Defect tolerance in as-deposited selenium-alloyed cadmium telluride solar cells

The efficiency of cadmium telluride (CdTe) solar cells is limited primarily by voltage, which is known to depend on the carrier concentration and carrier lifetimes within the absorber layer of the cell. Here, cathodoluminescence measurements are made on an as-deposited CdSeTe/CdTe solar cell that show that selenium alloyed CdTe material luminesces much more strongly than non-alloyed CdTe. This reduction in non-radiative recombination in the CdSeTe suggests that the selenium gives it a certain defect tolerance. This has implications for carrier lifetimes and voltages in cadmium telluride solar cells

Effect of CdCl2 passivation treatment on microstructure and performance of CdSeTe/CdTe thin-film photovoltaic devices

The effects of the CdCl2passivation treatment on thin-film CdTe photovoltaic films and devices have been extensively studied. Recently, with an addition of CdSeTe layer at the front of the absorber layer, device conversion efficiencies in excess of 19% have been demonstrated. The effects of the CdCl2passivation treatment for devices using CdSeTe has not been studied previously. This is the first reported study of the effect of the treatment on the microstructure of the CdSeTe /CdTe absorber. The device efficiency is < 1% for the as-deposited device but this is dramatically increased by the CdCl2treatment. Using Scanning Transmission Electron Microscopy (STEM), we show that the CdCl2passivation of CdSeTe/CdTe films results in the removal of high densities of stacking faults, increase in grain size and reorientation of grains. The CdCl2treatment leads to grading of the absorber CdSeTe/CdTe films by diffusion of Se between the CdSeTe and CdTe regions. Chlorine decorates the CdSeTe and CdTe grain boundaries leading to their passivation. Direct evidence for these effects is presented using STEM and Energy Dispersive X-ray Analysis (EDX) on device cross-sections prepared using focused ion beam etching. The grading of the Se in the device is quantified using EDX line scans. The comparison of CdSeTe/CdTe device microstructure and composition before and after the CdCl2treatment provides insights into the important effects of the process and points the way to further improvements that can be made

Investigations to improve CdTe-based solar cell open circuit voltage and efficiency using a passivation and selectivity theoretical framework

Includes bibliographical references.2022 Fall.The voltage of CdTe-based solar cells has remained conspicuously low despite years of efforts focused directly on its improvement. The efforts here have been primarily in increasing the equilibrium carrier concentration of the CdTe or its alloys which are used to absorb the light. This direction has been guided by a theory of solar cells that views the cell only as a single p/n junction. The modelling which has been used to confirm this as an appropriate direction indicated that with a moderate carrier lifetime, relatively small front interface recombination velocity, and large equilibrium carrier concentration in the absorber, efficiencies greater than the current record of 22.1% will be possible with open circuit voltages reaching over 1V. However, cells with these properties have been measured and increases in Voc and efficiency have not been attained. In the c-Si community, notably, the "passivation – selectivity" framework has been developed. In particular, it rejects the view that a singular p/n junction is responsible for the function of a solar cell. Instead, this framework operates with the understanding that the potential in the cell which can be turned into useful electrical energy and an increase in open circuit voltage comes only from the excess carriers generated by sunlight forcing a deviation from the equilibrium condition. As such there are two main components: 1) passivation – which refers to the recombination behavior in the cell and development of a large internal potential difference and 2) selectivity – which refers to the asymmetry of conduction in the cell that allows for production of a unidirectional current and an external voltage approaching that within the cell. This framework tends to break the cell into 3, sometimes overlapping, regions: an absorber region that is used to produce as large a potential difference as possible, and two contact regions in which the transport properties are modified to prefer transport of one carrier or the other. Here this framework is applied to CdTe-based solar cells to determine what limits current cells and how to overcome these limitations. In the investigation of passivation, first the electron contact interface is evaluated, resulting in the determination that this interface is not currently limiting the recombination in the cell. As a result, the current baseline is compared to structures hypothesized to provide improvement in the recombination behavior. It is found that cells with CdSeTe as the only material in the bulk exhibit more ideal recombination behavior when compared to a CdSeTe/CdTe structure as is currently used. This comparison demonstrates a pathway for cells to overcome their current limitation due to recombination, with the possibility of reaching up to 25% efficiency and 970 mV Voc with the material that currently is produced at CSU. A native oxide of TeOx is found to passivate the surface, reducing the rate non-radiative recombination, and forms during dry air exposure, providing a pathway to passivate contacts that would be ideal if not for the recombination at the interface. In the investigation related to selectivity, the electron contact is evaluated and it is demonstrated that MgZnO is appropriately selective when deposited with the correct conditions. It therefore is expected that hole selectivity is the primary loss to open circuit voltage in structures determined to have longer excess carrier lifetimes and large radiative efficiencies. Efforts to investigate novel routes to hole selectivity by use of heterojunction contacts are presented. Such routes did not yield improvements in cell Voc and efficiency, and through this work it was determined that a major source of selectivity losses in these cells is the high resistance to hole transport through the bulk semiconductor. Increasing hole concentration or thinning the absorber provide pathways to overcome this specific limitation, but it is modelled that such cells will require structures with hole selective materials that internally cause a reduction of electron current to see improvement in Voc and efficiency

