Top Cell Research Articles

Halogenated Polycyclic Aromatic Hydrocarbon for Hole Selective Layer/Perovskite Interface Modification and Passivation for Efficient Perovskite‐Organic Tandem Solar Cells with Record Fill Factor

AbstractPerovskite whentandemed with organic photovoltaics (OPV) for double‐junctions have efficiencypotentials over 40%. However, there is still room for improvement suchas better current matching, higher fill factor, as well as lower voltage and fill factor losses in the top perovskite cell. Here weaddress the issue associated with the top perovskite cell by utilising anovel halogenated polycyclic aromatic hydrocarbon compound, 1‐naphthylammoniumchloride (NA─Cl) playing dual roles of surface modification for the hole selectivelayer (HSL) and passivation of HSL/perovskiteinterface. Results of X‐ray photoelectron spectroscopy and density functionaltheory calculations reveal that NA─Cl retains self‐assembly property for the HSLwhile demonstrating high dipole moment and polarizability. This induces asurface dipole at the HSL/perovskite interface reducing the energetic barrierfor hole extraction by 210 meV thereby enhancing voltage output and fill factorof the device. Such scheme when implemented in a high bandgap (1.78 eV)perovskite solar cell, results in a respectable efficiency of 19.7% and thehighest fill factor of 85.4% amongst those of 1.78 eV perovskite cells reported.We have also achieved 23% cell efficient monolithic perovskite‐OPV tandem withan impressive fill factor of 84%, which is the highest for perovskite‐OPVtandem cells reported to‐date.

Perovskite/Silicon Tandem Solar Cells Above 30% Conversion Efficiency on Submicron-Sized Textured Czochralski-Silicon Bottom Cells with Improved Hole-Transport Layers.

In perovskite/silicon tandem solar cells, the utilization of silicon heterojunction (SHJ) solar cells as bottom cells is one of the most promising concepts. Here, we present optimization strategies for the top cell processing and their integration into SHJ bottom cells based on industrial Czochralski (Cz)-Si wafers of 140 μm thickness. We show that combining the self-assembled monolayer [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) with an additional phosphonic acid (PA) with different functional groups, can improve film formation when used as a hole transport layer improving wettability, minimizing shunt fraction and reducing nonradiative losses at the buried interface. Transient surface photovoltage and transient photoluminescence measurements confirm that the combined Me-4PACz/PA layer has similar charge transport properties to Me-4PACz alone. Moreover, this work demonstrates the potential for thin, double-side submicron-sized textured industry-relevant silicon bottom cells yielding a high accumulated short-circuit current density of 40.2 mA/cm2 and reaching a stabilized power conversion efficiency of >30%. This work paves the way toward industry-compatible, highly efficient tandem cells based on a production-compatible SHJ bottom cell.

Tuning Perovskite Crystal Growth Dynamics Using Additives on Textured Silicon Substrates

Double‐sided textured silicon solar cells with micrometer‐sized pyramid structure are used as bottom cells in monolithic tandem structures to decrease reflection losses. As top cell material, frequently perovskites are used. In this work, various additives are investigated to enhance the perovskite absorber quality, as a top cell fabricated using the hybrid route. In the context of the hybrid route, it is found that urea or methylammonium chloride (MACl) can effectively increase the grain size and improve the absorber quality, while formamidinium chloride (FACl) cannot. With urea, the crystallization can be tuned without leaving any voids in the film (unlike MACl). However, when annealed at a high annealing temperature, the excessive crystal growth with urea causes non‐conformal coating and high defect density. By adjusting the annealing conditions and additive concentration, the crystal growth of the perovskite top cell on the micrometer‐sized silicon pyramids can be fine‐tuned, ensuring that the perovskite layer conformally coated the pyramids. The use of additives not only improves crystallization but also enhances the conversion of the inorganics, particularly at the hole transport layer (HTL) interface. Moreover, this work contributes to a better understanding of perovskite crystallization dynamics and how to control it, especially on textured substrates.

