13·9%‐efficient CdTe polycrystalline thin‐film solar cells with an infrared transmission of ∼50%

To fabricate a high‐efficiency polycrystalline thin‐film tandem cell, the most critical work is to make a high‐efficiency top cell ( > 15%) with high bandgap (E_g = 1·5–1·8 eV) and high transmission (T > 70%) in the near‐infrared (NIR) wavelength region. The CdTe cell is one of the candidates for the top cell, because CdTe state‐of‐the‐art single‐junction devices with efficiencies of more than 16% are available, although its bandgap (1·48 eV) is slightly lower for a top cell in a current‐matched dual‐junction device. In this paper, we focus on the development of a: (1) thin, low‐bandgap Cu_xTe transparent back‐contact; and (2) modified CdTe device structure, including three novel materials: cadmium stannate transparent conducting oxide (TCO), ZnSnO_x buffer layer, and nanocrystalline CdS:O window layer developed at NREL, as well as the high‐quality CdTe film, to improve transmission in the NIR region while maintaining high device efficiency. We have achieved an NREL‐confirmed 13·9%‐efficient CdTe transparent solar cell with an infrared transmission of ∼50% and a CdTe/CIS polycrystalline mechanically stacked thin‐film tandem cell with an NREL‐confirmed efficiency of 15·3%. Copyright © 2005 John Wiley & Sons, Ltd.     

CdTe/CdS thin film solar cells grown in substrate configuration

The ability to grow efficient CdTe/CdS solar cells in substrate configuration would not only allow for the use of non‐transparent and flexible substrates but also enable a better control of junction formation. Yet, the problems of barrier formation at the back contact as well as the formation of a p–n junction with reduced recombination losses have to be solved. In this work, CdTe/CdS solar cells in substrate configuration were developed, and the results on different combinations of back contact materials are presented. The Cu content in the electrical back contact was found to be a crucial parameter for the optimal CdCl₂‐treatment procedure. For Cu‐free cells, two activation treatments were applied, whereas Cu‐containing cells were only treated once after the CdTe deposition. A recrystallization behavior of the CdTe layer upon its activation similar to superstrate configuration was found; however, no CdTe–CdS intermixing could be observed when the layers were treated consecutively. Remarkably high V_OC and fill factor of 768 mV and 68.6%, respectively, were achieved using a combination of MoO₃, Te, and Cu as back contact buffer layer resulting in 11.3% conversion efficiency. With a Cu‐free MoO₃/Te buffer material, a V_OC of 733 mV, a fill factor of 62.3%, and an efficiency of 10.0% were obtained. Copyright © 2012 John Wiley & Sons, Ltd.     

Stable CdTe thin film solar cells with a MoOx back‐contact buffer layer

MoO_x thin films were employed as a buffer layer in the back contact of CdTe solar cells. A monograined CdS layer was employed as the window layer to reduce light absorption. The insertion of a MoO_x buffer layer in the back contact greatly reduced the Schottky barrier leading to increased fill factor and open‐circuit voltage. A CdTe solar cell, with an efficiency as high as 14.2%, was fabricated. The use of a MoO_x buffer layer made it possible to fabricate high‐efficient CdTe solar cell with much less Cu in the back contact, thus greatly enhancing the cell stability. Copyright © 2015 John Wiley & Sons, Ltd.     

Application of copper thiocyanate for high open‐circuit voltages of CdTe solar cells

Copper thiocyanate (CuSCN) has proven to be a low‐cost, efficient hole‐transporting material for the emerging organic–inorganic perovskite solar cells. Herein, we report that CuSCN can also be applied to CdTe thin‐film solar cells to achieve high open‐circuit voltages (V_OCs). By optimizing the thickness of the thermally evaporated CuSCN films, CdTe cells fabricated by close space sublimation in the superstrate configuration have achieved V_OCs as high as 872 mV, which is about 20–25 mV higher than the highest V_OC for the reference cells using the standard Cu/Au back contacts. CuSCN is a wide bandgap p‐type conductor with a conduction band higher than that of CdTe, leading to a conduction band offset that reflects electrons in CdTe, partially explaining the improved V_OCs. However, due to the low conductivity of CuSCN, CdTe cells using CuSCN/Au back contacts exhibited slightly lower fill factors than the cells using Cu/Au back contacts. With optimized CdS:O window layers, the power conversion efficiency of the best CdTe cell, using CuSCN/Au back contact, is 14.7%: slightly lower than that of the best cell (15.2%) using Cu/Au back contact. Copyright © 2015 John Wiley & Sons, Ltd.     

