Potential‐induced optimization of ultra‐thin rear surface passivated CIGS solar cells

Ultra‐thin Cu(In,Ga)Se₂ (CIGS) solar cells with an Al₂O₃ rear surface passivation layer between the rear contact and absorber layer frequently show a “roll‐over” effect in the J–V curve, lowering the open circuit voltage (V_OC), short circuit current (J_SC) and fill factor (FF), similar to what is observed for Na‐deficient devices. Since Al₂O₃ is a well‐known barrier for Na, this behaviour can indeed be interpreted as due to lack of Na in the CIGS absorber layer. In this work, applying an electric field between the backside of the soda lime glass (SLG) substrate and the SLG/rear‐contact interface is investi‐gated as potential treatment for such Na‐deficient rear surface passivated CIGS solar cells. First, an electrical field of +50 V is applied at 85 °C, which increases the Na concentration in the CIGS absorber layer and the CdS buffer layer as measured by glow discharge optical emission spectroscopy (GDOES). Subsequently, the field polarity is reversed and part of the previously added Na is removed. This way, the J –V curve roll‐over related to Na deficiency disappears and the V_OC (+25 mV), J_SC(+2.3 mA/cm²) and FF (+13.5% absolute) of the rear surface passivated CIGS solar cells are optimized. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Investigation of fill factor losses on 20.2% efficient n‐type mono‐like silicon solar cells with laser contact opening

Large area (243.36 cm²) back‐junction passivated emitter, rear totally diffused (PERT) solar cells with laser contact opening (LCO) on n‐type mono‐like crystalline Si with efficiencies of 20.2% are presented. Boron emitters with high electrical quality (implied open circuit voltage iV_OC up to 700 mV) are formed during a co‐diffusion step using SiO_x:B layers. Increasing the rear metal contact coverage, we observed a decrease in fill factor (FF) instead of the expected increase due to the decrease of the back side series resistance. We show that it can be attributed to recombination centers (RCs) in the space charge region underneath the contact spots inducing an increasing second diode contribution. The presented empirical model for the RCs implemented in Synopsys Sentaurus TCAD allows for a successful reproduction of the FF, pseudo FF and V_OC behaviour with contact coverage. According to this model, the RCs induced by laser ablation and subsequently evaporation of Al have a shallow exponential distribution with a characteristic length of L_T = 0.2 µm and an effective surface density of N *_T0 = 25 cm^–1. (© 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)     

Microcrystalline silicon‐carbon alloys as anti‐reflection window layers in high efficiency thin film silicon solar cells

Microcrystalline silicon‐carbide (μc‐SiC:H) films were prepared using hot wire chemical vapor deposition at low substrate temperature. The μc‐SiC:H films were employed as window layers in microcrystalline silicon (μc‐Si:H) solar cells. The short‐circuit current density (J_SC) in these n‐side illuminated n–i–p cells increases with increasing the deposition time t_W of the μc‐SiC:H window layer from 5 min to 60 min. The enhanced J_SC is attributed to both the high transparency and an anti‐reflection effect of the μc‐SiC:H window layer. Using these favourable optical properties of the μc‐SiC:H window layer in μc‐Si:H solar cells, a J_SC value of 23.8 mA/cm² and cell efficiencies above 8.0% were achieved with an absorber layer thickness of 1 μm and a Ag back reflector. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface passivation schemes for high‐efficiency n‐type Si solar cells

An effective passivation on the front side boron emitter is essential to utilize the full potential of solar cells fabricated on n‐type silicon. However, recent investigations have shown that it is more difficult to achieve a low surface recombination velocity on highly doped p‐type silicon than on n‐type silicon. Thus, the approach presented in this paper is to overcompensate the surface of the deep boron emitter locally by a shallow phosphorus diffusion. This inversion from p‐type to n‐type surface allows the use of standard technologies which are used for passivation of highly doped n‐type surfaces. Emitter saturation current densities (J_0e) of 49 fA/cm² have been reached with this approach on SiO₂ passivated lifetime samples. On solar cells a certified conversion efficiency of 21.7% with an open‐circuit voltage (V_oc) of 676 mV was achieved. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface passivation of phosphorus‐diffused n+‐type emitters by plasma‐assisted atomic‐layer deposited Al2O3

