Novel Atmospheric Growth Technique to Improve Both Light Absorption and Charge Collection in ZnO/Cu2O Thin Film Solar Cells

In low temperature grown ZnO/Cu₂O solar cells, there is a discrepancy between collection length and depletion width in the Cu₂O which makes the simultaneous achievement of efficient charge collection and high open‐circuit voltage problematic. This is addressed in this study by fabricating ZnO/Cu₂O/Cu₂O⁺ back surface field devices using an atmospheric atomic layer deposition (AALD) printing method to grow a sub‐200‐nm Cu₂O⁺ film on top of electrodeposited ZnO and Cu₂O layers. The AALD Cu₂O⁺ has a carrier concentration around 2 orders of magnitude higher than the electrodeposited Cu₂O, allowing the electrodeposited Cu₂O layer thickness in a back surface field cell to be reduced from 3 μm to the approximate charge collection length, 1 μm, while still allowing a high potential to be built into the cell. The dense conformal nature of the AALD layer also blocks shunt pathways allowing the voltage enhancement to be maintained. The thinner cell design reduces recombination losses and increases charge collection from both incident light and light reflected off the back electrode. Using this design, a short circuit current density of 6.32 mA cm^?2 is achieved–the highest reported J_SC for an atmospherically deposited ZnO/Cu₂O device to date.     

Cu2ZnSnSe4 thin film solar cells produced by selenisation of magnetron sputtered precursors

Polycrystalline thin films of Cu₂ZnSnSe₄ (CZTSe) were produced by selenisation of Cu(Zn,Sn) magnetron sputtered metallic precursors for solar cell applications. The p‐type CZTSe absorber films were found to crystallize in the stannite structure (a = 5·684 Å and c = 11·353 Å) with an electronic bandgap of 0·9 eV. Solar cells with the indium tin oxide structure (ITO)/ZnO/CdS/CZTSe/Mo were fabricated with device efficiencies up to 3·2% measured under standard AM1·5 illumination. Copyright © 2009 John Wiley & Sons, Ltd.     

All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

High efficiency screen printed bifacial solar cells on monocrystalline CZ silicon

We present industrialized bifacial solar cells on large area (149 cm²) 2 cm CZ monocrystalline silicon wafers processed with industrially relevant techniques such as liquid source BBr₃ and POCl₃ open‐tube furnace diffusions, plasma enhanced chemical vapor deposition (PECVD) SiN_x deposition, and screen printed contacts. The fundamental analysis of the paste using at boron‐diffused surface and the bifacial solar cell firing cycle has been investigated. The resulting solar cells have front and rear efficiencies of 16.6 and 12.8%, respectively. The ratio of the rear J_SC to front J_SC is 76.8%. It increases the bifacial power by 15.4% over a conventional solar cell at 20% of 1‐sun rear illumination, which equals to the power of a conventional solar cell with 19.2% efficiency. We also present a bifacial glass–glass photovoltaic (PV) module with 30 bifacial cells with the electrical characteristics. Copyright © 2010 John Wiley & Sons, Ltd.     

A Novel Buffering Technique for Aqueous Processing of Zinc Oxide Nanostructures and Interfaces,and Corresponding Improvement of Electrodeposited ZnO‐Cu2O Photovoltaics

A novel buffering method is presented to improve the stability of zinc oxide processed in aqueous solutions. By buffering the aqueous solution with a suitable quantity of sacrificial zinc species, the dissolution of functional zinc oxide structures and the formation of unwanted impurities can be prevented. The method is demonstrated for ZnO films and nanowires processed in aqueous solutions used for the selective etching of mesoporous anodic alumina templates and the electrochemical deposition of Cu₂O. In both cases, improved ZnO stability is observed with the buffering method. ZnO‐Cu₂O heterojunction solar cells (bilayer and nanowire cells) synthesized using both traditional and buffered deposition methods are characterized by impedance spectroscopy and solar simulation measurements. Buffering the Cu₂O deposition solution is found to reduce unwanted recombination at the heterojunction and improve the photovoltaic performance.     

