Realization of conformal doping on multicrystalline silicon solar cells and black silicon solar cells by plasma immersion ion implantation

Emitted multi-crystalline silicon and black silicon solar cells are conformal doped by ion implantation using the plasma immersion ion implantation （PⅢ） technique. The non-uniformity of emitter doping is lower than 5 %. The secondary ion mass spectrometer profile indicates that the PⅢ technique obtained 100-rim shallow emitter and the emitter depth could be impelled by furnace annealing to 220 nm and 330 nm at 850 ℃ with one and two hours, respectively. Furnace annealing at 850 ℃ could effectively electrically activate the dopants in the silicon. The efficiency of the black silicon solar cell is 14.84% higher than that of the mc-silicon solar cell due to more incident light being absorbed.     

Crystalline silicon solar cells with high resistivity emitter

The paper presents a part of research targeted at the modification of crystalline silicon solar cell production using screen-printing technology. The proposed process is based on diffusion from POCl₃ resulting in emitter with a sheet resistance on the level of 70 Ω/□ and then, shaped by high temperature passivation treatment. The study was focused on a shallow emitter of high resistivity and on its influence on output electrical parameters of a solar cell. Secondary ion mass spectrometry (SIMS) has been employed for appropriate distinguishing the total donor doped profile. The solar cell parameters were characterized by current-voltage characteristics and spectral response (SR) methods. Some aspects playing a role in suitable manufacturing process were discussed. The situation in a photovoltaic industry with emphasis on silicon supply and current prices of solar cells, modules and photovoltaic (PV) systems are described. The economic and quantitative estimation of the PV world market is shortly discussed.     

Study of detached back reflector designs for thin‐film silicon solar cells

We present a precise and flexible method to investigate the impact of diverse detached reflector designs on the optical response of p–i–n thin‐film silicon solar cells. In this study, the term detached reflectors refers to back reflectors that are separated from the silicon layers by an intermediate rear dielectric of several micrometers. Based on the utilization of a highly conductive n‐doped layer and a local electrical contact scheme, the method allows the use of non‐conductive rear dielectrics such as air or transparent liquids. With this approach, diverse combinations of back reflector and rear dielectric can be placed behind the same solar cell, providing a direct evaluation of their impact on the device performance. We demonstrate the positive effect of a rear dielectric of low refractive index on the light trapping and compare the performance of solar cells with an air/Ag and a standard ZnO/Ag back reflector design. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of annealing ambient on carrier recombination in boron implanted silicon

The selection of either an oxidising or inert ambient during high temperature annealing is shown to affect dopant activation and electron–hole recombination in boron implanted silicon samples. Samples implanted with B at fluence between 3 × 10¹⁴ cm^–2 to 3 × 10¹⁵ cm^–2 are shown to have lower dopant activation after oxidation at 1000 °C compared to an equivalent anneal in an inert ambient. In addition, emitter recombination is shown to be up to 15 times higher after oxidation compared with an inert anneal for samples with equivalent passivation from deposited Al₂O₃ films. The observed increase in recombination for oxidised samples is attributed to the enhanced formation of boron‐interstitial defect clusters and dislocation loops under oxidising conditions. It is also shown that an inert anneal for 10 minutes at 1000 °C prior to oxidation has no significant impact on sheet resistance or recombination compared with a standard oxidation process.

     

Influence of annealing on the concentration profiles of boron implantations in silicon

The influence of annealing on the concentration profiles of boron implanted into silicon with does of 10¹⁴ ions/cm² up to 10¹⁶ ions/cm² and an energy of 70 keV was studied. The concentration profiles were measured with Secondary Ion Mass Spectrometry (SIMS). The broadening of the concentration profiles during annealing can be described as a superposition of effects resulting from a relatively immobile and a mobile boron fraction. The properties of the immobile boron fraction were studied by measuring the influence of a boron implantation on the distribution of a homogeneous boron background dope. From these experiments it was concluded that the immobile boron fraction consists of boron precipitates. The properties of the mobile fraction were studied from concentration profiles that were obtained after annealing during different periods at the same temperature. It was found that during the initial stage of the annealing process a fast broadening of the profile occurs; this was assumed to be due to an interstitial type boron diffusion. After prolonged annealing the much slower substitutional type diffusion prevails, due to trapping of the interstitial boron atoms by vacancies. The reliability of the SIMS method, as applied to profile measurements, was checked for the high boron doses used in this investigation. Excessive boron precipitates, obtained after annealing of a high dose, such as 10¹⁶ ions/cm² at about 1000°C, appear to give some increase of the ion yield.     

