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At least 91 records · Page 5

Electro-Optical Stability in Gallium Magnesium Zinc Oxide Layers for CdTe Solar Cells

In CdTe solar cells, the emitter electron density, bandgap, and band alignment can be tuned by adjusting alloy composition and stoichiometry in gallium magnesium zinc oxide (GMZO) layers, thereby allowing for critical front interface engineering. For example, computational modeling indicates efficiency can change from 7% to 25% by adjusting these buffer properties even with fixed CdSeTe and CdTe material properties. However, the GMZO as-deposited electro-optical properties can shift during subsequent CdTe deposition, CdCl 2 annealing, and solar cell operation. Here, we examine these changes by sputtering GMZO films on glass, and measuring the electron density before and after post-deposition treatments over a range of temperatures and different ambients. We then compare GMZO to SnO 2 and MZO. The addition of Ga to MgZnO is found to have profound effects on both the electron density and electro-optical stability that should be advantageous for CdTe solar cells.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Novel n-type Device Architectures to Achieve 1 Volt V OC in Thin Film CdTe cells

The main goal of this project was to develop a novel thin film CdTe solar cell architecture based on an n-type absorber, which can overcome performance limitations associated with the typical p-Cd(Se)Te state-of-the-art architecture. Even today, the performance of the Cd(Se)Te cell continues to be limited by its open- circuit voltage, which is directly related to the net doping of the absorber. (currently @ approx. 900 mV for CdTe/CST device configuration). The proposed polycrystalline thin- film solar cell architecture was based on n-type CdTe (and CdSeTe) absorbers to overcome this limitation, since n-type CdTe absorbers offer advantages over p-type: (i) n-type dopability in CdTe is higher (than p), enabling higher doping and therefore higher V OC (ii) using a wide bandgap material as the p-contact, the n-CdTe cell can become a “bi-facial” cell, with the potential to increase energy yield up to 25% depending on environmental and mounting conditions.

14 SOLAR ENERGY↗

Sb doping via drive-in diffusion as an alternative to in-situ doping in VTD

Group-V doping can enhance the efficiency of CdTe photovoltaic devices by increasing the open-circuit voltage (Voc), if long lifetimes can be retained and radiative voltage loss can be avoided. In this preliminary study, ex-situ Sb doping via drive-in diffusion improved grain sizes compared to Sb-free films without CdCl2 treatment. Sb doping did not reduce the carrier lifetime for uniform CdSeTe absorbers. Additionally, the CST-air surface recombination decreased with Sb. No potential fluctuations were observed by PL at this doping level. The [Sb] and carrier concentration for this study are not yet measured so the conclusions drawn are all preliminary

14 SOLAR ENERGY↗

Investigation of Sub‐Bandgap Emission and Unexpected n‐Type Behavior in Undoped Polycrystalline CdSe x Te 1‐x

Abstract Se alloying has enabled significantly higher carrier lifetimes and photocurrents in CdTe solar cells, but these benefits can be highly dependent on CdSe x Te 1‐x processing. This work evaluates the optoelectronic, chemical, and electronic properties of thick (3 µm) undoped CdSe x Te 1‐x of uniform composition and varied processing conditions (CdSe x Te 1‐x evaporation rate, CdCl 2 anneal, Se content) chosen to reflect various standard device processing conditions. Sub‐bandgap defect emission is observed, which increased as Se content increased and with “GrV‐optimized CdCl 2 ” (i.e., CdCl 2 anneal conditions used for group‐V‐doped devices). Low carrier lifetime is found for GrV‐optimized CdCl 2 , slow CdSe x Te 1‐x deposition, and low‐Se films. Interestingly, all films (including CdTe control) exhibited n‐type behavior, where electron density increased with Se up to an estimated ≈10 17 cm −3 . This behavior appears to originate during the CdCl 2 anneal, possibly from Se diffusion leading to anion vacancy (e.g., V Se , V Te ) and Cl Te generation.