Development and advancement of thin CdTe-based solar cells for photovoltaic performance improvements

2020 Fall.Includes bibliographical references.Photovoltaic technologies, with an essentially infinite energy source, large total capacity, and demonstrated cost competitiveness, are well-positioned to meet growing global demand for clean energy. Cadmium-telluride (CdTe) thin-film photovoltaics is advantageous primarily for its direct optical band gap (approximately 1.48 eV) which is well-matched to the standard AM 1.5G solar spectrum, and its high absorption coefficient. These advantages, in tandem with innovations in fabrication and photovoltaic design in the past decade, have significantly increased CdTe photovoltaic device performance and reduced cost. Major advances in CdTe device performance have been achieved through improved current collection and fill factor, however, the open-circuit voltage (VOC) of CdTe devices remains limited compared to the band gap-determined maximum achievable VOC. The voltage deficit could be minimized through various approaches, and this work addresses it through progressive structural changes to a thin CdTe device. Absorbers of less than 2 µm were pursued for ultimate electron-reflector devices which incorporate a wide band-gap material behind the absorber to induce a back-surface field via a back-side conduction-band offset for improved VOC. An optimized and stable base structure is necessary to quantify characteristics and improvements in progressive devices with additional material layers. Thin, 0.4-1.2 µm CdTe absorber devices were optimized and demonstrated respectable and repeatable performance parameters, and a maximum efficiency of 15.0% was achieved with only 1.2 µm CdTe. Capacitance measurements also showed that thinner devices had fully-depleted absorbers into forward bias. To improve device performance through increased current collection, a 1.4-eV band gap CdSeTe layer was introduced as an additional absorber material preceding CdTe. Prior understanding of the effects of the additional CdSeTe material was incomplete, and this work deepens and expands this understanding. Performance improvement was achieved for thin, 1.5-µm absorber devices with no intentional interdiffusion of the CdSeTe and CdTe. The importance of the CdSeTe thickness was demonstrated, where performance was consistently reduced for CdSeTe thickness greater than CdTe thickness, independent of CdSe composition in the close-space sublimation (CSS) CdSeTe source material. Longer time-resolved photoluminescence (TRPL) tail lifetimes in CdSeTe/CdTe devices compared to CdTe devices suggested better bulk properties, and current loss analysis showed that CdSeTe is the dominant absorber in 0.5-µm CdSeTe/1.0-µm devices. 1.5-µm CdSeTe/CdTe devices demonstrated increased current collection and 30-mV voltage deficit reduction due to the 100-meV narrower band gap of CdSeTe compared to CdTe and passivating effects of selenium, for an ultimate efficiency improvement to 15.6%. Lattice-constant matching to CdTe and wide, ~1.8-eV band-gap requirements directed the selection of CdMgTe as the electron-reflector layer. CdMgTe was incorporated into the CdSeTe/CdTe device structure first through CSS, but sputter deposition was found to be more favorable to address the material complexities of CdMgTe (temperature-induced magnesium diffusion and CdCl2 passivation loss, doping, and MgO formation), and produced higher performing CdMgTe electron-reflector devices. Low substrate temperature achievable in sputtered CdMgTe deposition proved the greatest advantage over CSS-CdMgTe: CdCl2 passivation and magnesium can be appropriately maintained with a corresponding maintenance of device performance, whereas temperature-induced CdCl2 passivation loss or magnesium loss will occur for CSS-deposited CdMgTe with incumbent performance reduction. Through low-temperature depositions, doping optimization, and small structural adjustments, 16.0% efficiency was achieved with CdMgTe sputtered on 0.5-µm CdSeTe/1.0-µm CdTe absorbers, the highest-known CdMgTe electron-reflector device performance. The CdMgTe and non-CdMgTe-containing device VOC's suggested that electron reflection was enacted with partial success for the sputter CdMgTe-incorporated structure, but the significant improvements expected based on simulation have not been realized due to MgO formation and a negative valence-band offset which somewhat impedes hole transport to the back contact. Suggestions to overcome or circumvent these limitations are presented and discussed in the context of progressed understanding of CdMgTe electron-reflector devices