Low‐temperature atomic layer deposition of MoOx for silicon heterojunction solar cells

The preparation of high‐quality molybdenum oxide (MoO_x) is demonstrated by plasma‐enhanced atomic layer deposition (ALD) at substrate temperatures down to 50 °C. The films are amorphous, slightly substoichiometric with respect to MoO₃, and free of other elements apart from hydrogen (&11 at%). The films have a high transparency in the visible region and their compatibility with a‐Si:H passivation schemes is demonstrated. It is discussed that these aspects, in conjunction with the low processing temperature and the ability to deposit very thin conformal films, make this ALD process promising for the future application of MoO_x in hole‐selective contacts for silicon heterojunction solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Laser illumination for manipulation of hydrogen charge states in silicon solar cells

This Letter investigates the important parameters of illumination for control of hydrogen charge states in p‐type silicon solar cells. Through variations in the wavelength and intensity of illumination, evidence is provided for the importance of the neutral charge state of interstitial hydrogen, H⁰, for the passivation of defects in upgraded metallurgical grade (UMG) silicon. It is shown that through this approach minority carrier lifetimes may be achieved in excess of those realised through previous techniques, resulting in open‐circuit voltages (iV_OC) over 710 mV. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Ion implantation into amorphous Si layers to form carrier‐selective contacts for Si solar cells

This paper reports our findings on the boron and phosphorus doping of very thin amorphous silicon layers by low energy ion implantation. These doped layers are implemented into a so‐called tunnel oxide passivated contact structure for Si solar cells. They act as carrier‐selective contacts and, thereby, lead to a significant reduction of the cell's recombination current. In this paper we address the influence of ion energy and ion dose in conjunction with the obligatory high‐temperature anneal needed for the realization of the passivation quality of the carrier‐selective contacts. The good results on the phosphorus‐doped (implied V_oc = 725 mV) and boron‐doped passivated contacts (iV_oc = 694 mV) open a promising route to a simplified interdigitated back contact (IBC) solar cell featuring passivated contacts. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Thermal annealing induced photocarrier radiometry enhancement for ion implanted silicon wafers

An experimental study on the photocarrier radiometry signals of As⁺ ion implanted silicon wafers before and after rapid thermal annealing is performed. The dependences of photocarrier radiometry amplitude on ion implantation dose (1×10¹¹--1×10¹⁶/cm²), implantation energy (20--140 keV) and subsequent isochronical annealing temperature (500--1100 du are investigated. The results show that photocarrier radiometry signals are greatly enhanced for implanted samples annealed at high temperature, especially for those with a high implantation dose. The reduced surface recombination rate resulting from a high built-in electric field generated by annealing-activated impurities in the pn junction is believed to be responsible for the photocarrier radiometry signal enhancement. Photocarrier radiometry is contactless and can therefore be used as an effective in-line tool for the thermal annealing process monitoring of the ion-implanted wafers in semiconductor industries.     

