Chalcopyrite Semiconductors Research Articles

TB-mBJ for doping concentration effects on magneto-optical properties in [formula omitted] spintronics materials

An investigation for electronic, magnetic, and optical properties of Mn-doped ZnSnAs2 compound performed using advanced computational methods. Using spin-polarized density functional theory (DFT) calculations with local orbital linearized augmented plane wave (lo-LAPW) method and Tran–Blaha’s modified Becke–Johnson (TB-mBJ) functional, Mn-doped n-type chalcopyrite semiconductor ZnMnxSn(1−x)As2, studied within varying Mn doping concentration range 0≤x≤0.5. Doping of Mn to Sn site in pure ZnSnAs2 creates a strong spin effect, which makes it useful spintronic materials. We observed with increase the Mn concentration in ZnSnAs2, energy bandgap changes while the magnetic strength of the unit cell remains unchanged, showing stability of system’s magnetism. Optical properties of the Mn doped ZnSnAs2 compounds analysed in term of dielectric function, absorption spectra, and refractive index. Optical properties show, compound is optically low active in the Infrared (IR) region and more active in visible and ultraviolet (UV) region. The electronic and optical properties of Mn-doped ZnSnAs2, offer potential technological advancements in semiconductor device design technology and engineering.

Dependence of Crystal‐Field Energy on Strain/Stress Sensed by Temperature Variation of Chalcopyrite Semiconductor (Optical) Band‐Gap for Efficient Band‐Gap Tuning in the CIS/CIGS Photovoltaic

Chalcopyrite selenide single crystals and epitaxial layers (CuIn1−xGaxSe2, x = 0.00, 0.08, 0.19, 1.00) were characterized by temperature‐dependent photoreflectance (PR), photoluminescence (PL), photoluminescence–excitation (PLE), and variable excitation‐energy photoluminescence (VEPL) spectroscopy. The transition energies Ea, Eb, and Ec of both CuInSe2 (CIS) and CuGaSe2 (CGS) layers sensed by PR were higher than the energies of single crystals. CuInSe2 and CuGaSe2 grown on GaAs(001) underlie compressive and tensile stresses, respectively, which lead to band‐gap broadening in CIS and band‐gap narrowing in CGS. The increase of the Ea, Eb, Ec energies of tensely stressed CuGaSe2 layers to energies higher than those of the bulk originates from the stress dependence of the non‐cubic crystal field. Band‐gap scanning of the CuGaSe2 layer with continuous‐wave Ti:sapphire‐laser confirmed the absence of correlation between band‐gap readjustment and intrinsic defects. The energy of the band‐edge exciton EFE, in the PL‐spectra, was lower than the Ea transition energy, in the PR‐spectra, which is assigned to partial quenching of ΔCF with the increase of external tensile stress by gallium‐segregation at the chalcopyrite/GaAs‐interface. The stress dependence of ΔCF is negligible in CuInSe2 and linear, with a rate of 9 meV/100 MPa, in CuGaSe2. It is revealed that the energy band‐gap of photovoltaic chalcopyrite absorbers can be tuned by simultaneous built‐in and external lattice‐tuning.

Colloidal hot injection synthesis of Cu2FeSnS4 nanoparticles towards an enhanced capacity anode material for Li-ion batteries

The increasing demand for portable energy storage devices has prompted a considerable exploration into advanced anode material with higher Li-ion battery capacities. Quaternary chalcopyrite semiconductors have generated significant attention as promising materials in applications such as optoelectronic devices, energy conversion, and energy storage devices. In this paper, Cu2FeSnS4 (CFTS) nanoparticles were prepared through a colloidal hot injection method (HIM). The structural analysis indicates that the CFTS nanoparticles exhibit a pure tetragonal structure characterized by high crystallinity. The morphological and elemental analysis shows the stoichiometric synthesis of CFTS nanoparticles with significant agglomeration of crystallites, accompanied by variation in size. The CFTS nanoparticles, employed as an anode material for Li-ion batteries, demonstrated significant performance characterized by high reversible capacity and stability at ambient temperature. The initial discharge capacity is achieved at 1181 mAhg−1 and retains 528 mAhg−1 during charge-discharge cycles within the voltage range of 0.005 to 3.0 V (versus Li/Li+) after 5 cycles. The CFTS nanoparticle performance findings indicate its promising implementation as an anode electrode in Li-ion batteries.