How the selenium is affecting the physical and electrical properties of ultra-thin CdSeTe/CdTe solar cells

The incorporation of selenium into the CdTe has recently enhanced the performance of the solar cells to 23.1 %. The narrower band gap of the CdSeTe/CdTe absorber boosts the short-circuit current density; also, Se introduction increases the carrier's lifetime. Optimizing CdSexTe1-x band-grading is crucial for achieving highperformance CdTe photovoltaics. Another current goal is to reduce the thickness of the absorber to further reduce production costs and environmental impact. Thus, studying the effects of Se introduction in ultra-thin CdTe absorbers is essential. To investigate Se concentration's impact on ultra-thin CdTe, we fabricated CdSeTe/CdTe devices with an absorber thickness of 0.8 mu m by depositing different CdSe/CdTe ratios. Our 0.8 mu m thick cells have currently achieved an efficiency of 12.8 %, but most important this study shows that Se introduction in ultra-thin CdTe results in structural properties different from those of thicker absorbers, impacting the device performance

Polycrystalline CdSeTe/CdTe absorber cells with 28 mA/cm2 short-circuit current

An 800-nm CdSeTe layer was added to the CdTe absorber used in high-efficiency CdTe cells to increase the current and produce an increase in efficiency. The CdSeTe layer employed had a band gap near 1.41 eV, compared to 1.5 eV for CdTe. This lower band-gap allowed a current increase from approximately 26 to over 28 mA/cm2. Voltage same as earlier demonstrated high efficiency CdTe-only device was maintained. The fill-factor was not significantly affected. Improving the short-circuit current and maintaining the open-circuit voltage lead to device efficiency over 19%. QE implied that the approximately half the current was generated in the CdSeTe layer and half in the CdTe. Cross-section STEM and EDS showed good grain structure throughout and diffusion of Se into the CdTe layer was observed. To the best of authors’ knowledge this is the highest efficiency polycrystalline CdTe photovoltaic device demonstrated amongst universities and national labs

Development of ZnO Buffer Layers for As‐Doped CdSeTe/CdTe Solar Cells with Efficiency Exceeding 20%

