing out shadowing effects from the AFM tip that can strongly impact the SPV assessment. Several strategies in terms of AFM tip shape and illumination orientation have been put in place to minimize this effect. Local SPV measurements on isolated radial junction SiNWs increase logarithmically with the illumination power and demonstrate a linear behavior with the V OC. The results show notably that contactless measurements of the V OC become feasible at the scale of single photovoltaic SiNW devices.

We used in situ transmission electron microscopy (TEM) to observe the dynamic changes of Si nanowires under electron beam irradiation. We found evidence of structural evolutions under TEM observation due to a combination of electron beam and thermal effects. Two types of heating holders were used: a carbon membrane, and a silicon nitride membrane. Different evolution of Si nanowires on these membranes was observed. Regarding the heating of Si nanowires on a C membrane at 800 °C and above, a serious degradation dependent on the diameter of the Si nanowire was observed under the electron beam, with the formation of Si carbide. When the membrane was changed to Si nitride, a reversible sectioning and welding of the Si nanowire was observed.

Hydrogenated microcrystalline silicon (µc-Si:H) and epitaxial silicon (epi-Si) films have been produced from SiF4, H2 and Ar mixtures by plasma enhanced chemical vapor deposition (PECVD) at 200 °C. Here, both films were produced using identical deposition conditions, to determine if the conditions for producing µc-Si with the largest crystalline fraction (XC), will also result in epi-Si films that encompass the best quality and largest crystalline silicon (c-Si) fraction. Both characteristics are of importance for the development of thin film transistors (TFTs), thin film solar cells and novel 3D devices since epi-Si films can be grown or etched in a selective manner. Therefore, we have distinguished that the H2/SiF4 ratio affects the XC of µc-Si, the c-Si fraction in epi-Si films, and the structure of the epi-Si/c-Si interface. Raman and UV-Vis ellipsometry were used to evaluate the crystalline volume fraction (Xc) and composition of the deposited layers, while the structure of the films were inspected by high resolution transmission electron microscopy (HRTEM). Notably, the conditions for producing µc-Si with the largest XC are different in comparison to the fabrication conditions of epi-Si films with the best quality and largest c-Si fraction.

In this work, we report the same trends for the contact potential difference measured by Kelvin probe force microscopy and the effective carrier lifetime on crystalline silicon (c-Si) wafers passivated by AlOx layers of different thicknesses and submitted to annealing under various conditions. The changes in contact potential difference values and in the effective carrier lifetimes of the wafers are discussed in view of structural changes of the c-Si/SiO2/AlOx interface thanks to high resolution transmission electron microscopy. Indeed, we observed the presence of a crystalline silicon oxide interfacial layer in as-deposited (200 °C) AlOx, and a phase transformation from crystalline to amorphous silicon oxide when they were annealed in vacuum at 300 °C.

The ability to program periodic morphology into nanowires affords control over photonic and electronic transport properties. Here, the authors stimulate Plateau-Rayleigh transformations in silicon nanowires through an oscillating catalyst droplet, resulting in nanowires with island-chain morphology.

Epitaxial silicon layers were grown on highly doped c-Si substrates using the plasma-enhanced chemical vapour deposition process (PECVD) at low temperature (175 °C). The transport and defect-related properties of these epi-Si layers were characterized by current density-voltage (J–V) and capacitance–voltage (C–V) techniques. The results show that the epi-Si layers exhibit a non-intentional n-type doping with a low apparent doping density of about 2 × 1015 cm−3. The admittance spectroscopy technique is used to investigate the presence of deep-level defects in the structure. An energy level at 0.2 eV below the conduction band has been found with a density in the range of 1015 cm−3 which may explain the observed apparent doping profile.

Passivating contacts are becoming a mainstream option in current photovoltaic industry due to their ability to provide an outstanding surface passivation along with a good conductivity for carrier collection. However, their integration usually requires long annealing steps which are not desirable in industry. In this work we study PECVD as a way to carry out all deposition steps: silicon oxide (SiOx), doped polycrystalline silicon (poly-Si) and silicon nitride (SiNx:H), followed by a single firing step. Blistering of the poly-Si layer has been avoided by depositing (p+) microcrystalline silicon (μc-Si:H). We report on the impact of this deposition step on the SiOx layer deposited by PECVD, and on the passivation properties by comparing PECVD and wet-chemical oxide in this hole-selective passivating contact stack. We have reached iVoc > 690 mV on p-type FZ wafers for wet-chemical SiOx\(p+) μc-Si\SiNx:H with no annealing step.