First-principles investigations of structural, electronic and optical properties of ternary chalcopyrite semiconductors [formula omitted] ([formula omitted], [formula omitted] and [formula omitted])

The copper-indium-based tetragonal chalcopyrite semiconductors CuInY2Y=S, Se and Te) have garnered significant attention due to their suitable bandgap for solar cell applications. In this study, we investigate the structural, electronic, and optical properties of CuInY2 using state-of-the-art density functional theory (DFT) with the modified Becke-Johnson (mBJ) semilocal exchange functional. Our band structure calculations reveals that these compounds exhibit a p-type semiconductors character with a direct band gap at the Γ point. The calculated band gaps are in good agreement with the experimental data. Density of state analysis shows that these compounds are primarily influenced by Cud-states at the upper valence band and their hybridization with Yp-states bellow the first valence band. Furthermore, we validate our results by calculating optical properties, including the dielectric function, absorption coefficient, the real part of optical conductivity, optical reflectivity, and the refractive index. Our refractive index findings show reasonable agreement with the experimental data. Our findings indicate that all three compounds exhibit high absorption (≈105cm−1) in the visible light range with CuInTe2 showing the highest absorption compared to CuInS2 and CuInSe2. Additionally, CuInS2 is less reflective (0.21%) in the visible light range in this series. These structures, with their suitable band gaps, are capable of absorbing a significant amount of light, making them prospective choices for solar cell applications.

Role of anion–cation antisites in Zn-based II–IV–V2 chalcopyrite semiconductors

Role of anion–cation antisites in Zn-based II–IV–V2 chalcopyrite semiconductors

Co-sensitization of Copper Indium Gallium Disulfide and Indium Sulfide on Zinc Oxide Nanostructures: Effect of Morphology in Electrochemical Carbon Dioxide Reduction.

Recent advances in nanoparticle materials can facilitate the electro-reduction of carbon dioxide (CO2) to form valuable products with high selectivity. Copper (Cu)-based electrodes are promising candidates to drive efficient and selective CO2 reduction. However, the application of Cu-based chalcopyrite semiconductors in the electrocatalytic reduction of CO2 is still limited. This study demonstrated that novel zinc oxide (ZnO)/copper indium gallium sulfide (CIGS)/indium sulfide (InS) heterojunction electrodes could be used in effective CO2 reduction for formic acid production. It has been determined that Faradaic efficiencies for formic acid production using ZnO nanowire (NW) and nanoflower (NF) structures vary due to structural and morphological differences. A ZnO NW/CIGS/InS heterojunction electrode resulted in the highest efficiency of 77.2% and 0.35 mA cm-2 of current density at a -0.24 V (vs. reversible hydrogen electrode) bias potential. Adding a ZTO intermediate layer by the spray pyrolysis method decreased the yield of formic acid and increased the yield of H2. Our work offers a new heterojunction electrode for efficient formic acid production via cost-effective and scalable CO2 reduction.

Investigation of structural, electronic, mechanical, and thermoelectric properties of the defect chalcopyrite semiconductor ZnIn[formula omitted]Se[formula omitted] from density functional theory

In this study, the detailed structural, electronic, mechanical, and thermoelectric properties of ZnIn2Se4 defect chalcopyrite semiconductor are carried out using density functional theory & semi-classical Boltzmann transport theory. From the band structure analysis, the compound is confirmed to be a direct band gap semiconductor with a band gap of 1.20 eV. The presence of flat valence bands near the Fermi level indicates a higher effective mass of holes. From the elastic and mechanical properties, it has been found that the compound is mechanically stable and revealed to be ductile. The phonon dispersion study of the compounds shows that the compound is dynamically stable with no imaginary phonon modes. The electronic transport properties were studied within a temperature range of 300K to 900K as a function of chemical potential (μ), temperature(T), and carrier concentrations (n). The μ dependent electronic transport properties show enhanced values in the p-type doping region because of the cationic site vacancy. The dependency of electronic transport properties on n and T agrees well with Mott’s relation. The highest ZT is found to be 0.96 at 900K for a low carrier concentration of 1019cm−3. The phonon thermal conductivity of the compound is found to be 2.52 W/mK near room temperature and 0.84 W/mK at 900K using the Slack method. All these results support ZnIn2Se4, a defect chalcopyrite semiconductor, as a favorable candidate for thermoelectric applications.

Nanohardness and Young’s modulus of II-IV-V2 chalcopyrite nonlinear optical crystals: a comparative study

Nanohardness and Young’s modulus of oriented monocrystalline II-IV-V2 chalcopyrite semiconductors are measured by nanoindentation for the first time. The tests are performed on (100) and (001) surfaces. Anisotropy is observed for Young’s modulus only. It is most pronounced for CdSiP2. The hardness results display linear dependence on the melting temperature (except for CdSiP2) and the values decrease with the molar mass. They can be well fitted as a function of the molar mass and the unit cell volume. Young’s modulus dependences show similar trends.