14 SOLAR ENERGY↗

Investigating the Role of Copper in Arsenic Doped Cd(Se,Te) Photovoltaics

The open circuit voltage (VOC) deficit in Cd(Se,Te)-based photovoltaics remains a critical obstacle for pushing the technology closer to theoretical performance limits. Arsenic doping has become a dominant and promising route to achieve the higher p-type carrier concentrations necessary for higher VOC, but challenges associated with this alternate defect chemistry and higher doping density have hindered progress. Here we show that while arsenic doping enables high carrier concentrations (>1016 cm-3), co-doping with copper can provide a boost to VOC without a significant change to carrier concentration. A large data set is initially used to explore current-voltage and capacitance-voltage trends associated with arsenic doped devices with and without copper. A smaller subset is then used to probe these trends using a wide variety of characterization techniques. Copper is found to facilitate reduced interface recombination and potentially improved bulk absorber characteristics, though the mechanisms for these improvements are not yet clear. Despite the improved performance of co-doped devices, VOC is still far below its potential especially for highly doped devices. Low emitter doping in conjunction with high absorber doping seems to be a plausible cause for this significant deficit, though other device properties may exacerbate this problem.

CdSeTe↗

Effects of Absorber Near-Interface Compensation on Cd(Se,Te) Solar Cell Performance

Arsenic (As) has been shown to be an effective p-type dopant for CdTe, although high performance in As-doped devices remains difficult to achieve. Arsenic is prone to self-compensation in CdTe, as evidenced by the accumulation of dopant atoms in CdTe/Cd(Se,Te) near the interface with MgxZn1-xO (MZO). In this study, we use SCAPS 1D modeling software to investigate the effect of near-interface compensation, helping elucidate loss pathways in present-day As-doped devices and informing future growth directions. We consider three possible results of As accumulation: shallow donors, deep recombination centers, and a thin layer of excess acceptor accumulation. The reduction in near-interface carrier concentration caused by shallow donors is shown to improve open-circuit voltages (VOC), whereas deep levels are detrimental to all performance parameters. The thin charge layer affects capacitance-voltage (CV) measurements by reducing the depletion width while maintaining the same carrier concentration, replicating CV behavior that has been observed in actual devices. These results illustrate the importance of monitoring dopant accumulation within 100 nm of the interface, and suggest that reducing or eliminating the As concentration in this region would be beneficial. An undoped Cd(Se,Te) layer at the interface is suggested as a possible device structure to boost performance.

absorber↗

Imaging local luminescence variations in CdSe 0.1 Te 0.9 thin films grown by the colossal grain growth process

Clear visualization and understanding of luminescence properties of grain interiors and grain boundaries in polycrystalline thin-film photovoltaic materials are crucial to achieving high-performance solar cells. Luminescence-based measurements, for example, reveal sub-bandgap energetic disorder or impurity-related radiative transitions in these materials, and when performed in the absolute scale, they can show the extent of voltage-limiting non-radiative recombination. Here we use a hyperspectral imaging technique to investigate inter- and intra-grain photoluminescence variations in polycrystalline CdSe 0.1 Te 0.9 films made by the colossal grain growth process. We observe that grain boundaries show higher luminescence than grain interiors for all energies below the bandgap energy. Multiple distinct sub-bandgap defect transitions are detected and determined to be related to donor-acceptor pair impurities. A comparison of the excitation-intensity-dependent photoluminescence at the grain boundaries with grain interiors suggests that carrier concentration is higher at grain boundaries. This finding is supported by photoemission electron microscopy imaging of the films, showing approximately 70 meV upward energy shift in the band structure at the grain boundaries. Finally, we investigate a dramatic thermal quenching behavior related to the donor-acceptor pairs luminescence over a temperature range and use a rate-equation model to attribute it to the sudden redirection of the radiative recombination channels to non-radiative channels with increasing temperature.

14 SOLAR ENERGY↗

Impact of the Annealing Temperature on the Local Se Distribution and Optical Properties in CdSexTe1-x Solar Cells by Multimodal X-ray Microscopy

The introduction of Se in CdTe solar-cell absorbers has led to multiple beneficial effects in the devices, including an increased short-circuit current and an extended charge-carrier lifetime. A critical manufacturing step of CdSexTe1-x solar cells is CdCl2 annealing at high temperatures, during which Se diffuses through the absorber layer. Understanding the local Se distribution in the absorber and its impact on optical properties of the material is key for the further development of this thin-film solar cell technology. In a multimodal x-ray scanning microscopy approach, we investigated the impact of the annealing temperature of CdSexTe1-x solar cells on the Se distribution and on optical characteristics of the material. For this purpose, we exploited an upgraded x-ray excited optical luminescence (XEOL) detection unit that enables simultaneous spectrally and temporally resolved XEOL mapping at synchrotron facilities that are ideal for studying thin-film solar-cell materials with hard x-rays featuring high penetration depth and lateral resolution.