The front buffer layer plays an important role in CdSeTe/CdTe solar cells and helps achieve high conversion efficiencies. Incorporating ZnO buffer layers in the CdSeTe/CdTe device structure has led to highly efficient and stable solar cells. In this study, the optimization of ZnO buffer layers for CdSeTe/CdTe solar cells is reported. The ZnO films are radio frequency sputter‐deposited on SnO2:F coated soda‐lime glass substrates. The substrate temperature for the ZnO deposition is varied from 22 to 500 °C. An efficiency of 20.74% is achieved using ZnO deposited at 100 °C. The ZnO thickness is varied between 40 nm and 75 nm. Following the ZnO depositions, devices were fabricated using First Solar's CdSeTe/CdTe absorber, CdCl2 treatment, and back contact. The optimal ZnO deposition temperature and thickness is 100 °C and 65 nm, respectively. The STEM‐EDX analysis shows that within the detection limits, chlorine is not detected at the front interface of the devices using ZnO deposited at 22 °C and 100 °C. However, depositing ZnO at 500 °C results in chlorine segregation appearing at the ZnO/CdSeTe boundary. This suggests that chlorine is not needed to passivate the ZnO/CdSeTe interface during the lower temperature depositions. The nanocrystalline ZnO deposited at lower temperatures results in a high‐quality interface

Investigation of Group V doping and passivating oxides to reduce the voltage deficit in CdTe solar cells

Includes bibliographical references.2022 Fall.Thin film cadmium telluride is one of the most successful photovoltaic technologies on the market today. Second only to silicon in yearly output and accounting for 40% of U.S. utility-scale photovoltaic installation, CdTe is known for its ease of manufacture, ideal bandgap, and low levelized cost of energy. Despite its commercial success, CdTe underperforms compared to its theoretical potential. The current world record CdTe device is only 21.0% compared to a theoretical maximum of 33.1%. This significant discrepancy in efficiencies can mostly be attributed to the poor open-circuit voltage of CdTe devices. Compared to silicon technologies, CdTe has a large voltage deficiency, exceeding 250 mV. While copper doping has traditionally been used for CdTe devices, it has proven to be incapable of sufficiently doping CdTe. Copper typically dopes CdTe in the 1014 to 1015 holes/cm3 range where most models predict that 1016–1017 is needed. Additionally, interstitial copper is a fast diffuser in CdTe, and can lead to numerous stability issues. As an alternative to copper, this work explores arsenic as a dopant for CdTe. Using a novel arsenic doping technique, hole concentrations greater than 1015 cm-3, microsecond lifetimes, and increased radiative efficiency are achieved. These are important prerequisites to achieving higher voltages. Achieving high doping levels alone is not sufficient to achieve higher device performance. A well-passivated and carrier selective contact is needed to ensure that electron-hole pairs do not recombine and are extracted as useable energy. Aluminum oxide has been shown to passivate CdTe surfaces. This work illustrates the explorations of using Al2O¬3 as a passivation layer, pairing it with highly doped amorphous silicon as a hole contact, resulting in excess-carrier lifetimes up to 8 µs, the highest reported to date for polycrystalline Cd(Se)Te. Although the inclusion of arsenic doping and an aluminum oxide back contact are each explored separately, the combination of both methods result in massive improvements to the carrier lifetime, interface passivation and radiative efficiency. Through this combination, microsecond lifetime and External Radiative Efficiency of over 4% are achieved. The excellent ERE values measured here are indicative of large quasi-Fermi level splitting, leading to an implied voltage with multiple device structures of nearly 1 V and an implied voltage of 25%. Finally, while CdSeTe serves as a more promising photovoltaic absorber candidate compared to CdTe, certain difficulties remain which must be addressed. Careful selection of processing conditions is shown to create a dense and large-grained film while eliminating wurtzite-phase crystal growth, which has been shown to degrade device performance. Surprisingly, as-deposited CdSeTe is shown to be n-type or nearly intrinsic rather than the previously supposed p-type. This necessitates additional steps to account for very poor hole conductivity, which can produce zero-current devices if not addressed. Challenges notwithstanding, CdSeTe absorbers are shown to be a key component in devices capable of a photovoltaic conversion efficiency of greater than 25%