21.0%‐efficient co‐diffused screen printed n‐type silicon solar cell with rear‐side boron emitter

Plasma enhanced chemical vapor deposition (PECVD) is applied to deposit boron silicate glasses (BSG) acting as boron diffusion source during the fabrication of n‐type silicon solar cells. We characterize the resulting boron‐diffused emitter after boron drive‐in from PECVD BSG by measuring the sheet resistances R_sheet,B and saturation current densities J_0,B. For process optimization, we vary the PECVD deposition parameters such as the gas flows of the precursor gases silane and diborane and the PECVD BSG layer thickness. We find an optimum gas flow ratio of SiH₄/B₂H₆= 8% and layer thickness of 40 nm. After boron drive in from these PECVD BSG diffusion sources, a low J_0,B values of 21 fA/cm² is reached for R_sheet,B = 70 Ω/□. The optimized PECVD BSG layers together with a co‐diffusion process are implemented into the fabrication process of passivated emitter and rear totally diffused (PERT) back junction (BJ) cells on n‐type silicon. An independently confirmed energy conversion efficiency of 21.0% is achieved on 15.6 × 15.6 cm² cell area with a simplified process flow. This is the highest efficiency reported for a co‐diffused n‐type PERT BJ cell using PECVD BSG as diffusion source. A loss analysis shows a small contribution of 0.13 mW/cm² of the boron diffusion to the recombination loss proving the high quality of this diffusion source. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

19.4%‐efficient large‐area fully screen‐printed silicon solar cells

We demonstrate industrially feasible large‐area solar cells with passivated homogeneous emitter and rear achieving energy conversion efficiencies of up to 19.4% on 125 × 125 mm² p‐type 2–3 Ω cm boron‐doped Czochralski silicon wafers. Front and rear metal contacts are fabricated by screen‐printing of silver and aluminum paste and firing in a conventional belt furnace. We implement two different dielectric rear surface passivation stacks: (i) a thermally grown silicon dioxide/silicon nitride stack and (ii) an atomic‐layer‐deposited aluminum oxide/silicon nitride stack. The dielectrics at the rear result in a decreased surface recombination velocity of S_rear = 70 cm/s and 80 cm/s, and an increased internal IR reflectance of up to 91% corresponding to an improved J_sc of up to 38.9 mA/cm² and V_oc of up to 664 mV. We observe an increase in cell efficiency of 0.8% absolute for the cells compared to 18.6% efficient reference solar cells featuring a full‐area aluminum back surface field. To our knowledge, the energy conversion efficiency of 19.4% is the best value reported so far for large area screen‐printed solar cells. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optimized emitter contacting on multicrystalline silicon thin film solar cells

We present an optimized contacting scheme for multicrystalline silicon thin film solar cells on glass based on epitaxially crystallized emitters with a thin Al₂O₃ layer and a silver back reflector. In a first step a 6.5 µm thick amorphous silicon absorber layer is crystallized by a diode laser. In a second step a thin silicon emitter layer is epitaxially crystallized by an excimer laser. The emitter is covered by an Al₂O₃ layer with a thickness ranging from 1.0 nm to 2.5 nm, which passivates the surface and acts as a tunnel barrier. On top of the Al₂O₃ layer a 90–100 nm thick silver back reflector is deposited. The Al₂O₃ layer was found to have an optimal thickness of 1.5 nm resulting in solar cells with back reflector that achieve a maximum open‐circuit voltage of 567 mV, a short‐circuit current density of 27.9 mA/cm², and an efficiency of 10.9%. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Dopant‐free back contact silicon heterojunction solar cells employing transition metal oxide emitters

The present study investigates the electrical properties of transition metal oxide (TMO) emitters in dopant‐free n‐Si back contact solar cells by comparing the properties of solar cells employing three TMOs (WO_x, MoO_x and V₂O_x) with varying electrical properties acting as p‐type contacts. The TMOs are found to induce large band bending in n‐Si, which reduces the injection level dependent interfacial recombination speed S_eff and contact resistivity ρ_c. Among the TMO/n‐Si contacts considered, the V₂O_x/n‐Si contact achieves the lowest S_eff of 138 cm/s and ρ_c of 0.034 Ω cm², providing the significant advantages over heavily doped a‐Si:H(p)/n‐Si contacts. The best device performance was achieved by the V₂O_x/n‐Si solar cell, demonstrating an efficiency of 16.59% and an open‐circuit voltage of 610 mV relative to solar cells based on MoO_x/n‐Si (15.09%, 594 mV) and WO_x/n‐Si (12.44%, 539 mV). Furthermore, the present work is the first to employ WO_x, V₂O_x and Cs₂CO₃ in back contact solar cells. The fabrication process employed offers great potential for the mass production of back contact solar cells owing to simple, metal mask patterning with high alignment quality and dopant‐free steps conducted at a lower temperature.     