Contact wetting angle as a characterization technique for processing CdTe/CdS solar cells

The feasibility of measuring contact wetting angles to characterize processing induced changes to thin film semiconductors in CdTe/CdS solar cells is evaluated. The contact angles of water and formamide are used to determine the polar and dispersive surface energies of the thin films using two analysis methods. Changes in surface energies resulting from processing are correlated to changes in surface chemistry and structure detected by glancing incidence X‐ray diffraction (GIXRD), X‐ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Surface energies are evaluated for sputtered In₂O₃:SnO₂, chemical surface‐deposited CdS, and physical vapor‐deposited (PVD) CdTe thin films under as‐deposited and treated conditions. Treatments include thermal anneal in air, argon, and CdCl₂ ambient as well as surface etching. Indium tin oxide (ITO) and CdS films exhibit increased polar surface energy corresponding to enhanced crystallization of surfaces resulting from processing and increasing CdS growth temperature. Native oxidation of PVD CdTe (111)‐oriented film surfaces occurs rapidly and is readily detected by changes in contact angle. Surface energies of PVD (111)‐oriented CdTe stored under various humidities prior to processing are energetically similar due to native oxidation. The polar energy of CdTe surfaces is affected by the addition or removal of crystalline surface oxides during film processing. Copyright © 2006 John Wiley & Sons, Ltd.     

Factors Affecting the Stability of CdTe/CdS Solar Cells Deduced from Stress Tests at Elevated Temperature

CdTe/CdS solar cells were subjected to heat stress at 200 °C in the dark under different environments (in N₂ and in air), and under illumination (in N₂). We postulate that two independent mechanisms can explain degradation phenomena in these cells: i) Excessive Cu doping of CdS: Accumulation of Cu in the CdS with stress, in the presence of Cl, will increase the photoconductivity of CdS. With limited amounts of Cu in CdS, this does NOT affect the photovoltaic behavior, but explains the crossover of light/dark current–voltage (J–V) curves. Overdoping of CdS with Cu can be detrimental to cell performance by creating deep acceptor states, acting as recombination centers, and compensating donor states. Under illumination, the barrier to Cu cations at the cell junction is reduced, and, therefore, Cu accumulation in the CdS is enhanced. Recovery of light‐stress induced degradation in CdTe/CdS cells in the dark is explained by dissociation of the acceptor defects. ii) Back contact barrier: Oxidation of the CdTe back surface in O₂/H₂O‐containing environment to form an insulating oxide results in a back‐contact barrier. This barrier is expressed by a rollover in the J–V curve. Humidity is an important factor in air‐induced degradation, as it accelerates the oxide formation. Heat treatment in the dark in inert atmosphere can stabilize the cells against certain causes of degradation, by completing the back contact anneal.     

Performance enhancement of III–V compound multijunction solar cell incorporating transparent electrode and surface treatment

To enhance the performance of tandem‐type III–V compound multijunction solar cells, the transparent indium‐tin‐oxide (ITO) film was used to replace conventional metal electrode for increasing the incident light area. For performing ohmic contact between the n‐AlInP window layer and the ITO film, a transition layer of Au/AuGeNi thin metals was used and investigated. Besides, to improve ohmic performance and to passivate the surface states, (NH₄)₂S_x surface treatment was used. The conversion efficiency of the (NH₄)₂S_x‐treated triple‐junction solar cells was increased more than 3.09%. Furthermore, an improved oblique SiO₂/SiO₂/ITO triple antireflection structure was designed to reduce the reflectivity of illuminating sunlight. The conversion efficiency of the (NH₄)₂S_x‐treated triple‐junction solar cell with improved antireflection structure could be improved more than 4.23%. Simple and effective approaches were designed to improve the performances of tandem‐type III–V triple‐junction solar cells. Copyright © 2010 John Wiley & Sons, Ltd.     