Efficient wide-bandgap perovskite photovoltaics with homogeneous halogen-phase distribution

Wide-bandgap (WBG) perovskite solar cells (PSCs) are employed as top cells of tandem cells to break through the theoretical limits of single-junction photovoltaic devices. However, WBG PSCs exhibit severe open-circuit voltage (Voc) loss with increasing bromine content. Herein, inhomogeneous halogen-phase distribution is pointed out to be the reason, which hinders efficient extraction of carriers. We thus propose to form homogeneous halogen-phase distribution to address the issue. With the help of density functional theory, we construct a double-layer structure (D-2P) based on 2-(9H-Carbazol-9-yl)ethyl]phosphonic acid molecules to provide nucleation sites for perovskite crystallization. Homogeneous perovskite phase is achieved through bottom-up templated crystallization of halogen component. The efficient carrier extraction reduces the Shockley-Read-Hall recombination, resulting in a high Voc of 1.32 V. As a result, D-2P-treated device (1.75 eV) achieves a record power conversion efficiency of 20.80% (certified 20.70%), which is the highest value reported for WBG (more than 1.74 eV) PSCs.

Improving current-matching in textured perovskite/silicon tandem solar cells via a thickness control strategy

This study presents an analysis of a two-terminal tandem solar cell that integrates metal-doped, lead-free double Cs2AgBi0.75Sb0.25Br6 perovskite with silicon to enhance overall energy conversion efficiency. This study explores how the thicknesses of the top and bottom sub-cells affect current-matching in two-terminal tandem perovskite/silicon solar cells with two separate planar and textured configurations. Using numerical modeling in MATLAB, and considering dominant recombination effects, we calculated the performance parameters of the device. We investigated the optical and electrical properties of textured tandem structures, focusing on current- matching and the influence of layer thickness on device performance. Given the complexity, time, and expense involved in constructing tandem solar cells, being able to analytically determine the thickness at which current-matching occurs can be highly advantageous. This approach offers the benefit of providing a precise analytical relationship for this purpose. Our findings demonstrate that increasing the top cell thickness enhances current density and power conversion efficiency, but at the cost of the bottom cell’s efficiency due to increased light absorption. Moreover, we discovered a nearly linear behavior between the thickness of the top and bottom cells for achieving current-matching. The study highlights the critical balance required to optimize layer thicknesses, thereby improving the design and performance of tandem solar cells. These insights are significant as they pave the way for more efficient and cost-effective tandem solar cell designs in the future, potentially accelerating the adoption of advanced photovoltaic technologies. The results show good agreement with experimental data, validating our model.

Performance Enhancement of Hole Transport Layer-Free Carbon-Based CsPbIBr2 Solar Cells through the Application of Perovskite Quantum Dots.

CsPbIBr2, with its suitable bandgap, shows great potential as the top cell in tandem solar cells. Nonetheless, its further development is hindered by a high defect density, severe carrier recombination, and poor stability. In this study, CsPbI1.5Br1.5 quantum dots were utilized as an additive in the ethyl acetate anti-solvent, while a layer of CsPbBr3 QDs was introduced between the ETL and the CsPbIBr2 light-harvester film. The combined effect of these two QDs enhanced the nucleation, crystallization, and growth of CsPbIBr2 perovskite, yielding high-quality films characterized by an enlarged crystal size, reduced grain boundaries, and smooth surfaces. And a wider absorption range and better energy band alignment were achieved owing to the nano-size effect of QDs. These improvements led to a decreased defect density and the suppression of non-radiative recombination. Additionally, the presence of long-chain organic molecules in the QD solution promoted the formation of a hydrophobic surface, significantly enhancing the long-term stability of CsPbIBr2 PSCs. Consequently, the devices achieved a PCE of 9.20% and maintained an initial efficiency of 85% after 60 days of storage in air. Thus, this strategy proves to be an effective approach for the preparation of efficient and stable CsPbIBr2 PSCs.