Modeling the formation of local highly aluminum‐doped silicon regions by rapid thermal annealing of screen‐printed aluminum

The formation of local highly aluminum‐doped (Al‐p⁺) regions by rapid thermal annealing (firing) of screen‐printed aluminum strongly depends on the temperature profile and the contact geometry. We measure the local Al‐p⁺ layer thickness W_Al‐p+ as a function of the point and line contact size. Using quantitative yet simple analytical modeling, the time‐dependent silicon concentration in the Al melt is described by elementary differential equations. From this we calculate W_Al‐p+ and find agreement with the measurements. In contrast to the formation of full area Al‐p⁺ layers we find a smaller silicon concentration at the end of the firing process compared to the equilibrium concentration. This is a result of the process dynamics such as the dissolution rate of solid silicon and the transport of silicon in the Al melt. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect‐band photoluminescence imaging on multi‐crystalline silicon wafers

Defect‐band emission photoluminescence (PL) imaging with an indium‐gallium‐arsenide (InGaAs) camera was applied to multi‐crystalline silicon (mc‐Si) wafers, which were taken from different heights of different Si bricks. Neighboring wafers were picked at six different processing steps, from as‐cut to post‐metallization. By using different cut‐off filters, we were able to separate the band‐to‐band emission images from the defect‐band emission images. On the defect‐band emission images, the bright regions that originate from extend‐ ed defects were extracted from the PL images. The area fraction percentage of these regions at various processing stages shows a correlation with the final cell electrical parameters. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Contacting boron emitters on n‐type silicon solar cells with aluminium‐free silver screen‐printing pastes

In the production of n‐type Si solar cells, B diffusion is commonly applied to form the p⁺ emitter. Up to now, Ag screen‐printing pastes, generally used to contact P emitters, had been incapable of reliably contact B emitters. Therefore, a small amount of Al is generally added to Ag pastes to allow for reasonable contact resistances. The addition of Al, however, results in deep metal spikes growing into the Si surface that can penetrate the emitter. Losses in open‐circuit voltage are attributed to these deep metal spikes. In this investigation we demonstrate, that state‐of‐the‐art Al‐free Ag screen‐printing pastes are capable to contact BBr₃‐based B emitters covered with different dielectric layers and reach specific contact resistances <1 mΩ cm². Bifacial n‐type solar cells with Al‐free Ag pastes on both sides show efficiencies of up to 18.3% and series resistances <0.5 Ω cm². (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Micro‐photoluminescence spectroscopy on heavily‐doped layers of silicon solar cells

We report and explain the photoluminescence spectra emitted from silicon solar cells with heavily‐doped layers at the surface. A micro‐photoluminescence spectroscopy system is employed to investigate the total spectrum emitted from both the heavily‐doped layer and the silicon substrate with micron‐scale spatial resolution. The two regions of the device give rise to separate photoluminescence peaks, due to band‐gap narrowing effects in the highly‐doped layer. Two key parameters, the absorption depth of the excitation wavelength, and the sample temperature, are shown to be critical to reveal the separate signatures from the two regions. Finally, this technique is applied to locally diffused and laser‐doped regions on silicon solar cell pre‐cursors, demonstrating the potential value of this micron‐scale technique in studying and optimizing locally doped regions. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Extended defects in hydrogen-implanted (111) silicon wafer treated by high temperature annealing process

Hydrogen impurity has been an active topic of research in material science and en-gineering[1—3]. Many studies indicated that chemically active hydrogen can affect theproperties of the materials including silicon. For example, hydrogen may lead to theembrittlement of silicon crystals[4] and the passivation of the deep-level impurities[5].More interestingly, high dose of hydrogen in silicon by ion implantation can evidentlychange the material structure. {111} and {100} platelet defects were ob…