Phosphorous emitter etch back and bulk hydrogenation by means of an ECR-hydrogen plasma applied to form a selective emitter structure on mc-Si

In this paper, we study the effect of hydrogen-electron cyclotron resonance plasma (ECR plasma) on the phosphorous-doped emitter of a solar cell based on multicrystalline silicon (POLIX^®). The purpose of this experiment is to realise a selective emitter structure, using the front metal contacts as a mask. We show that hydrogen plasma etches the surface of the emitter away, and simultaneously diffuses into the silicon and increase the bulk lifetime. Both minority carrier lifetime and etch rate depend on the grain orientation. Hydrogen diffusion is hindered by the high phosphorous concentration of the emitter, as shown on the SIMS profiles. Besides, SIMS profiles are revealing an anomalous behaviour of phosphorous, which diffuses into the silicon at temperatures as low as 350°C on (1 0 0) oriented grains.     

The influence of porous silicon on junction formation in silicon solar cells

In this work the results of a structural investigation by SEM of porous silicon (PS) before and after diffusion processes are reported. The formation of PS n⁺/p structures were carried out on PS p/p silicon wafers with two methods: from POCl₃ in a conventional furnace and from a phosphorous doped paste in an infrared furnace. Sheet resistance was found to be a strong function of PS structure. Further details on sheet resistance distribution are reported. The electrical contacts in prepared solar cells were obtained by screen printing process, with a Du Ponte photovoltaic silver paste for front contacts and home-prepared silver with 3% aluminium paste for the back ones. Metallization was done in the infrared furnace. Solar cell current–voltage characteristics were measured under an AM 1.5 global spectrum sun simulator. The average results for multi-crystalline silicon solar cells without antireflection coating are: I_sc=720 (mA), V_oc=560 (mV), FF=69%, Eff=10.6% (area 25 cm²).     

Simple analytical solution and efficiency improvement of polysilicon emitter solar cells

A simple analytical model has been developed to simulate the performance of solar cells with polysilicon contact on the front surface. The polysilicon layer with a columnar grain structure is modeled by an effective recombination velocity using a two-dimensional transport equation. A one-dimensional transport equation in the single-crystal emitter is solved, taking into account bulk recombination and non-uniformly doped emitter. Then, simple analytical expressions for the emitter reverse saturation current and light-generated current densities are obtained. The collection of the light-generated carriers in polysilicon layer has been discussed and an analytical solution of the light-generated current is derived. The results show that the polysilicon layer can result in a decrease in emitter reverse saturation current density and an increase in solar cell photovoltaic parameters. In fact, the emitter region should not be treated as a ‘dead layer’ because thin polysilicon layer front surface contact gives an improvement of about 60 mV for the open-circuit voltage, 3.6 mA/cm² for the photocurrent, and 3.9% for the cell efficiency.     

A simple fabrication process for 20% efficient silicon solar cells

Recently, a substantially simplified PERC silicon solar cell has been developed at ISFH with independently confirmed 1-sun efficiencies of up to 20.0%. This paper describes the details of the relatively simple cell fabrication process and experimentally characterizes the new cells. The simplified design involves reflection control by means of random pyramids, the direct evaporation of the front metal grid onto the random pyramids, elimination of the need for nontextured areas underneath the contact grid, and the use of a single phosphorous diffusion (1-step emitter).     

Self-aligned locally diffused emitter (SALDE) silicon solar cell

This paper presents, for the first time, a low-cost, high-throughput manufacturing approach for fabricating n-base dendritic web silicon solar cells with selectively doped emitters and self-aligned aluminum contacts using rapid thermal processing (RTP) and screen printing. The self-aligned locally diffused emitter (SALDE) structure is p⁺ nn⁺⁺ where aluminum is screen-printed on a boron-doped emitter and fired in a belt furnace to form a deep self-doped p⁺-layer and a self-aligned positive contact to the emitter according to the well-known aluminum-silicon (Al---Si) alloying process. The SALDE structure preserves the shallow emitter (20.2 μm) everywhere except directly beneath the emitter contact. There the junction depth is greater than 5 μm, as desired, in order to shield carriers in the bulk silicon from that part of the silicon surface covered by metal where the recombination rate is high. This structure is realized by using n-base (rather than p-base) substrates and by utilizing screen-printed aluminum (rather than silver) emitter contacts. Prototype dendritic web silicon (web) cells (25 cm² area) with efficiencies up to 13.2% have been produced.     