One-Stone-for-Multiple-Birds Additive Strategy for Highly Efficient and Stable Carbon-Based Hole-Transport-Layer-Free CsPbI2Br Solar Cells.

During fabrication and operation of perovskite solar cells (PSCs), defects commonly arise within the crystals as well as at grain boundaries. However, conventional additive strategies typically only serve to mitigate the occurrence of a single defect and fail to significantly enhance device performance. Herein, carbon-based hole-transport-layer-free CsPbI2Br devices are focused on, one kind of important PSCs with more stable structure and an appropriate bandgap for a semitransparent solar cell or a top cell in a tandem configuration, and present a highly efficient one-stone-for-multiple-birds additive strategy based on lanthanide trifluoromethanesulfonates (Ln(OTF)3, Ln: neodymium (Nd), europium (Eu), dysprosium (Dy), thulium (Tm)). Density functional theory calculations reveal that the Ln3+ ions with a smaller radius can elevate defect formation energy for Pb and I vacancies within the crystals, while the presence of OTF- can effectively passivating uncoordinated Pb2+ at grain boundaries. In addition, Ln(OTF)3 addition increases the grain size and meanwhile reduces the surface roughness of the CsPbI2Br layers. All these positive contributions lead to a significant enhancement in power conversion efficiency (PCE) to 15.13% which is among the top PCEs reported for the corresponding solar cells, from 11.80% of the pristine device without Tm(OTF)3 addition, while notably boosting long-term stability and reducing current-voltage hysteresis.

A Prediction of All-Inorganic Lead-Free Halide Perovskites for Photovoltaic Application: Rb3Mo2Br9 and Rb3Mo2Cl9.

Lead-based organic-inorganic hybrid perovskites show promise as photovoltaic materials due to their high energy conversion efficiencies. However, concerns regarding lead toxicity and the poor environmental and operational stability of the organic cationic group have limited their widespread application. To address these challenges, the design of all-inorganic lead-free halide perovskites offers potential solutions for photovoltaic applications. Here, two layered perovskite derivatives, Rb3Mo2Cl9 and Rb3Mo2Br9, are explored, and their electronic, structural, and photovoltaic properties are analyzed using advanced theoretical calculations. Rb3Mo2Br9 exhibits a suitable direct bandgap of 1.60eV, making it a promising candidate for use as a light absorber in low-cost, high-efficiency solar cells. On the other hand, Rb3Mo2Cl9 demonstrates a wide direct bandgap exceeding 1.70eV, positioning it as a viable option for use as a top cell in tandem photovoltaic systems alongside silicon. Both materials display ideal optical properties in the visible light region and hold promise as excellent inorganic lead-free perovskite alternatives.

Effect of Ga Variation on the Bulk and Grain‐Boundary Properties of Cu(In,Ga)Se2 Absorbers in Thin‐Film Solar Cells and Their Impacts on Open‐Circuit Voltage Losses

ABSTRACTPolycrystalline widegap Cu(In,Ga)Se2 (CIGSe) absorbers for top cells in photovoltaic tandem devices can be synthesized via [Ga]/([Ga] + [In]) (GGI) ratios of > 0.5. However, the power conversion efficiencies of such high‐GGI devices are smaller than those of the record cells with GGI < 0.5. In the present work, the effects of the GGI ratio on various CIGSe material properties were studied and correlated with the radiative and nonradiative open‐circuit voltage (VOC) deficits of the thin‐film solar cells. Average grain sizes, grain boundary (GB) recombination velocities, fluctuations in luminescence energy distribution, barrier heights at GBs, effective electron lifetimes, and Urbach energies were investigated in five solar cells with GGI ratios from 0.13 to 0.83. It was found that the GGI variation affects GB recombination velocities, fluctuations in spatial luminescence distributions, the average grain size, the electron lifetime, and the Urbach energy. In contrast, the detected ranges of barrier heights at GBs are independent of the GGI ratio. Mainly Ga/In gradients give rise to substantial radiative VOC losses in all solar cells. Nonradiative VOC deficits are dominant especially for solar cells with GGI > 0.5, which can be attributed to low bulk lifetimes and enhanced recombination at GBs in CIGSe absorbers in this compositional range.