Structural and Electrical Properties of Atomic Layer Deposited Al‐Doped ZnO Films

Structural and electrical properties of Al‐doped ZnO (AZO) films deposited by atomic layer deposition (ALD) are investigated to study the extrinsic doping mechanism of a transparent conducting oxide. ALD‐AZO films exhibit a unique layer‐by‐layer structure consisting of a ZnO matrix and Al₂O₃ dopant layers, as determined by transmission electron microscopy analysis. In these layered AZO films, a single Al₂O₃ dopant layer deposited during one ALD cycle could provide ≈4.5 × 10¹³ cm^?2 free electrons to the ZnO. The effective field model for doping is suggested to explain the decrease in the carrier concentration of ALD‐AZO films when the interval between the Al₂O₃ layers is reduced to less than ≈2.6 nm (>3.4 at% Al). By correlating the electrical and structural properties, an extrinsic doping mechanism of ALD‐AZO films is proposed in which the incorporated Al atoms take oxygen from the ZnO matrix and form doubly charged donors, such as oxygen vacancies or zinc interstitials.     

绒面掺铝氧化锌透明导电薄膜研究进展

绒面掺铝氧化锌(AZO)透明导电薄膜由于电阻率低、在可见光区域透过率高、绒面结构能有效散射入射光,提高太阳电池光电转换效率,被广泛应用于太阳电池前电极。概述了绒面AZO薄膜的制备方法,重点介绍了磁控溅射技术沉积AZO薄膜后再进行湿法刻蚀制绒面方法,制备的样品呈现"坑状"或"类月球地貌"的绒面,并讨论了工艺对薄膜结构、光电性能和刻蚀行为的影响,最后介绍了绒面AZO薄膜在硅薄膜太阳电池中的应用,进一步降低生产成本和实现大规模产业化生产是绒面AZO薄膜的发展趋势。     

8.2% pure selenide kesterite thin‐film solar cells from large‐area electrodeposited precursors

Cu₂ZnSnSe₄ solar cell absorbers are synthesized by large‐area electrodeposition of metal stack precursors followed by selenization. A champion solar cell exhibits 8.2% power conversion efficiency, a new record for Cu₂ZnSnSe₄ solar cells prepared from electrodeposited metallic precursors. Significant improvements of device performance are achieved by the application of two etching procedures and buffer layer optimization. These results validate electrodeposition as a credible alternative to vacuum processes (sputtering, co‐evaporation) for earth‐abundant thin‐film solar cell fabrication at low cost. Copyright © 2015 John Wiley & Sons, Ltd.     

Ligand‐Free Synthesis of Aluminum‐Doped Zinc Oxide Nanocrystals and their Use as Optical Spacers in Color‐Tuned Highly Efficient Organic Solar Cells

The color of polymer solar cells using an opaque electrode is given by the reflected light, which depends on the composition and thickness of each layer of the device. Metal‐oxide‐based optical spacers are intensively studied in polymer solar cells aiming to optimize the light absorption. However, the low conductivity of materials such as ZnO and TiO₂ limits the thickness of such optical spacers to tenths of nanometers. A novel synthesis route of cluster‐free Al‐doped ZnO (AZO) nanocrystals (NCs) is presented for solution processing of highly conductive layers without the need of temperature annealing, including thick optical spacers on top of polymer blends. The processing of 80 nm thick optical spacers based on AZO nanocrystal solutions on top of 200 nm thick polymer blend layer is demonstrated leading to improved photocurrent density of 17% compared to solar cells using standard active layers of 90 nm in combination with thin ZnO‐based optical spacers. These AZO NCs also open new opportunities for the processing of high‐efficiency color tuned solar cells. For the first time, it is shown that applying solution‐processed thick optical spacer with polymer blends of different thicknesses can process solar cells of similar efficiency over 7% but of different colors.     

Effects of Photo‐oxidation on the Performance of Poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene]:[6,6]‐Phenyl C61‐Butyric Acid Methyl Ester Solar Cells

A study of the photo‐oxidation of films of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV) blended with [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM), and solar cells based thereon, is presented. Solar‐cell performance is degraded primarily through loss in short‐circuit current density, J_SC. The effect of the same photodegradation treatment on the optical‐absorption, charge‐recombination, and charge‐transport properties of the active layer is studied. It is concluded that the loss in J_SC is primarily due to a reduction in charge‐carrier mobility, owing to the creation of more deep traps in the polymer during photo‐oxidation. Recombination is slowed down by the degradation and cannot therefore explain the loss in photocurrent. Optical absorption is reduced by photo‐bleaching, but the size of this effect alone is insufficient to explain the loss in device photocurrent.     