Copper (I) Oxide (Cu2O) based back contact for p‐i‐n CdTe solar cells

In this paper a promising solution for the notorious problem of manufacturing a stable low ohmic back contact of a CdTe thin film superstrate solar cell is presented without using elemental copper. Instead we have used a Cu₂O layer inserted between the CdTe absorber and metal contact (Au). In contrast to the barrier free band alignment gained by using the transitivity rules, XPS measurements show a barrier in the valence band of the Cu₂O layers directly after deposition, which results in a low performing JV curve. The contact can be improved by a short thermal treatment resulting in efficiencies superior to copper based contacts for standard CdS/CdTe hetero junction solar cells prepared on commercial glass/FTO substrates. By replacing the CdS window layer with a CdS:O buffer layer efficiencies of >15% could be achieved. Copyright © 2016 John Wiley & Sons, Ltd.     

CdS/CdTe thin‐film solar cells with Cu‐free transition metal oxide/Au back contacts

Superstrate CdS/CdTe thin‐film solar cells with Cu‐free transition metal oxide (TMO)/Au and Au‐only back contacts have been fabricated. The TMOs include MoO_3‐x, V₂O_5‐x, and WO_3‐x. The incorporation of the TMO buffer layers at the back contacts resulted in significant improvement on open‐circuit voltage (V_OC) as compared with the cells with Cu‐free Au‐only back contacts. Among the cells using TMO buffer layers, the ones with MoO_3‐x buffer layers exhibited the best performance, yielding an efficiency of 14.1% under AM1.5 illumination with V_OC of 815 mV and a fill factor of 67.9%. Though the performance is slightly behind the best reference cell with a Cu/Au back contact fabricated in our lab with V_OC of 844 mV, fill factor of 76.3%, and efficiency of 15.7%, the use of Cu‐free back contacts may lead to improved long‐term cell stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Flexible CdTe solar cells on polymer films

Lightweight and flexible CdTe/CdS solar cells on polyimide films have been developed in a ‘superstrate configuration’ where the light is absorbed in CdTe after passing through the polyimide substrate. The average optical transmission of the approximately 10‐μm‐thin spin‐coated polyimide substrate layer is more than ∼75% for wavelengths above 550 nm. RF magnetron sputtering was used to grow transparent conducting ZnO:Al layers on polyimide films. CdTe/CdS layers were grown by evaporation of compounds, and a CdCl₂ annealing treatment was applied for the recrystallization and junction activation. Solar cells of 8·6% efficiency with V_oc = 763 mV, I_sc = 20·3 mA/cm² and FF = 55·7% were obtained. Copyright © 2001 John Wiley & Sons, Ltd.     

Optimization of CdTe thin‐film solar cell efficiency using a sputtered,oxygenated CdS window layer

A major source of loss in cadmium sulfide/cadmium telluride (CdS/CdTe) solar cells results from light absorbed in the CdS window layer, which is not converted to electrical current. This film can be made more transparent by oxygen incorporation during sputter deposition at ambient temperature. Prior to this work, this material has not produced high‐efficiency devices on tin oxide‐coated soda‐lime‐glass substrates used industrially. Numerous devices were fabricated over a variety of process conditions to produce an optimized device. Although the material does not show a consistent increase in band gap with oxygenation, absorption in this layer can be virtually eliminated over the relevant spectrum, leading to an increase in short‐circuit current. Meanwhile, fill factor is maintained, and open‐circuit voltage increases relative to baseline devices with sublimated CdS. The trend of device parameters with oxygenation and thickness is consistent with an increasing conduction band offset at the window/CdTe interface. Optimization considering both initial efficiency and stability resulted in a National Renewable Energy Laboratory verified 15.2%‐efficient cell on 3.2‐mm soda‐lime glass. This window material was shown to be compatible with SnO₂‐based transparent conducting oxide and high resistance transparent coated substrates using in‐line compatible processes. Copyright © 2015 John Wiley & Sons, Ltd     