Local aluminum-silicon contacts by layer selective laser ablation

We demonstrate damage free selective laser ablation of silicon nitride from a silicon nitride/amorphous silicon double layer. This approach allows local contact formation to passivated silicon. Thereby the remaining amorphous silicon dissolves in evaporated aluminum by annealing. This technique is especially useful for contacting thin emitters since it avoids any damage to the silicon substrate. We demonstrate a local contact resistivity of 0.8±0.3 mΩ cm² on a phosphorous diffused emitter with a peak doping density of 2×10²⁰ cm⁻³. Laser treated as well as non-treated areas show the same carrier lifetime of 2000 μs on 100 Ω cm mono-crystalline silicon, proving the selective ablation.     

Phosphorus-diffused silicon solar cell emitters with plasma enhanced chemical vapor deposited silicon carbide

We propose the use of annealed phosphorus doped amorphous silicon carbide layers (a-SiC:H(n)) deposited by PECVD as emitters in solar cells and explore the effect of the annealing time on the emitter saturation current density (J_oe). We use the quasy-steady state photoconductance method to determine the dependence of effective lifetime on excess carrier density and from these measurements we obtain J_oe values in the range of 300 fA cm⁻² for sheet resistances around 100 Ωsq. Finally, we obtain effective surface recombination velocity values around 10⁴ cm s⁻¹ by fitting the measured J_oe values with PC1D simulated ones.     

Analysis of free-carrier optical absorption used for characterization of microcrystalline silicon films

The analysis of free-carrier optical absorption was applied to investigation of electrical properties for doped microcrystalline silicon films formed at 100–180°C by the RF-plasma-enhanced chemical vapor deposition method. The analysis gave in-depth characteristics of the carrier mobility and the carrier density. The electron mobility was 8 cm²/Vs (phosphorous doped) and 6 cm²/Vs (boron doped) at the surface region and it decreased to 1 cm²/Vs at bottom film/substrate interfaces. The carrier mobility and density were much higher than those obtained by Hall effect current measurements. It shows the existence of substantial non-activated and disordered regions among crystalline grains.     

Development of an emitter for industrial silicon solar cells using the doped oxide solid source diffusion technique

The aim of this paper is to demonstrate for the first time the feasibility of fabricating large-area screen-printed monocrystalline silicon solar cells using the Doped Oxide Solid Source (DOSS) diffusion technique. This process was applied to form the n⁺p emitter junction from highly doped sources prepared in a POCl₃ ambient. The diffusions were performed under a pure nitrogen flow in the temperature range 900–1050°C. In this investigation attention was devoted to the influence of the source doping level on the fill factor. The solar cells were fabricated on industrial quality 4-inch Cz wafers using a simple processing sequence incorporating screen-printed contacts and a TiO₂ antireflection coating deposited by spin-on. Fill factors as high as 79% were obtained. The potential benefit of retaining for passivation purposes the thin residual oxide grown during phosphorus diffusion was evaluated. These first experiments led to a cell efficiency close to 10%.     

Sheet resistance uniformity in drive-in step for different multi-crystalline silicon wafer dispositions