Highly passivated TOPCon bottom cells for perovskite/silicon tandem solar cells

Tunnel oxide passivated contact (TOPCon) silicon solar cells are rising as a competitive photovoltaic technology, seamlessly blending high efficiency with cost-effectiveness and mass production capabilities. However, the numerous defects from the fragile silicon oxide/c-Si interface and the low field-effect passivation due to the inadequate boron in-diffusion in p-type polycrystalline silicon (poly-Si) passivated contact reduce their open-circuit voltages (VOCs), impeding their widespread application in the promising perovskite/silicon tandem solar cells (TSCs) that hold a potential to break 30% module efficiency. To address this, we have developed a highly passivated p-type TOPCon structure by optimizing the oxidation conditions, boron in-diffusion, and aluminium oxide hydrogenation, thus pronouncedly improving the implied VOC (iVOC) of symmetric samples with p-type TOPCon structures on both sides to 715 mV and the VOC of completed double-sided TOPCon bottom cells to 710 mV. Consequently, integrating with perovskite top cells, our proof of concept of 1 cm2 n-i-p perovskite/silicon TSCs exhibit VOCs exceeding 1.9 V and a high efficiency of 28.20% (certified 27.3%), which paves a way for TOPCon cells in the commercialization of future tandems.

A Broadband Light‐Trapping Nanostructure for InGaP/GaAs Dual‐Junction Solar Cells Using Nanosphere Lithography‐Assisted Chemical Etching

III–V‐based multijunction solar cells have become the leading power generation technology for space applications due to their high power conversion efficiency and reliable performance in extraterrestrial environments. Thinning down the absorber layers of multijunction solar cells can considerably reduce the production cost and improve their radiation hardness. Recent advances in ultrathin GaAs single‐junction solar cells suggest the development of light‐trapping nanostructures to increase light absorption in optically thin layers within III–V‐based multijunction solar cells. Herein, a novel and highly scalable nanosphere lithography‐assisted chemical etching method to fabricate light‐trapping nanostructures in InGaP/GaAs dual‐junction solar cells is studied. Numerical models show that integrating the nanostructured Al2O3/Ag rear mirror significantly enhances the broadband absorption within the GaAs bottom cell. Results demonstrate that the light‐trapping nanostructures effectively increase the short‐circuit current density in GaAs bottom cells from 14.04 to 15.06 mA cm−2. The simulated nanostructured InGaP/GaAs dual‐junction structure shows improved current matching between the GaAs bottom cell and the InGaP top cell, resulting in 1.12x higher power conversion efficiency. These findings highlight the potential of light‐trapping nanostructures to improve the performance of III‐V‐based multijunction photovoltaic systems, particularly for high‐efficiency applications in space.

Engineering Coatings Inspired by Cell Membrane Thermal Dynamics to Enhance Photothermal Therapy and Osteogenesis for Implant Infections.