Theoretical studies on phase stability, electronic, optical, mechanical and thermal properties of chalcopyrite semiconductors HgXN2 (X=Si, Ge and sn): A comprehensive DFT analysis

In this study, the ground state physical properties of Hg-based chalcopyrite semiconductors, HgXN2 (X = Si, Ge and Sn), are investigated using the density functional theory (DFT), which is based on full potential linearized augmented plane wave (FP-LAPW) method. The structural, electronic, optical, mechanical and thermal properties of the body-centered tetragonal (BTC) phase, HgXN2 (X = Si, Ge and Sn), have been calculated using the modified Becke-Johnson exchange-correlation potential (TB-mBJ). The obtained lattice parameters and volume are in good agreement with the values reported earlier, indicating that the results are reliable and reproducible. The phase stability of the titled compounds is elaborately studied and it is confirmed that all are thermodynamically, dynamically and mechanically stable. The electronic band structure demonstrated a direct band gap of 1.70 eV, 0.99 eV, and 0.94 eV for the HgXN2 (X = Si, Ge and Sn) compounds, respectively. Both HgGeN2 and HgSnN2 compounds have a notably lighter carrier effective mass, resulting in higher carrier mobility and conductivity than HgSiN2. The order of the mechanical hardness is as follows: HgSiN2> HgGeN2> HgSnN2. The studied materials are also anisotropic in mechanically and optically. All the title compounds exhibit ductile behavior. The charge density contour plots indicates the dominant covalent nature of the bonds in HgXN2 (X = Si, Ge and Sn). All these compounds have a high absorption coefficient and low optical reflectivity in the visible light range. Due to the favorable band gap and high absorption coefficient, these compounds could be suitable for optoelectronic or photovoltaic device applications. Moreover, the thermal expansion coefficient, thermal conductivity, melting point and fracture toughness behavior have been calculated, which also showed promise for thermal barrier coating (TBC) applications.

Magnetic properties of the copper chalcopyrite semiconductor CuGaSe2 material

This manuscript presents a model and simulation of the copper chalcopyrite semiconductor CuGaSe2 in order to predict its magnetic properties. In the semiconductor material CuGaSe2 (CGS), the atom Cu is the only magnetic element with a magnetic moment value S = 1/2. We propose a Hamiltonian to calculate the energies corresponding to different configurations of the system. In a first step, we presented the magnetization behavior by using the Monte Carlo simulations (MCS). The magnetizations as a function of the temperature, the exchange coupling have been studied and discussed. We have also deduced and studied the magnetic susceptibilities. To complete this study, we have established and discussed the magnetic hysteresis loops of the studied compound. Finally, we have calculated the corresponding critical exponents and compared them with the standard 3D Ising model.

First-principle investigation of structural, electronic, and phase stabilities in chalcopyrite semiconductors: insights from Meta-GGA functionals

We undertake a comprehensive first-principles investigation into the factors influencing the optoelectronic efficiencies of P I Q III R 2VI chalcopyrite semiconductors. The structural attributes, electronic properties, and phase stabilities are explored using various meta-GGA exchange-correlation (XC) functionals within the density functional framework. In particular, we assess the relative performance of these XC functionals in obtaining estimates of various relevant parameters. The structural parameter u in chalcopyrite semiconductors is a noteworthy aspect, as it is intrinsically tied to the extent of orbital hybridization between distinct atoms and thereby strongly influences the electronic properties. In general, the application of widely used GGA-PBE XC functional to these chalcopyrites results in unreliable predictions of band gaps and ‘u’ parameter due to delocalization errors that in turn arise due to the inclusion of d and f core electrons. While hybrid functionals offer remarkable accuracy through state-of-the-art methods, their main drawback lies in their computational expense and resource demands. Our findings strongly suggest that in comparison to GGA-PBE, the meta-GGA XC functionals perform quite well and provide results that closely align with experimental values. In particular, the r 2SCAN and rMGGAC XC functionals are preferable and superior for investigating chalcopyrites and other solid-state systems. This preference is rooted in their excellent performance and substantially reduced computational costs compared to hybrid functionals.