Voltage dependent photocurrent collection in CdTe/CdS solar cells

The voltage dependence of the photocurrent J_L(V) of CdTe/CdS solar cells has been characterized by separating the forward current from the photocurrent at several illumination intensities. J_L(V) reduces the fill factor (FF) of typical cells by 10–15 points, the open circuit voltage (V_OC) by 20–50 mV, and the efficiency by 2–4 points. Eliminating the effect of J_L(V) establishes superposition between light and dark J(V) curves for some cells. Two models for voltage dependent collection give reasonable fits to the data: (1) a single carrier Hecht model developed for drift collection in p‐i‐n solar cells in which fitting yields a parameter consistent with lifetimes of 10⁻⁹ s as measured by others; or (2) the standard depletion region and bulk diffusion length model fits almost as well. The simple Hecht‐like drift collection model for photocurrent gives very good agreement to J(V) curves measured under AM1·5 light on CdTe/CdS solar cells with FF from 53% to 70%, CdTe thickness from 1·8 to 7·0 µm, in initial and stressed states. Accelerated thermal and bias stressing increases J_L(V) losses as does insufficient Cu. This method provides a new metric for tracking device performance, characterizes transport in the high field depletion region, and quantifies a significant FF loss in CdTe solar cells. Copyright © 2007 John Wiley & Sons, Ltd.     

Copper migration in cdte heterojunction solar cells

CdTe solar cells were fabricated by depositing a Au/Cu contact with Cu thickness in the range of 50 to 150Å on polycrystalline CdTe/CdS/SnO₂/glass structures. The increase in Cu thickness improves ohmic contact and reduces series resistance (R_s), but the excess Cu tends to diffuse into CdTe and lower shunt resistance (R_sh) and cell performance. Light I-V and secondary ion mass spectros-copy (SIMS) measurements were performed to understand the correlations between the Cu contact thickness, the extent of Cu incorporation in the CdTe cells, and its impact on the cell performance. The CdTe/CdS/SnO₂/glass, CdTe/ CdS/GaAs, and CdTe/GaAs structures were prepared in an attempt to achieve CdTe films with different degrees of crystallinity and grain size. A large grain polycrystalline CdTe thin film solar cell was obtained for the first time by selective etching the GaAs substrate coupled with the film transfer onto a glass substrate. SIMS measurement showed that poor crystallinity and smaller grain size of the CdTe film promotes Cu diffusion and decreases the cell performance. Therefore, grain boundaries are the main conduits for Cu migration and larger CdTe grain size or alternate method of contact formation can mitigate the adverse effect of Cu and improve the cell performance.     

CuxS背接触层制备及在碲化镉薄膜太阳电池中应用研究

本文采用化学水浴法沉积CuxS薄膜,通过改变Cu元素比例研究其对碲化镉电池效率的影响。研究表明化学水浴法沉积的CuxS是非晶的,采用适当退火条件可以使其晶化,随着退火温度的提高,薄膜变得致密且结晶明显。CuxS薄膜厚度对电池性能有很大的影响,结果表明,随着CuxS薄膜厚度增加,电池性能先增加后减少。薄膜厚度为75nm时,CdS/CdTe电池性能最佳,达到了最高转化效率(η)为12.19%,填充因子(FF)为68.82%,开路电压(Voc)为820mV。     

Fabrication procedures and process sensitivities for CdS/CdTe solar cells

This paper details the laboratory processes used to fabricate CdS/CdTe solar cells at the National Renewable Energy Laboratory. The basic fabrication technique includes low‐pressure chemical vapor deposited SnO₂ , chemical‐bath deposited CdS, close‐spaced sublimated CdTe, solution‐CdCl₂ treatment, and an acid‐contact etch, followed by application of a doped‐graphite paste. This paper also describes the results of a reproducibility study in which cells were produced by multiple operators with an average AM1·5 efficiency of 12·6%. And finally, this paper discusses process sensitivities and alternative cell fabrication procedures and reports the fabrication of a cell with an AM1·5 efficiency of 15·4%. Copyright © 1999 John Wiley & Sons, Ltd.     