Photothermal therapy (PTT) encounters challenges of rapid thermal loss and potential tissue damage. In response, we propose a Heat-Boost and Lock implant coating strategy inspired by the thermal adaptation of biological membranes, enabling precise local photothermal utilization. This coating incorporates a poly(tannic acid) (pTA) bridging layer on implants, facilitating stable layer-by-layer integration of a black phosphorus (BP) photothermal layer and a top cell membrane Heat-Boost and Lock layer. The cell membrane layer significantly curtails photothermal loss (extending the heat retention by 17.62%) and stores energy within its phospholipid bilayer, boosting photothermal effects near implants (achieving a temperature increasement of 275%). Theoretical analysis indicates that these local heat preservation properties of the cell membrane arise from its low thermal conductivity and phase-change properties. In a Staphylococcus aureus-infected bone implant model, our coating demonstrates precise antibacterial action around implants (reach an antibacterial ratio of 99.52%). The synergetic locking function of cell membrane and pTA delays BP biodegradation, ensuring favorable photothermal stability and long-term osteo-inductive performance (increasing the bone volume fraction by 53.45%). Beyond providing an endogenic biointerface, this strategy extends the application of cell membrane in local thermal management, offering possibilities for effective and safe PTT modalities.

Optical Simulations of Nanotextured All‐Perovskite Tandem Solar Cells

AbstractThis numerical study investigates, how textures at various locations of all‐perovskite tandem solar cells affect their optical performance. For this, hexagonal sinusoidal textures with 750 nm period and aspect ratios (height‐to‐period) of 27% (moderate) and 54% (pronounced) are considered. The optical simulations are performed with the finite element method and an algorithm to correct for the thick glass superstrate. The complex refractive index data of the wide‐bandgap (WBG) and narrow‐bandgap (NBG) perovskites with spectroscopic ellipsometry is determined. Texturing between the glass superstrate and the WBG perovskite top cell has an antireflective effect across the whole wavelength region. In contrast, texturing between the WBG perovskite top cell and the NBG perovskite bottom cell has no additional effect for a moderate texture but leads to light trapping in the NBG perovskite for a pronounced texture. Moderate texturing between the NBG perovskite absorber and the metal back contact leads to light trapping in the NBG perovskite but also excites surface plasmons in the copper back contact. Dielectric interlayers between the NBG perovskite and the metal back contact can reduce the plasmonic absorption losses. Texturing potentially allows to increase the current‐matched short‐circuit current density beyond 17 mA .

Unveiling recombination in top cells: SCAPS-1D simulations for high-efficiency bifacial planar perovskite/silicon tandem solar cells

Bifacial two-terminal (2T) perovskite/silicon tandem solar cells (TSCs) can enhance the current matching by utilizing albedo, thereby achieving higher power generation densities (PGDs) compared to their monofacial counterparts. Nevertheless, the PGDs of recently fabricated bifacial TSCs lag considerably behind the theoretical limit, primarily attributed to recombination losses in the top perovskite solar cells (PSCs). Herein, we model a bifacial planar perovskite/silicon 2T TSC using SCAPS-1D and analyze how radiative, Shockley-Read-Hall (SRH), Auger, and interface recombination in the PSC constrain the PGD of the bifacial 2T TSC under current matching/pseudo-matching conditions. Our findings indicate that recombination influences the PGD in the following order: interface (ETL/PVSK) > SRH > radiative > Auger > interface (PVSK/HTL). Furthermore, PGD losses escalate significantly with increasing albedo due to radiative/SRH recombination. Ultimately, we achieve a PGD of 30.45–39.90 mW/cm2 by mitigating all recombination channels, representing a 13.14–21.87 % increase over the initial device. This study offers guidance for developing bifacial 2T TSCs with improved efficiency.

Toward sustainable manufacturing of highly efficient and stable semi-transparent perovskite solar cells: The critical role of green solvent properties