In this work, we present a study of emitters realized using different configurations of the silicon wafers in the quartz boat. The phosphorous liquid source is sprayed onto p-type multi-crystalline silicon substrates and the drive-in is made at high temperature in a muffle furnace. Three different configurations of the wafers in the boat are tested: separated, back to back and compact block of wafers. A fourth configuration is also used in source-receptor mode. The emitter phosphorous concentration profile is obtained by SIMS analysis. The resulting emitters are characterized by sheet resistance measurements and a comparison is made between the wafers within the same batch and from one batch to another. The uniformity and the standard deviation of the sheet resistance are calculated in each case. The emitter sheet resistance mapping of the wafer set in the middle of the boat for a given process gives a mean R_sq 14.66 Ω/sq with a standard deviation of 1.76% and uniformity of 18.7%. Standard deviations of 2.116% and 1.559% are obtained for wafers in the batch when using the spaced and compact configurations, respectively. The standard deviation is reduced to 0.68% when the wafers are used in source/receptor mode. A comparison is also made between wafers with different dilution of phosphorous source in ethanol.From these results we can conclude that the compact configuration offers better uniformity and lower standard deviation. Furthermore, when combined with the source-receptor configuration these parameters are significantly improved.This study allows the experimenter to identify the technological parameters of the solar cell emitter manufacturing and target precisely the desired values of the sheet resistance while limiting the number of rejected wafers.     

Progress in emitter wrap-through solar cell fabrication on boron doped Czochralski-grown silicon

We report on RISE-EWT (Rear Interdigitated Single Evaporation-Emitter Wrap-Through) solar cells on full area (12.5×12.5 cm²) pseudo square boron doped Czochralski-grown silicon wafers. We investigate the main efficiency optimisation factors of these cells by investigating the dependence of RISE-EWT cell parameters on the base dopant concentration N_A. We furthermore detail the effects of large feature sizes in base and emitter regions at the rear of the solar cell and investigate these effects with particular attention to the edge regions. EWT solar cells typically exhibit rather low fill factors. However, our results show that the improved fill factors can be achieved by increasing N_A, which in return leads to optimised efficiency values. For our RISE-EWT solar cells made from boron doped Cz-Si wafers, this benefit is maintained even after light-induced degradation. Our investigation of edge area related effects shows the importance of proper cell design in these areas, leading to a further 2.8% absolute improvement in the fill factor. Combining increased base dopant concentration with optimised edge design, we achieve 19.0% efficiency on (12.5×12.5 cm²) boron doped Cz silicon wafers before light-induced degradation, resulting in 18.1% efficiency in the light-degraded state.     

The electrical properties and hydrogen passivation effect in mono crystalline silicon solar cell with various pre-deposition times in doping process

The doping process in diffusion furnace consisting of pre-deposition and drive-in steps is essential to create p–n junction in crystalline silicon solar cell fabrication, and its optimization is necessary to obtain the high conversion efficiency. In this work, pre-deposition time was varied to study the electrical properties of solar cells and its effect on the hydrogen passivation with various phosphorous doping profiles. As a result, solar cell conversion efficiency of 17.8% with 7 min pre-deposition was achieved. Dopant (phosphorous) concentration in the emitter measured by SIMS indicated that the surface with shorter pre-deposition time had lower dopant concentration. High concentration of phosphorous on the surface appears to be the source for the electron consumed by the stored hydrogen in making the neutral H₂ gas during firing. The formation of neutral hydrogen gas is thermodynamically and stochastically more favorable than the reaction between Si with dangling bond and H. This means that the passivation by the stored H during firing is strongly controlled by the dopant on the surface. This result obtained herein lays the foundations to understand the relationship between the doping profile of diverse dopant species and its passivation effect.     

Determination of front surface recombination velocity of silicon solar cells using the short-wavelength spectral response

A method of determination of recombination velocity S_f of minority carriers at the front surface of an n⁺–p–p⁺(p⁺–n–n⁺) silicon solar cell in which the n⁺(p⁺) front emitter is made by diffusion of dopant impurity in the p(n) region is presented. This method uses the short-wavelength spectral response of the cell to determine S_f and is applicable if the front emitter of the cell has a linearly varying built-in field. It was applied to a p⁺–n–n⁺ solar cell that had a Gaussian distribution of the dopant impurity in the p⁺ front emitter up to a depth of 0.078 μm from the surface. Using the spectral response data of cell in 380 nm<λ< 500 nm range S_f was found to have a nearly constant value 6×10⁵ cm s⁻¹ in 400 nm<λ<460 nm range. Below and above this wavelength range the value of S_f was found to be slightly smaller. For comparison the value of S_f was also determined assuming the p⁺ region to be uniformly doped, and this value was found to be significantly smaller than based on the diffused emitter model. The analysis showed that for a diffused junction cell, the assumption that the front emitter is uniformly doped, ignores the presence of the built-in field in the emitter region and leads to overestimation of minority carrier recombination in the emitter. Consequently for a given contribution of the front emitter region to the spectral response of the cell, this assumption underestimates the front surface recombination and determines a smaller value of S_f. On the other hand, the present method can be expected to determine a realistic value of S_f independent of λ for most diffused junction silicon solar cells using the spectral response data in a suitable short-wavelength range since each such cell indeed has a built-in electric field in the emitter region.     