Highly Robust Indium‐Free Transparent Conductive Electrodes Based on Composites of Silver Nanowires and Conductive Metal Oxides

A hybrid approach for the realization of In‐free transparent conductive layers based on a composite of a mesh of silver nanowires (NWs) and a conductive metal‐oxide is demonstrated. As metal‐oxide room‐temperature‐processed sol–gel SnO_x or Al:ZnO prepared by low‐temperature (100 °C) atomic layer deposition is used, respectively. In this concept, the metal‐oxide is intended to fuse the wires together and also to “glue” them to the substrate. As a result, a low sheet resistance down to 5.2 Ω sq^‐1 is achieved with a concomitant average transmission of 87%. The adhesion of the NWs to the substrate is significantly improved and the resulting composites withstand adhesion tests without loss in conductivity. Owing to the low processing temperatures, this concept allows highly robust, highly conductive, and transparent coatings even on top of temperature sensitive objects, for example, polymer foils, organic devices. These Indium‐ and PEDOT:PSS‐free hybrid layers are successfully implemented as transparent top‐electrodes in efficient all‐solution‐processed semitransparent organic solar cells. It is obvious that this approach is not limited to organic solar cells but will generally be applicable in devices which require transparent electrodes.     

Incompatible Length Scales in Nanostructured Cu2O Solar Cells

Electrodeposited Cu₂O‐ZnO heterojunctions are promising low‐cost solar cells. While nanostructured architectures improve charge collection in these devices, low open‐circuit voltages result. Bilayer and nanowire Cu₂O‐ZnO heterojunction architectures are systematically studied as a function of the Cu₂O layer thickness, ZnO nanowire length, and nanowire seed layer. It is shown that a thick depletion layer exists in the Cu₂O layer of bilayer devices, owing to the low carrier density of electrodeposited Cu₂O, such that the predominant charge transport mechanisms in the Cu₂O and ZnO are drift and diffusion, respectively. This suggests that the low open‐circuit voltage of the nanowire cells is due to an incompatibility between the nanostructure spacing required for good charge collection (<1 μm) and the heterojunction thickness necessary to form the full built‐in potential that inhibits recombination (>2 μm). The work shows the way to improve low‐cost Cu₂O cells: increasing the carrier concentration or mobility in Cu₂O synthesized at low temperatures.     

Highly Interconnected Porous Electrodes for Dye‐Sensitized Solar Cells Using Viruses as a Sacrificial Template

A novel means of generating highly interconnected and nano‐channeled photoelectrodes by employing one‐dimensionally shaped M13 viruses as a sacrificial template is proposed for highly efficient dye‐sensitized solar cells (DSSCs). The electrostatic binding between oppositely charged TiO₂ nanoparticles and M13 viruses provides a uniform complexation and suppresses random aggregation of TiO₂ nanoparticles. After the calcination process, the traces of viruses leave porously interconnected channel structures inside TiO₂ nanoparticles, providing efficient paths for electrolyte contact as well as increased surface sites for dye adsorption. As a result, DSSCs generated using a sacrificial virus template exhibit an enhanced current density (J_SC) of 12.35 mA cm‐² and a high photoconversion efficiency (η) of 6.32%, greater than those of conventional photoelectrodes made of TiO₂ nanoparticles (J_SC of 8.91 mA cm‐² and η of 4.67%). In addition, the stiffness and shape of the M13 virus can be varied, emphasizing the usefulness of the one‐dimensional structural characteristics of M13 viruses for the highly interconnected porous structure of DSSC photoelectrodes.     