Perovskite solar cells, promising a bright future in the energy market, are now being prioritized for high-throughput production to match their remarkable success at the laboratory scale. However, the use of toxic solvents proved to be one of the major constraints on scaling up production. Herein, a green solvent system consist of dimethyl sulfoxide (DMSO) and 1-dodecyl-3-methylimidazolium chloride ([C12MIM]Cl) ionic liquids (ILs) was developed to modulate the crystallization of wide-bandgap (WBG) perovskite films combined with a antisolvent-free process, i.e., nitrogen (N2) quenching method. The [C12MIM]Cl IL promoted the crystallization of WBG perovskite films with large grain sizes, reduced photo-active PbI2, modulated residual strain, prolonged carrier lifetimes as well as improved energy alignment. Consequently, the [C12MIM]Cl-modified single-junction 1.77 eV perovskite solar cells (PSCs) achieved a champion efficiency of 18.75 % with an excellent operational stability, retaining an initial PCE of 93 % after 2000 h of maximum-power-point tacking test. Meanwhile, the positive effect of the [C12MIM]Cl ILs was universal in perovskite with different bandgaps at 1.53, 1.68 and 1.72 eV, respectively. Furthermore, stacking semi-transparent [C12MIM]Cl-modified 1.77 eV WBG PSCs as top cells coupled with 1.27 eV OPV or 1.24 eV Sn-Pb PSC as bottom cells for the 4 T tandem configuration showed impressive PCE of 26.01 % and 27.44 %, respectively. This study opens a new avenue toward the sustainable fabrication of highly efficient and stable perovskite-based semitransparent and tandem solar cells.

Device Simulation of 25.9% Efficient ZnOxNy${\rm ZnO}_x{\rm N}_y$/Si Tandem Solar Cell

AbstractThe novel, high electron mobility material has been investigated theoretically as an absorber in a two‐terminal tandem solar cell. In addition to its high mobility, can attain sufficiently low carrier concentration to enable ‐junctions, and has a tunable bandgap around the 1.7 eV range. It is therefore suitable for pairing with a Si‐based bottom cell. In addition to the layer, the tandem cell consists of a emitter and a Si heterojunction bottom cell. A buffer layer is introduced between the emitter and absorber in the top cell to mediate a large valence band offset that resulted in a poor fill factor, . A buffer layer bandgap of 1.5 eV gave the highest power conversion efficiency (PCE). The objective is to estimate the optimal performance of in a tandem solar cell. The dependence of current–voltage (–) characteristics on thickness, mobility and carrier concentration in the layer is evaluated, and found to yield maximum performance with 0.35 , 250 Vs–1 and , respectively. Using these conditions, the – parameters of the device under AM1.5 illumination are short circuit current density, mA , open circuit voltage, V, and . With this, it is reported on, to the best of the knowledge, the first device simulation based on .

Enhancing efficiency in a-Si:H/μc-Si micromorph tandem solar cells through advanced light-trapping techniques using ARC, TRJ, and DBR

In this study, the performance of a-Si:H/μc-Si:H tandem solar cells was comprehensively assessed through two-dimensional numerical simulations. Our work involved optimizing the layer thicknesses and exploring advanced light-trapping techniques to enhance photogenerated current in both sub-cells. To reduce surface reflections on the top cell, we proposed a two-layer antireflection coating, composed of SiO2/Si3N4. Additionally, we implemented a 1D photonic crystal as a broadband back reflector within the solar cell. In order to balance the current density between the sub-cells and prevent carrier accumulation at the interface, we introduced a tunnel recombination junction (TRJ). This TRJ consisted of n-μc-Si:H/p-μc-Si:H layers with a thickness of 10 nm. Under global AM 1.5G conditions, our proposed cell structure exhibited impressive electrical characteristics, including an open-circuit voltage of 1.38 V, a short-circuit current density of 12.51 mA/cm2, and a fill factor of 80.82%. These attributes culminated in a remarkable total area conversion efficiency of 14%.