In recent years Al₂O₃ has received tremendous interest in the photovoltaic community for the application as surface passivation layer for crystalline silicon. Especially p‐type c‐Si surfaces are very effectively passivated by Al₂O₃, including p‐type emitters, due to the high fixed negative charge in the Al₂O₃ film. In this Letter we show that Al₂O₃ prepared by plasma‐assisted atomic layer deposition (ALD) can actually provide a good level of surface passivation for highly doped n‐type emitters in the range of 10–100 Ω/sq with implied‐V_oc values up to 680 mV. For n‐type emitters in the range of 100–200 Ω/sq the implied‐V_oc drops to a value of 600 mV for a 200 Ω/sq emitter, indicating a decreased level of surface passivation. For even lighter doped n‐type surfaces the passivation quality increases again to implied‐V_oc values well above 700 mV. Hence, the results presented here indicate that within a certain doping range, highly doped n‐ and p‐type surfaces can be passivated simultaneously by Al₂O₃. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of III‐nitride polarization on VOC in p–i–n and MQW solar cells

We performed detailed studies of the effect of polarization on III‐nitride solar cells. Spontaneous and piezoelectric polarizations were assessed to determine their impacts upon the open circuit voltages (V_OC) in p–i(InGaN)–n and multi‐quantum well (MQW) solar cells. We found that the spontaneous polarization in Ga‐polar p–i–n solar cells strongly modifies energy band structures and corresponding electric fields in a way that degrades V_OC compared to non‐polar p–i–n structures. In contrast, we found that piezoelectric polarization in Ga‐polar MQW structures does not have a large influence on V_OC compared to non‐polar MQW structures. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High‐performance a‐Si1–xOx:H/c‐Si heterojunction solar cells realized by the a‐Si:H/a‐Si1–xOx:H stack buffer layer

We used amorphous silicon oxide (a‐Si_1–xO_x:H) and microcrystalline silicon oxide (µc‐Si_1–xO_x:H) as buffer layer and p‐type emitter layer, respectively, in n‐type silicon hetero‐junction (SHJ) solar cells. We proposed to insert a thin (2 nm) intrinsic amorphous silicon (a‐Si:H) thin film between the thin (2.5 nm) a‐Si_1–xO_x:H buffer layer and the p‐layer to form a stack buffer layer of a‐Si:H/a‐Si_1–xO_x:H. As a result, a high open‐circuit voltage (V_OC) and a high fill factor (FF) were obtained at the same time. Finally, a high efficiency of 19.0% (J_SC = 33.46 mA/cm², V_OC = 738 mV, FF = 77.0%) was achieved on a 100 μm thick polished wafer using the stack buffer layer.

     

Contact passivation in silicon solar cells using atomic‐layer‐deposited aluminum oxide layers

Atomic‐layer‐deposited aluminum oxide (AlO_x) layers are implemented between the phosphorous‐diffused n⁺‐emitter and the Al contact of passivated emitter and rear silicon solar cells. The increase in open‐circuit voltage V_oc of 12 mV for solar cells with the Al/AlO_x/n⁺‐Si tunnel contact compared to contacts without AlO_x layer indicates contact passivation by the implemented AlO_x. For the optimal AlO_x layer thickness of 0.24 nm we achieve an independently confirmed energy conversion efficiency of 21.7% and a V_oc of 673 mV. For AlO_x thicknesses larger than 0.24 nm the tunnel probability decreases, resulting in a larger series resistance. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhanced rear‐side reflection and firing‐stable surface passivation of silicon solar cells with capping polymer films

Low refractive index polymer materials have been investigated with a view to form the back surface mirror of advanced silicon solar cells. SiO_x:H or AlO_y SiO_x:H polymer films were spun on top of an ultra‐thin (<10 nm) atomic‐layer‐deposited (ALD) Al₂O₃ layer, itself deposited on low‐resistivity (1 Ω cm) p‐type crystalline silicon wafers. These double‐layer stacks were compared to both ALD Al₂O₃ single layers and ALD Al₂O₃/plasma‐enhanced chemical vapour deposited (PECVD) SiN_x stacks, in terms of surface passivation, firing stability and rear‐side reflection. Very low surface recombination velocity (SRV) values approaching 3 cm/s were achieved with ALD Al₂O₃ layers in the 4–8 nm range. Whilst the surface passivation of the single ALD Al₂O₃ layer is maintained after a standard firing step typical of screen printing metallisation, a harsher firing regime revealed an enhanced thermal stability of the ALD Al₂O₃/SiO_x:H and ALD Al₂O₃/AlO_y SiO_x:H stacks. Using simple two‐dimensional optical modelling of rear‐side reflection it is shown that the low refractive index exhibited by SiO_x:H and AlO_y SiO_x:H results in superior optical performance as compared to PECVD SiN_x, with gains in photogenerated current of ～0.125 mA/cm² at a capping thickness of 100 nm. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High-Efficiency Silicon Solar Cells—Materials and Devices Physics