14 SOLAR ENERGY↗

Dual-Wavelength Time-Resolved Photoluminescence Study of CdSe x Te 1-x Surface Passivation via Mg y Zn 1-y O and Al 2 O 3

Voltage loss is currently one of the biggest challenges facing cadmium telluride (CdTe) based photovoltaics. Determining the location(s) of major voltage loss within the device stack (e.g., front/back interface, grain boundaries) is therefore of primary interest. Here, we present a custom-built time-resolved photoluminescence system with two excitation wavelengths - 670 (standard) and 405 nm - to probe the device stack at depths of approximately 130 and 35 nm, respectively; their comparison helps differentiate interface and bulk contributions to carrier lifetime. We apply this system to examine the passivation effect of two significant recent advances in CdTe: the incorporation of Se to form graded CdSe x Te 1-x and the replacement of CdS with Mg y Zn 1-y O. It is found that x = 0.2 Se is required to obtain lifetime improvements, primarily in the bulk. Additionally, evidence for trapping at the Mg y Zn 1-y O/CdSe x Te 1-x interface was observed. Furthermore, this indicates further work is required to sufficiently passivate the front interface.

CdSeTe↗

Carrier Lifetime as a Function of Se Content for CdSexTe1-x Films Grown on Al2O3 and MgZnO

Time-resolved photoluminescence (TRPL) with two excitation wavelengths – 670 (standard) and 405 nm – was used to examine the effect on carrier lifetime of two significant recent advances in CdTe: the incorporation of Se to form graded CdSe x Te 1-x and the use of Mg y Zn 1-y O buffers. The two excitation wavelengths probe depths of approximately 130 and 35 nm, respectively, and their comparison helps differentiate interface and bulk contributions to carrier lifetime. It was found that x = 0.2 Se was required to obtain lifetime improvements, primarily in the bulk. Additionally, TRPL traces for Mg y Zn 1-y O/CdSe x Te 1-x samples showed fast initial decay followed by a long-lived tail, which may be indicative of trap-dominated recombination. This behavior was not present for CdSe x Te 1-x films grown on Al 2 O 3 , which is currently state-of-the-art for surface passivation in CdTe. This indicates that further work is required to sufficiently passivate the front interface.

cadmium telluride↗

Optimization of Source Material for in-situ Arsenic Doping via Vapor Transport Deposition of CdTe Films

In-situ doping of CdTe/CdSeTe films with arsenic is performed using pre-doped source material prepared by high pressure Bridgman (HPB) melt growth. Arsenic level in the source material is varied from 1018-1020 cm-3. Correspondingly, dopant incorporation in the films prepared using vapor transport deposition (VTD) varied from 3x1017 cm-3–1x1018cm-3. In this range, dopant activation is found to inversely correlate with the dopant incorporation, suggesting compensation. The results from this study indicate film properties can be adjusted by source material.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Developing CdTe homojunctions applying high throughput deposition

In this project, we attempted to make CdTe homojunctions using single crystal p-type doped substrates and closed-space sublimation epitaxy (CSSE) n-type doped films. The project included modeling which determined the ideal thickness for the n-type layer as being <200 nm. Boules of high concentration indium-doped CdTe and CdSe 0.4 Te 0.6 (CST) were grown using modified vertical Bridgman (MVB) methods. Similarly, iodine-doped CdTe crystals were grown for the first time. Washington State University (WSU) stock phosphorus-doped CdTe was used as the p-type substrate layer. The crystals were characterized by Hall effect and time-resolved photoluminescence (TRPL, for electrical properties), photoluminescence microscopy (for uniformity), X-ray diffraction (for crystal structure), and glow discharge mass spectrometry (GDMS, for dopant and impurity concentration). CdTe:I crystals were also characterized by visible and infrared transmission measurements, and various Cd or Te heat treatments were performed to assess changes in optical and electrical properties. The grown n-type materials – CdTe:In, CdSe0.4Te0.6:In, and CdTe:I – were provided to the National Renewable Energy Laboratory (NREL) for growth of CSSE thick films for characterization by two photon TRPL (for carrier lifetime), electron back-scatter diffraction (EBSD, to assess epitaxy), and Hall effect. Several measurements of secondary ion mass spectroscopy (SIMS) were performed. Nearly 100% of the indium from the crystal was incorporated into the measured thick films, while only ~2-22% of the iodine from the crystal was incorporated. The net result of the diffusion issue is that homojunction devices created using CSSE have a buried homojunction, as indicated by the near infrared peak in the external quantum efficiency (EQE). Various parameterization of front and back contacts suggested that the poor device performance was primarily a result of this buried junction and not due to other effects. There may also be an issue with the CSSE film lifetime in addition to the dopant profile.