Effect of the front surface field on crystalline silicon solar cell efficiency

The present paper reports on a simulation study carried out to determine and optimize the effect of the high–low junction emitter (n⁺-n) on thin silicon solar cell performance. The optimum conditions for the thickness and doping level of the front surface layer with a Gaussian profile were optimized using analytical solutions for a one dimensional model that takes on the theory relevant for highly doped regions into account. The photovoltaic parameters of silicon solar cells with front surface field layer (n⁺-n-p structure) and those of the conventional one (n-p structure) are compared. The results indicate that the most important role played by the front surface field layer is to enhance the collection of light-generated free carriers, which improves the efficiency of the short wavelength quantum. This is achieved by a drastic reduction in the effective recombination at the emitter upper boundary, a property primarily responsible for the decrease in the emitter dark current density. The findings also indicate that the solar cell maximum efficiency increase by about 2.38% when the surface doping level of the n⁺-region and its thickness are equal to 2.10²⁰ cm^?3 and 0.07 μm, respectively.     

Effect of hydrogen dilution on intrinsic a-Si:H layer between emitter and Si wafer in silicon heterojunction solar cell

In silicon heterojunction solar cells, a thin intrinsic amorphous-silicon (a-Si:H) buffer layer between a doped emitter and a c-Si wafer is essential to minimize carrier recombination. This study examines the effect of H₂ dilution on the properties of the intrinsic a-Si:H layers deposited on Si wafers by plasma-enhanced chemical vapor deposition. A H₂/SiH₄ ratio of 24 led to improvements in the quality of intrinsic a-Si:H films and in the performance of passivation compared to a-Si:H film without H₂ dilution. A high H₂-dilution ratio, however, degraded the passivation of the a-Si:H film. The Si heterojunction solar cells with an optimal intrinsic a-Si:H layer showed an efficiency of 12.3%.     

Electrocatalytic oxidation of hydrogen peroxide on the surface of nano zeolite modified carbon paste electrode

This study investigated the use of synthesized nanozeolite Y to prepare modified carbon paste electrode for electrocatalytic oxidation of hydrogen peroxide. In order to prepare the modified electrodes, the nickel ions were doped to Y zeolite framework through ion exchange mechanism and the electrochemical behaviour of the proposed modified electrode was studied using the cyclic voltammetry technique. The obtained results revealed that modified carbon paste electrode in the form of Ni/NiYCPE is the best electrode for the oxidation of hydrogen peroxide in the alkaline media. The hydrogen peroxide transfer coefficient (α) and the current density were calculated as 0.54 and 6.7 mA/cm², respectively. The catalytic rate constant (K) for this electrocatalytic reaction was calculated through the chronoamperometric technique (K = 0.43 × 10⁴ cm²s^?1mol^?1).     