Current matching and filtered spectrum analysis of wide-bandgap/narrow-bandgap perovskite/CIGS tandem solar cells: A numerical study of 34.52 % efficiency potential

Perovskite (PVK) materials with wide-bandgap (WBG) play a crucial role in achieving high-performance tandem devices but phase segregation and open-circuit voltage (VOC) loss hinders in surpassing the efficiency of single-junction solar cells. Present work discloses a numerical simulation which has been carried out using a WBG material CH3NH3PbI3-xClx of bandgap (Eg) 1.65eV as an absorber layer of the top cell (TCELL) and a Cu(In,Ga)Se2-based cell having narrow-bandgap (NBG) of Eg (1.27eV) has been used as bottom cell (BCELL). The TCELL utilizes polyethyleneimine ethoxylated (PEIE) interfacial layer to promote charge-collection and charge-tunneling. The TCELL and BCELL have been optimized by various optimization processes such as simultaneous thickness variation of active-region with defect density (DD), variation of interface defect density (IDD) with solar-cell parameters a commendable power conversion efficiency (PCE) of 27.06 %, and 26.77 % has been achieved for respective solar-devices. Variations of numerous electron transport layer (ETL) and hole transport layer (HTL) have also been performed to acquire highly optimized TCELL. Thus, a perovskite/CIGS tandem solar cell (PVK/CIGS-TSC) device has been obtained using filtered-spectra analysis and current-matching (method which display a promising photovoltaic (PV) parameter with a high VOC of 2.29 V, short-circuit current density (JSC) of 17.41 mA/cm2, fill factor (FF) of 86.45 % and PCE of 34.47 %. These discoveries hold significant promise for the future development of TSCs.

Additive engineering for efficient wide-bandgap perovskite solar cells with low open-circuit voltage losses.

High-performance wide-bandgap (WBG) perovskite solar cells are used as top cells in perovskite/silicon or perovskite/perovskite tandem solar cells, which possess the potential to overcome the Shockley-Queisser limitation of single-junction perovskite solar cells (PSCs). However, WBG perovskites still suffer from severe nonradiative recombination and large open-circuit voltage (Voc) losses, which restrict the improvement of PSC performance. Herein, we introduce 3,3'-diethyl-oxacarbo-cyanine iodide (DiOC2(3)) and multifunctional groups (C=N, C=C, C-O-C, C-N) into perovskite precursor solutions to simultaneously passivate deep level defects and reduce recombination centers. The multifunctional groups in DiOC2(3) coordinate with free Pb2+ at symmetric sites, passivating Pb vacancy defects, effectively suppressing nonradiative recombination, and maintaining considerable stability. The results reveal that the power conversion efficiency (PCE) of the 1.68eV WBG perovskite solar cell with an inverted structure increases from 18.51% to 21.50%, and the Voc loss is only 0.487V. The unpackaged device maintains 95% of its initial PCE after 500h, in an N2 environment at 25°C.

Low‐Temperature Synthesis of Stable CaZn2P2 Zintl Phosphide Thin Films as Candidate Top Absorbers

AbstractThe development of tandem photovoltaics and photoelectrochemical solar cells requires new absorber materials with bandgaps in the range of ≈1.5–2.3 eV, for use in the top cell paired with a narrower‐gap bottom cell. An outstanding challenge is finding materials with suitable optoelectronic and defect properties, good operational stability, and synthesis conditions that preserve underlying device layers. This study demonstrates the Zintl phosphide compound CaZn2P2 as a compelling candidate semiconductor for these applications. Phase‐pure, ≈500 nm‐thick CaZn2P2 thin films are prepared using a scalable reactive sputter deposition process at growth temperatures as low as 100 °C, which is desirable for device integration. Ultraviolet‐visible spectroscopy shows that CaZn2P2 films exhibit an optical absorptivity of ≈104 cm−1 at ≈1.95 eV direct bandgap. Room‐temperature photoluminescence (PL) measurements show near‐band‐edge optical emission, and time‐resolved microwave conductivity (TRMC) measurements indicate a photoexcited carrier lifetime of ≈30 ns. CaZn2P2 is highly stable in both ambient conditions and moisture, as evidenced by PL and TRMC measurements. Experimental data are supported by first‐principles calculations, which indicate the absence of low‐formation‐energy, deep intrinsic defects. Overall, this study shall motivate future work integrating this potential top cell absorber material into tandem solar cells.