14 SOLAR ENERGY↗

Development of High-Quality, Very Large-Grained Cd(Se,Te) Thin Films for CdTe Solar Modules (Final Technical Report)

TCF-21-25048 is a one-year project to quantify the potential attributes of recent NREL inventions where CdTe devices with grain sizes exceeding 100's of microns in lateral dimension can be fabricated using a novel seeded-epitaxial process. A CdSe0.1Te0.9 film is evaporated on commercially available transparent conducting oxide (TCO) where the latter surface roughness (Ra) has been reduced to < 1-nm. After NREL's colossal grain growth (CGG) process, the grain size of this "seed" layer is increased to 100-1000 um. CdTe is then deposited epitaxially resulting in a large-grain CdTe device structure without use of CdCl2. As of this report, we have: Demonstrated the feasibility of using Tec-15 substrates after surface roughness (Ra) reduction (nexTC); Developed reproducible CGG processes for this commercially available substrate; Developed a close-spaced sublimation (CSS) process for CdTe epitaxy using these substrates; Demonstrated that large-grain CdTe films have less sub-band (band tail) absorption than conventional, small-grain CdTe; Demonstrated that large-grain CdTe films (no CdCl2) have carrier lifetimes up to 1.5 ns; Demonstrated that carrier lifetimes in epi-CdTe films (no CdCl2) have comparable lifetimes when compared to the best pX-CdTe films (FSLR) treated with CdCl2; Started making large-grain CdTe devices using CGG templates and epitaxially deposited CdTe.

14 SOLAR ENERGY↗

Understanding Defect Activation and Kinetics in Next Generation CdTe Absorbers

This project investigated the role of defects and dopants in cadmium telluride (CdTe) solar cells to improve efficiency and long-term stability. Advanced X-ray microscopy and spectroscopy techniques were used to map composition, identify defect structures, and measure charge collection at the nanoscale. These experimental results were combined with computational modeling to understand how dopants such as copper and arsenic interact with other elements during processing. The study found that many dopants become electrically inactive due to the formation of complexes with chlorine and oxygen, limiting carrier concentration and device performance. It also showed that selenium, used to enhance efficiency, can migrate within the material during both manufacturing and operation, altering local structure and potentially affecting stability. The project developed new diagnostic and analysis tools for studying photovoltaic materials and provided a mechanistic understanding of key performance limitations. These insights support the development of more efficient, stable, and cost-effective CdTe solar technologies for large-scale energy deployment.

14 SOLAR ENERGY↗

Emitter Reconstruction for Cleaved CdSexTe1-x Devices with Cu vs. As Doping

CdTe absorbers have had historically low carrier densities of ~10^14 cm-3 due to the self-compensating nature of copper dopants. Recent advances in group-V (e.g., arsenic) doping have increased this to 10^16-10^17 cm-3, but modeling suggests that the front interface and emitter properties become limiting in this case. By cleaving arsenic- and copper-doped CdTe device stacks at the emitter/absorber interface, we gain the ability to reconstruct emitters with known properties, which will not change during subsequent device processing, and directly test the modeling. By doing so, we find a much larger performance drop in arsenic devices; this is attributed to insufficient electron density in the emitter and increased sensitivity to interface changes due to collapsed depletion width. This work can help guide emitter engineering for highly-doped CdTe devices in both the as-grown-superstrate- and cleaved-substrate configurations.

As-doped↗