Silicon thin‐film solar cells with rectangular‐shaped grating couplers

As an alternative to randomly textured transparent conductive oxides as front contact for thin‐film silicon solar cells the application of transparent grating couplers was studied. The grating couplers were prepared by sputtering of aluminium‐doped zinc oxide (ZnO) on glass substrate, a photolithography and a lift‐off process and were used as periodically textured substrates. The period size and groove depth of these transparent gratings were tuned independently from each other and varied between 1 and 4 μm and 100–600 nm. The optical properties of rectangular‐shaped gratings and the opto‐electronic behaviour of amorphous and microcrystalline silicon solar cells with integrated grating couplers as a function of the grating parameters (period size P and groove depth h_g) are presented. The optical properties of the gratings are discussed with respect to randomly textured substrates and the achieved solar cell results are compared with the opto‐electronic properties of solar cells deposited on untextured (flat) and randomly textured substrates. Copyright © 2005 John Wiley & Sons, Ltd.     

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.     

太阳电池中CdS薄膜的制备及其性能的研究

分别采用化学池沉积(CBD)和真空蒸发法,在三种衬底(玻片、ITO玻片、SnO2玻片)上沉积CdS薄膜,并利用扫描电镜(SEM)、透射光谱、X射线衍射(XRD)等方法对沉积膜进行了测试分析,同时阐述了两种不同方法下CdS膜的生长沉积机制。     

Bifacial concentrator Ag‐free crystalline n‐type Si solar cell

We report results obtained using an innovative approach for the fabrication of bifacial low‐concentrator thin Ag‐free n‐type Cz‐Si (Czochralski silicon) solar cells based on an indium tin oxide/(p⁺nn⁺)Cz‐Si/indium fluorine oxide structure. The (p⁺nn⁺)Cz‐Si structure was produced by boron and phosphorus diffusion from B‐ and P‐containing glasses deposited on the opposite sides of n‐type Cz‐Si wafers, followed by an etch‐back step. Transparent conducting oxide (TCO) films, acting as antireflection electrodes, were deposited by ultrasonic spray pyrolysis on both sides. A copper wire contact pattern was attached by low‐temperature (160°C) lamination simultaneously to the front and rear transparent conducting oxide layers as well as to the interconnecting ribbons located outside the structure. The shadowing from the contacts was ~4%. The resulting solar cells, 25 × 25 mm² in dimensions, showed front/rear efficiencies of 17.6–17.9%/16.7–17.0%, respectively, at one to three suns (bifaciality of ~95%). Even at one‐sun front illumination and 20–50% one‐sun rear illumination, such a cell will generate energy approaching that produced by a monofacial solar cell of 21–26% efficiency. Copyright © 2014 John Wiley & Sons, Ltd.     

Interface Engineering for Both Cathode and Anode Enables Low‐Cost Highly Efficient Solution‐Processed CdTe Nanocrystal Solar Cells

Low‐cost solution‐processed CdTe nanocrystal (NC) solar cells always suffer from a high interface energy barrier and unbalanced hole/electron transport as well as anisotropic atom diffusion on the CdTe surface due to the limited amount of hole/electron interface materials or the difficulty in interface processing. In this work, a novel strategy is first adopted with gradient electron transport layer (CdS/CdSe) modification in the cathode and a new crosslinkable hole transport polymer (P‐TPA) implantation in the anode. The carrier recombination at interfaces is greatly decreased and thus the carrier collection is increased. Moreover, the light harvesting is improved both in short and long wavelength regions, making J_sc and V_oc increase simultaneously. A champion solar cell shows a very high power conversion efficiency of 9.2% and an outstanding J_sc of 25.31 mA cm^?2, which are among the highest values for all solution‐processed CdTe NC solar cells with a superstrate structure, and the latter value is even higher than that of traditional thick CdTe thin‐film solar cells (2 µm) via the high temperature close space sublimation method. This work demonstrates that facile surface modifications in both the cathode and anode with stepped extraction and organic–inorganic hybridization are very promising in constructing next‐generation highly efficient NC photovoltaic devices.