Investigation of series resistance losses by illuminated lock‐in thermography

A measurement mode (J_SC‐ILIT) for the recently introduced Illuminated Lock‐In Thermography (ILIT) method and a new interpretation of the images obtained is proposed. This mode is especially adapted for the investigation of series resistance, in particular contact resistance, in solar cells. Comparison of J_SC‐ILIT results to emitter potential maps obtained by Corescan demonstrate good agreement between the poorly contacted areas, proving the practical applicability of the technique. J_SC‐ILIT provides a quasi‐contactless and fast measurement. Comparison is made with the recently introduced method of R_S‐ILIT. The capability of both methods to detect series resistance problems is demonstrated. Possible distortions due to inhomogeneities of bulk material quality are discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

High rate (~7 nm/s), atmospheric pressure deposition of ZnO front electrode for Cu(In,Ga)Se2 thin‐film solar cells with efficiency beyond 15%

Undoped zinc oxide (ZnO) films have been grown on a moving glass substrate by plasma‐enhanced chemical vapor deposition at atmospheric pressure. High deposition rates of ~7 nm/s are achieved at low temperature (200 °C) for a substrate speed from 20 to 60 mm/min. ZnO films are highly transparent in the visible range (90%). By a short (~minute) post‐deposition exposure to near‐ultraviolet light, a very low resistivity value of 1.6·10⁻³ Ω cm for undoped ZnO is achieved, which is independent on the film thickness in the range from 180 to 1200 nm. The photo‐enhanced conductivity is stable in time at room temperature when ZnO is coated by an Al₂O₃ barrier film, deposited by the industrially scalable spatial atomic layer deposition technique. ZnO and Al₂O₃ films have been used as front electrode and barrier, respectively, in Cu(In,Ga)Se2 (CIGS) solar cells. An average efficiency of 15.4 ± 0.2% (15 cells) is obtained that is similar to the efficiency of CIGS reference cells in which sputtered ZnO:Al is used as electrode. Copyright © 2013 John Wiley & Sons, Ltd.     

Optical and electrical properties of epitaxial (Mg,Cd)xZn1−xO, ZnO, and ZnO:(Ga,Al) thin films on c-plane sapphire grown by pulsed laser deposition

A consistent set of epitaxial, n-type conducting ZnO thin films, nominally undoped, doped with Ga or Al, or alloyed with Mg or Cd, was grown by pulsed laser deposition (PLD) on single-crystalline c-plane sapphire (0 0 0 1) substrates, and characterized by Hall measurement, and UV/VIS optical transmission spectroscopy.The optical band gap of undoped ZnO films at nearly 3.28 eV was shifted by alloying with Mg up to 4.5 eV and by alloying with Cd down to 3.18 eV, dependent on the alloy composition. In addition, highly doped ZnO:Al films show a blue-shifted optical absorption edge due to filling of electronic states in the conduction band.The Hall transport data of the PLD (Mg,Zn,Cd)O:(Ga,Al) thin films span a carrier concentration range of six orders of magnitude from 3 × 10¹⁴ to 3 × 10²⁰ cm⁻³, which corresponds to a resistivity from 5 × 10⁻⁴ to 3 × 10³ Ω cm. Structurally optimized, nominally undoped ZnO films grown with ZnO nucleation and top layer reached an electron mobility of 155 cm²/V s (300 K), which is among the largest values reported for heteroepitaxial ZnO thin films so far.Finally, we succeeded in combining the low resistivity of ZnO:Ga and the band gap shift of MgZnO in MgZnO:Ga thin films. This results demonstrate the unique tunability of the optical and electrical properties of the ZnO-based wide-band gap material for future electronic devices.     

A Cross‐Linkable Donor Polymer as the Underlying Layer to Tune the Active Layer Morphology of Polymer Solar Cells

For polymer solar cells (PSCs) with conventional configuration, the vertical composition profile of donor:acceptor in active layer is detrimental for charge carrier transporting/collection and leads to decreased device performance. A cross‐linkable donor polymer as the underlying morphology‐inducing layer (MIL) to tune the vertical composition distribution of donor:acceptor in the active layer for improved PSC device performance is reported. With poly(thieno[3,4‐b]‐thiophene/benzodithiophene):[6,6]‐phenyl C₇₁‐butyric acid methyl ester (PTB7:PC₇₁BM) as the active layer, the MIL material, PTB7‐TV , is developed by attaching cross‐linkable vinyl groups to the side chain of PTB7. PSC device with PTB7‐TV layer exhibits a power conversion efficiency (PCE) of 8.55% and short‐circuit current density (J_SC) of 15.75 mA cm^?2, in comparison to PCE of 7.41% and J_SC of 13.73 mA cm^?2 of the controlled device. The enhanced device performance is ascribed to the much improved vertical composition profile and reduced phase separation domain size in the active layer. These results demonstrate that cross‐linked MIL is an effective strategy to improve photovoltaic performance of conventional PSC devices.     