We investigate low-temperature (

Amorphous silicon (a-Si:H) / micro-crystalline silicon (μc-Si:H), "micromorph" tandem solar cells have been investigated using a detailed electrical - optical model. Although such a tandem has good light absorption over the entire visible spectrum, the a-Si:H top cell suffers from strong light-induced degradation (LID). To improve matters, we have replaced a-Si:H by hydrogenated polymorphous silicon (pm-Si:H), a nano-structured silicon thin film with lower LID than a-Si:H. But the latter’s low current carrying capacity necessitates a thicker top cell for current-matching, again leading to LID problems. The solution is to introduce a suitable intermediate reflector (IR) at the junction between the sub-cells, to concentrate light of the shorter visible wavelengths into the top cell. Here we assess the suitability of N-type micro-crystalline silicon oxide (μc-SiOx:H) as an IR. The sensitivity of the solar cell performance to the complex refractive index, thickness and texture of such a reflector is studied. We conclude that N-μc-SiOx:H does concentrate light into the top sub-cell, thus reducing its required thickness for current-matching. However the IR also reflects light right out of the device; so that the initial efficiency suffers. The advantage of such an IR is ultimately seen in the stabilized state since the LID of a thin top cell is low. We also find that for high stabilized efficiencies, the IR should be flat (having no texture of its own). Our study indicates that we may expect to reach 15% stable tandem micromorph efficiency.

Controlling the doping profile in solar cells emitter and front/back surface field is mandatory to reach high efficiencies. In the current state of the art, these doped layers are made by dopant diffusion at around 900°C, which implies potential temperature induced damages in the c-Si absorber and for which a precise control of doping is difficult. An alternative solution based on boron-doped epitaxial silicon layers grown by plasma-enhanced chemical vapor deposition (PECVD) from 200°C using SiF4/H2/Ar/B2H6 chemistry is reported. The structural properties of the doped and undoped epitaxial layers were assessed by spectroscopic ellipsometry (SE), high resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD). The incorporation of boron has been studied via plasma profiling time of flight mass spectrometry (PP-TOFMS) and secondary ion mass spectrometry (SIMS) measurements. The boron-doped epitaxial layers revealed excellent structural and electrical properties even for high carrier concentrations (>1019cm-3). Sheet resistances between 100 and 130 Ω/sq can been obtained depending on the thickness and the doping concentration, which is within the range of targeted values for emitters in c-Si solar cells. Electrochemical capacitance voltage (ECV) revealed a uniform doping profile around 3.1019 cm-3 and by comparing with SIMS measurement a doping efficiency around 50% has been found.

Heterojunction solar cells based on crystalline silicon (c-Si) passivated by hydrogenated amorphous silicon (a-Si:H) thin films are one of the most promising architectures for high energy conversion efficiency. Indeed, a-Si:H thin films can passivate both p-type and n-type wafers and can be deposited at low temperature (

We study the effect of the addition of p- or n-type doping gases, trimethylboron (TMB) or phosphine, respectively, on cluster formation in the SiH4/H2 plasma used for the deposition of hydrogenated polymorphous silicon thin films. The formation of clusters is monitored using time-resolved measurements of the second harmonic of the radio frequency current J2. We show that the addition of PH3 does not change the cluster formation, while the addition of a small amount of trimethylboron strongly affects its charging behavior, preventing to some extent its agglomeration. The most ordered pm-Si:H thin films are obtained under conditions from which not only clusters but also larger silicon agglomerates are formed in the plasma and contribute to the deposition. The inhibiting role of TMB on the agglomeration and powder formation is evidenced by the smoothness of p-type films at high rates, as deduced from the sample surface topography obtained by atomic force microscopy measurements. [ABSTRACT FROM AUTHOR]

We report on unusual low temperature (175 °C) heteroepitaxial growth of germanium thin films using a standard radio-frequency plasma process. Spectroscopic ellipsometry and transmission electron microscopy (TEM) reveal a perfect crystalline quality of epitaxial germanium layers on (100) c-Ge wafers. In addition direct germanium crystal growth is achieved on (100) c-Si, despite 4.2% lattice mismatch. Defects rising from Ge/Si interface are mostly located within the first tens of nanometers, and threading dislocation density (TDD) values as low as 106 cm−2 are obtained. Misfit stress is released fast: residual strain of −0.4% is calculated from Moiré pattern analysis. Moreover we demonstrate a striking feature of low temperature plasma epitaxy, namely the fact that crystalline quality improves with thickness without epitaxy breakdown, as shown by TEM and depth profiling of surface TDD.

In heterojunction solar cells, a-Si:H/c-Si heterointerface is of significant importance, since the heterointerface characteristics directly affect junction properties and thus solar cell efficiency. In this study, we have performed time resolved microwave conductivity (TRMC) measurements on n-type c-Si wafers passivated on both sides with intrinsic and doped a-Si:H layers in order to investigate electrical property and passivation quality of the a-Si:H/c-Si heterojunctions. It was found that the TRMC decay time and decay curve shape varied with the laser wavelength and power intensity and also depended on sample structures. By using 1064 nm laser pulse with high excitation, differences in the decay curve shape between samples with and without p-n junction were observed. The samples containing p-n junction(s) had unique slow decay mode, after the initial fast decay, which we ascribed to the release of carriers from the low-mobility amorphous layer into the high-mobility crystalline wafer as the built-in field of the junction was restored. Experimental results suggest that the TRMC is useful nondestructive technique which is suitable for primary check of the a-Si:H/c-Si heterojunctions during the solar cell fabrication process.