High-efficiency Si solar cells have attracted great attention from researchers, scientists, engineers of photovoltaic (PV) industry for the past few decades. Many researchers, scientists, and engineers in both academia and industry seek solutions to improve the cell efficiency and reduce the cost. This desire has drawn stronger support from major funding agencies and industry and stimulated a growing number of major research and research infrastructure programs, and a rapidly increasing number of publications in this filed. This article reviews materials, devices, and physics of high-efficiency Si solar cells developed over the last 20 years and presents representative examples of superior performances and competitive advantages. In this paper there is a fair number of topics, not only from the material viewpoint, introducing various materials that are required for high-efficiency Si solar cells, such as base materials (FZ-Si, CZ-Si, MCZ-Si, and multi-Si), emitter materials (diffused emitter and deposited emitter), passivation materials (Al-BSF, high-low junction, SiO₂, SiO_x, SiN_x, Al₂O₃ and a-Si:H), and other functional materials (antireflective layer, transparent conductive oxide and metal electrode), but also from the device and physics point of view, elaborating on physics, cell concept, development, and status of most types of high-efficiency Si solar cells, including passivated emitter and rear contact (PERC), passivated emitter and rear locally diffused (PERL), passivated emitter and rear totally-diffused (PERT), Pluto, PANDA, interdigitated back-contacted (IBC), emitter-wrap-through (EWT), metallization-wrap-through (MWT), heterojunction with intrinsic thin-layer (HIT), and so on. Finally, the technical data of these high-efficiency Si solar cells has been tabulated.     

Effective surface passivation of crystalline silicon using ultrathin Al2O3 films and Al2O3/SiNx stacks

We measure surface recombination velocities (SRVs) below 10 cm/s on p‐type crystalline silicon wafers passivated by atomic–layer–deposited (ALD) aluminium oxide (Al₂O₃) films of thickness ≥10 nm. For films thinner than 10 nm the SRV increases with decreasing Al₂O₃ thickness. For ultrathin Al₂O₃ layers of 3.6 nm we still attain a SRV < 22 cm/s on 1.5 Ω cm p‐Si and an exceptionally low SRV of 1.8 cm/s on high‐resistivity (200 Ω cm) p‐Si. Ultrathin Al₂O₃ films are particularly relevant for the implementation into solar cells, as the deposition rate of the ALD process is extremely low compared to the frequently used plasma‐enhanced chemical vapour deposition of silicon nitride (SiN_x). Our experiments on silicon wafers passivated with stacks composed of ultrathin Al₂O₃ and SiN_x show that a substantially improved thermal stability during high‐temperature firing at 830 °C is obtained for the Al₂O₃/SiN_x stacks compared to the single‐layer Al₂O₃ passivation. Al₂O₃/SiN_x stacks are hence ideally suited for the implementation into industrial‐type silicon solar cells where the metal contacts are made by screen‐printing and high‐temperature firing of metal pastes. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Efficient interdigitated back‐contacted silicon heterojunction solar cells

We present back‐contacted amorphous/crystalline silicon heterojunction solar cells (IBC‐SHJ) on n‐type substrates with fill factors exceeding 78% and high current densities, the latter enabled by a SiN_x /SiO₂ passivated phosphorus‐diffused front surface field. V_oc calculations based on carrier lifetime data of reference samples indicate that for the IBC architecture and the given amorphous silicon layer qualities an emitter buffer layer is crucial to reach a high V_oc, as known for both‐side contacted silicon heterojunction solar cells. A back surface field buffer layer has a minor influence. We observe a boost in solar cell V_oc of 40 mV and a simultaneous fill factor reduction introducing the buffer layer. The aperture‐area efficiency increases from 19.8 ± 0.4% to 20.2 ± 0.4%. Both, efficiencies and fill factors constitute a significant improvement over previously reported values. (© 2011 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)     

Understanding of a-Si:H(p)/c-Si(n) heterojunction solar cell through analysis of cells with point-contacted p/n junction