Metal oxides as buffer layers in polycrystalline CdTe thin-film solar cells

2021 Fall.Includes bibliographical references.The optical band-gap of 1.5 eV and absorption coefficient the order of 105 cm-1 makes CdTea very attractive absorber for thin-film solar cells. This dissertation explores methods to improve both the front, or emitter, part of the cell and the back contact to the CdTe-based thin-film solar cells. The choice of an n-type emitter partner for CdTe based solar cells is crucial to the overall power conversion efficiency. In comparison to the traditional CdS emitter, metal oxides such as ZnO, MgO, and the ternary alloy MgxZn1-xO have large optical band-gaps making them transparent to most of the solar spectrum and an ideal emitter layer adjacent to light-facing side of the absorber in a superstrate configuration. The optical and electrical properties of MgxZn1-xO emitters can be modulated by varying the elemental ratio of x = Mg:(Mg + Zn) in the ternary alloy. Tracing the variation of the conversion efficiency as a function of Mg fraction in MgxZn1-xO emitter, an optimal Mg fraction of x = 0.15 was found to produce highest efficiency for the CdTe-based thin-film solar cells. Photoelectron spectroscopy demonstrated the conduction band offset at the emitter/absorber interface transitions from a cliff like -0.1 eV for x = 0.00 to a spike like 0.2 eV at the optimal x = 0.15. Photoluminescence and low-temperature current-voltage measurements showed that the interface between MgZnO and the CdSeTe is well passivated for x = 0.15. Further increase in the Mg fraction however increases the band offset between the emitter/absorber leading to distortions of J-V curves under various illumination conditions. Light soaking experiments and numerical simulations show that an insufficient density of carriers in the MgZnO due to the compensating defects causes these distortions: a failure of superposition of light and dark curves referred to as cross over, and distortion from normal current voltage behavior under spectra filtered illumination. An extrinsic doping of the emitter is critical to rectify these distortions and Ga-doped MgZnO was employed to experimentally demonstrate a cure to these J-V distortions characteristic of an undoped MgZnO emitter. It paves pathway to increase the n-type carrier density in the MgZnO emitter. The group-V doping of CdTe has shown potential to improve open circuit voltage, with level of doping in absorber the order of 1016 cm-3 and lifetimes of hundreds of ns. Numerical device simulations demonstrate that doping the emitter layer is essential and a particular challenge if the doping in the absorber is high. The results find the carrier concentration in emitter should be higher than the doping in the absorber to attain high open-circuit voltage in the highly doped CdTe-absorbers possible with arsenic doping. Various back contact metals like Ag, Co, Pt and metalloids like Te, and Se with different work functions were used to make an ohmic contact with the CdTe back surface. The use of a buffer layer behind the bare CdTe surface is found to be critical to the device performance. A thin 30-nm layer of Te have become the preferred choice of back buffer layer. Metal oxides like TeOx has been introduced as back buffer between the CdTe absorber and Te back contact to study their effect in device performance. The study finds that a double CdCl2 passivation procedure before and after the deposition of oxides is critical to the performance of these solar cells. Devices with the TeOx and the Te layer as back buffer demonstrated a power conversion efficiency in excess of 17 % without the incorporation of dopant in the absorber. Such a result is significant, as extrinsic dopants in CdTe-based absorbers often introduce defects in the absorber leading to increased recombination and degradation of cell performance particularly if the absorber is doped with Cu. Spectral and time resolved photoluminescence measurements carried out with illumination from front glass side show such cells have improved minority carrier lifetimes. The rear TRPL illumination to probe a CdTe/TeOx surface measured lifetimes of few ns indicative of the TeOx as a back buffer layer to mitigate the effects of large defects on a free CdTe surface. These results demonstrate metal oxides as a promising candidates for back buffer layers, and passivating back contact for hole selectivity in the CdTe-based solar cells

Advanced co-sublimation hardware for deposition of graded ternary alloys in thin-film applications

© 2018 IEEE. CdTe photovoltaic devices with efficiency over 22% have been demonstrated. Sublimated CdTe photovoltaics with efficiency over 19% have been reported using graded alloying of Se in CdTe absorber films. Grading of alloy films has been identified as an important characteristic to achieve higher device performance using more complex device structures. An advanced co-sublimation source has been designed and developed to deposit highly controlled CdTe based ternary alloys. An advanced shutter mechanism enables changing the composition of the deposited films during sublimation. The hardware used for advanced co-sublimation and initial materials characterization is presented in this study