Characterization of the PSG/Si interface of H3PO4 doping process for solar cells

The precipitation of P in the emitter region of H₃PO₄ spray doped silicon for solar cell applications has been investigated by electron microscopy, X-ray microanalysis and electrical measurements after annealing for two different times. P, Si and O concentration profiles show that the composition of the phosphorous silicate glass (PSG) is in agreement with a solid solution of P₂O₅ in SiO₂ and that P concentration is peaked at the PSG/Si interface. TEM observations have shown for the shorter annealing the formation of a 20 nm thick defect layer at the silicon surface; this layer evolves into a network of large rod-like monoclinic (or orthorhombic) SiP precipitates, which extend in depth up to about 100 nm for the longer treatment. The SiP crystal structure and the habit planes are the same as previously reported in literature. No deeper defect that could interact with the junction located at about 300 nm has been detected. Although the SiP precipitation takes place entirely at the Si surface, it is not significantly affected by the orientation of the crystals and by the texturing process. The amounts of both electrically active and inactive P obtained by the H₃PO₄ spray technique have been compared with the ones obtained by the conventional POCl₃ technique. The former process presents a larger amount of inactive dopant, a finding that is in keeping with the microstructural and microanalytical observations. Instead the amount of active P is similar in the two cases, a result attributed to the precipitation and clustering phenomena of the excess dopant.     

Optimization of lead- and cadmium-free front contact silver paste formulation to achieve high fill factors for industrial screen-printed Si solar cells

Screen-printed n⁺–p–p⁺ solar cells were fabricated on Cz single crystalline Si material, with a 45 Ω/sq emitter and PECVD SiNx antireflective coating with a thickness of 700 Å, using different Ag pastes and commercial leaded reference paste (CN33-462, Ferro Corp.). Ag and Al contacts were co-fired using a mass-production line equipped with mesh belt conveyer furnace systems (Centrotherm thermal solution GmbH & Co. KG). The average results for single crystalline Si solar cells (156 cm²) are: I_sc=5.043 A, V_oc=0.621 V, R_s=0.0087 Ω, R_sh=15.3 Ω, FF=0.773, and E_ff=16.45%. R_sh and fill factor values of fabricated cells were slightly higher when compared with the commercial leaded Ag paste, although cells were fabricated by metallizing the lead-free silver pastes. For the lead-free Ag paste used in this study, the line pattern continuity is retained with improved edge definition in sharp contrast to that of reference Ag paste. Average value of R_s was also equivalent approximately to that of the leaded Ag paste.     

Optimization of paste formulation for TiO2 nanoparticles with wide range of size distribution for its application in dye sensitized solar cells

Dye sensitized solar cell (DSSC) can be an economically viable and technically simpler alternate to the silicon based solar cells. Films of nanocrystalline titanium dioxide (TiO₂) are considered as the most suitable photoelectrode for DSSC. For this study, TiO₂ powder of anatase phase, synthesized in acidic environment was used. The average diameter of the nanoparticles was ～20 nm and BET surface area was 64.68 m²/g. Different TiO₂ pastes were prepared by varying the proportion of TiO₂ powder, α-terpineol, and ethyl cellulose (EC) in their composition. The TiO₂ paste was cast on fluorine doped tin oxide (FTO) coated glass surface using doctor blade to prepare photoelectrode of TiO₂ film. Composition of the paste ingredients was optimized by comparing the conversion efficiencies of the DSSCs fabricated with the photoelectrode of thickness ～18 μm. The outcome of this study can be crucial for the preparation of reliable TiO₂ paste in a simple way for its application in DSSC.     

Internal quantum efficiency improvement of polysilicon solar cells with porous silicon emitter

The present study aimed to develop a simple analytical model to investigate the potential use and implications of porous silicon (PS) as an antireflective coating in thin polysilicon solar cells. It analytically solved the complete set of equations necessary to determine the contribution that this material has on the internal quantum efficiency (IQE) of the cell when acting as an antireflective coating agent. The increase in the IQE, the contribution of the different regions of the cell, and the effects of the physical parameters of each region were derived and investigated in comparison with conventional solar cells.The findings revealed that the internal quantum efficiency of the solar cell with PS emitter is higher than that of the conventional one particularly for short-wavelengths (λ < 0.6 μm). Furthermore, for photons with higher energy, the emitter contribution in the IQE is more significant than the base and depletion regions. For photons with smaller energy, on the other hand, the absorption coefficients are also smaller, which leads to a higher generation rate in the base region and, hence, to a more pronounced contribution from this region to IQE. Last but not least, the improvement of IQE is observed to increase with decreased PS thickness and with heavily doped PS emitter (N_d⁺⁺ = 10²⁰ cm⁻³).