We fabricated point-contacted a-Si:H(p)/c-Si(n) heterojunction solar cells using patterned SiO₂ and investigated their electrical properties using the light current–voltage (I–V) curve and Suns-V_oc measurements. The light I–V curves showed bias-dependent changes according to the applied voltage in the point-contacted cells, especially in the samples with a long distance between the point-contacted junctions. The Suns-V_oc measurements showed that the bias-dependence of the light I–V curves did not originate from the recombination in the SiO₂/Si or a-Si:H(p)/c-Si(n) interface, but from the series resistances. It is possible to explain the bias-dependent light I–V curve in terms of the conductivity of a-Si:H(p) and difference in the electrical contact properties between a-Si:H(p), ZnO and c-Si(n). These results mean that the electrical properties of the a-Si:H(p) layer and the contact properties with this layer are also critical to obtain a high J_sc and fill factor in n-type based Si heterojunction solar cells.     

Light Trapping and Down‐Shifting Effect of Periodically Nanopatterned Si‐Quantum‐Dot‐Based Structures for Enhanced Photovoltaic Properties

Periodically nanopatterned Si structures have been prepared by using a nanosphere lithography technique. The formed nanopatterned structures exhibit good anti‐reflection and enhanced optical absorption characteristics. The mean surface reflectance weighted by AM1.5 solar spectrum (300–1200 nm) is as low as 5%. By depositing Si quantum dot/SiO₂ multilayers (MLs) on the nanopatterned Si substrate, the optical absorption is higher than 90%, which is significantly improved compared with the same multilayers deposited on flat Si substrate. Furthermore, the prototype n‐Si/Si quantum dot/SiO₂ MLs/p‐Si heterojunction solar cells has been fabricated, and it is found that the external quantum efficiency is obviously enhanced for nanopatterned cell in a wide spectral range compared with the flat cell. The corresponding short‐circuit current density is increased from 25.5 mA cm^?2 for flat cell to 29.0 mA cm^?2 for nano‐patterned one. The improvement of cell performance can be attributed both to the reduced light loss and the down‐shifting effect of Si quantum dots/SiO₂ MLs by forming periodically nanopatterned structures.     

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.     

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)     

Investigation of Cu2ZnSnS4 solar cell buffer layer fabricated via spray pyrolysis

Copper zinc tin sulfide solar cells were fabricated by using spray pyrolysis from a window layer to an absorber layer. ZnS and In₂S₃ buffer layers were deposited on the TiO₂ layer, and the photovoltaic characteristics were investigated. The ZnS buffer demonstrated a poor photovoltaic performance because of its poor surface coverage and micro-cracks at fluorine-doped tin oxide/TiO₂ layers. The In₂S₃ buffer layer sprayed at low temperature (<360 °C) showed a large difference between photo and dark currents beyond the open-circuit voltage (V_OC). When the spraying temperature exceeded 390 °C, the devices showed high dark leakage currents at reverse biases because of the high conductivity of the buffer layer, resulting in decreased V_OC and short-circuit current density (J_SC). The optimum temperature for spraying In₂S₃ is 360 °C, and the best performing device showed 410 mV, 30.4 mA/cm², 35.3%, and 4.4% of V_OC, J_SC, fill factor, and efficiency, respectively.     

Fabrication and characterization of ZnTPP:PCBM bulk heterojunction (BHJ) solar cells

Bulk heterojunction (BHJ) solar cells were fabricated based on blended films of a porphyrin derivative 5,10,15,20-Tetraphenyl-21H,23H-porphine zinc (ZnTPP) and a fullerene derivative [6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) as the active layer. The ZnTTP:PCBM BHJ solar cells were fabricated by spin-casting of the blended layer. The weight ratios of ZnTPP and PCBM were varied from 1:1 to 0:10. The electronic and optical properties of each cell were investigated. Optical density (OD) of the blended film for each cell was extracted from its reflection and transmission curves. OD and average absorption coefficients of the active materials were used to determine film thicknesses. Absorption spectra of each component material were compared with the spectra of the blended films. Current density–Voltage (J–V) characteristics were recorded under dark as well as under the illumination of AM 1.5G (1 sun) solar spectrum. The BHJ solar cell with ZnTPP:PCBM ratio of 1:9 showed the best performance . The values of RR, V_OC , J_SC , FF and η for these ratios were 106.3, 0.4 V, 1.316 mA/cm², 0.4 and 0.21%, respectively. The cross-section of this device using SEM was also examined.