Optimization of interdigitated back contact silicon heterojunction solar cells: tailoring hetero‐interface band structures while maintaining surface passivation

Interdigitated back contact silicon heterojunction (IBC‐SHJ) solar cells have the potential for high open circuit voltage (V_OC) due to the surface passivation and heterojunction contacts, and high short circuit current density (J_SC) due to all back contact design. Intrinsic amorphous silicon (a‐Si:H) buffer layer at the rear surface improve the surface passivation hence V_OC and J_SC, but degrade fill factor (FF) from an “S” shape J–V curve. Two‐dimensional (2D) simulation using “Sentaurus device” demonstrates that the low FF is related to the valence band offset (energy barrier) at the hetero‐interface. Three approaches to the buffer layer are suggested to improve the FF: (1) reduced thickness, (2) increased conductivity, and/or (3) reduced band gap. Experimental IBC‐SHJ solar cells with reduced buffer thickness (<5 nm) and increased conductivity with low boron doping significantly improves FF, consistent with simulation. However, this has only marginal effect on efficiency since J_SC and V_OC also decrease due to poor surface passivation. A narrow band gap a‐Si:H buffer layer improves cell efficiency to 13.5% with unoptimized passivation quality. These results demonstrate that tailoring the hetero‐interface band structure is critical for achieving high FF. Simulations predicts that efficiences >23% are possible on planar devices with optimized pitch dimensions and achievable surface passivation, and 26% with light trapping. This work provides criterion to design IBC‐SHJ solar cell structures and optimize cell performance. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of Annealing in a Partially Reducing Atmosphere on Sputtered Al-Doped ZnO Thin Films

Aluminum-doped ZnO (AZO) films have been deposited by room-temperature radio frequency (RF) magnetron sputtering onto fused-quartz substrates using a ZnO:Al₂O₃ (98:2 wt.%) target. A post-deposition anneal in an N₂ flow has been shown to improve the electrical and optical properties of as-deposited AZO. All films were polycrystalline and exhibited a hexagonal wurtzite structure with the c-axis oriented perpendicular to the substrate. An increase in the estimated crystallite size was observed after annealing. Electrical resistivity was reduced from 3.7 × 10⁻³ Ω cm for as-deposited layers to 7.1 × 10⁻⁴ Ω cm for annealed films. An average optical transmittance >85% for annealed films was routinely measured. X-ray photoelectron spectroscopy measurements indicated that the surfaces of all layers investigated were oxygen deficient, and the density of oxygen vacancies was found to increase following the anneal.     

Back amorphous‐crystalline silicon heterojunction (BACH) photovoltaic device with facile‐grown oxide ‐ PECVD SiNx passivation

This article reports on the integration of facile native oxide‐based passivation of crystalline silicon surfaces within the back amorphous‐crystalline silicon heterojunction solar cell concept. The new passivation scheme consists of 1‐nm thick native oxide and nominally 70‐nm thick PECVD silicon nitride. The low temperature passivation scheme provides uniform high quality surface passivation and low parasitic optical absorption. The interdigitated doped hydrogenated amorphous silicon layers were deposited on the rear side of the silicon wafer using the direct current saddle field PECVD technique. A systematic analysis of a series of back amorphous‐crystalline silicon heterojunction cells is carried out in order to examine the influence of the various cell parameters (interdigital gap, n‐doped region width, ratio of widths of p, and n‐doped regions) on cell performance. A photovoltaic conversion efficiency of 16.7 % is obtained for an untextured cell illuminated under AM 1.5 global spectrum (cell parameters: V_OC of 641 mV, J_SC of 33.7 mA‐cm ^{− 2} and fill factor of 77.3 %). Copyright © 2014 John Wiley & Sons, Ltd.