Accurate and efficient prediction of the band gaps and optical spectra of chalcopyrite semiconductors from a nonempirical range-separated dielectric-dependent hybrid: Comparison with many-body perturbation theory

Accurate and efficient prediction of the band gaps and optical spectra of chalcopyrite semiconductors from a nonempirical range-separated dielectric-dependent hybrid: Comparison with many-body perturbation theory

Processing and characterization of chalcopyrite semiconductors for photovoltaic applications

Professor Joseph “Joe” Greene taught me a great deal about research, leadership, and how to succeed. He was a mentor and a tireless advocate for me over the course of my career. This article summarizes some of the work that my research group carried out, inspired by Prof. Greene but not in direct collaboration with him. Three examples of these efforts are provided, epitaxial growth of Cu(In,Ga)Se2 (CIGS) on GaAs by sputter deposition, synthesis of Cu-Mo metastable alloys by sputter deposition, and recrystallization of CIGS deposited at high rates by treatment with metal halides. These works were carried out with many collaborators who are acknowledged in the description of the research carried out by them and in the references where full details can be found.

Thermodynamic properties of chalcogenide and pnictide ternary tetrahedral semiconductors

In this paper, we present thermodynamic properties such as heat of formation, heat of fusion and entropy of fusion for chalcopyrite structured solids with the product of ionic charges and nearest neighbour distance d (Å). The heat of formation (∆Hf) of these compounds exhibit a linear relationship when plotted on a log-log scale against the nearest neighbour distance d (Å), but fall on different straight lines according to the ionic charge product of the compounds. On the basis of this result two simple heat of formation (∆Hf)heat of fusion (∆HF), and heat of formation (∆Hf)entropy of fusion (∆SF), relationship are proposed and used to estimate the heat of fusion (∆HF) and entropy of fusion (∆SF) of these semiconductors. We have applied the proposed relation to AIIBIVC2 V and AI BIIIC2 VI chalcopyrite semiconductor and found a better agreement with the experimental data than the values found by earlier researchers. The results for heat of formation differ from experimental values by the following amounts: 0.3% (CuGaSe2), 6.7% (CuInSe2), 5% (AgInSe2), 5% (ZnGeP2), 6% (ZnGeP2), 0.4% (ZnSnP2), 0.7% (ZnSiAs2), 2.6% (ZnGeAs2), 1.2% (ZnSnAs2), 3.8% (CdGeP2), 6.4% (CdGeAs2), the results for heat of fusion differ from experimental values by the following amounts: 2.6% (CuGaS2), 0.6% (CuInTe2), 6% (ZnGeAs2), 8.8% (ZnSiAs2) and the results for entropy of fusion differ from experimental values by the following amounts: 6% (CuInSe2), 8% (CdSiP2).

Structural, elastic, electronic, optical and thermoelectric properties of metal based ternary chalcopyrite semiconductor for photovoltaic application: First-principles studies

In this article, the physical properties of XCrS2 (X = Zn, Cd, and Hg) are studied by Density Functional Theory (DFT) using Wien2K code. Stability, along with certain parameters of the crystal structures of the compounds, was evaluated based on PBE-GGA. Mechanical properties reveal that the studied compounds XCrS2 (X = Zn, Cd) are stable, and their elastic constants and Paugh’s ratio exhibit that ZnCrS2 is brittle, whereas CdCrS2 is ductile in nature. Furthermore, HgCrS2 does not satisfy the Born stability criteria. The modified Becke-Johnson (mBJ) potential was used to improve the band gap properties and results depict that the XCrS2 (X = Zn, Cd) compounds have 1.30 and 1.27 eV direct band gaps, respectively. Thermoelectric properties exhibit the highest optical conductivity with energy loss and the strongest absorption is observed for CdCrS2 in the visible region, which also has the best photovoltaic activity. The higher obsorption nature makes this material a good candidate for solar devices. The electrical and thermal conductivity increase with an increase in temperature, and ZnCrS2 has a greater ZT compared to CdCrS2.

Effects of pressure on structural, mechanical, and electronic properties of chalcopyrite compound CuAlS2

First-principles method is performed to investigate the structural, electronic, elastic and mechanical characteristics of the tetragonal CuAlS2 in the pressure range from 0 to 10 GPa. The results indicated that both the lattice constant and cell volume decrease with the increase of pressure, which are matched well with available previous values. The pressure has a more significant influence on the c direction than the a and b direction. The obtained elastic constants reveal the tetragonal CuAlS2 is mechanically stable between 0 and 10 GPa. The bulk, shear, and Young’s modulus are evaluated by Voigt-Reuss-Hill approximation. All these elastic moduli exhibit a monotonic feature as a function of pressure. The Poisson’s ratio, Pugh’s criterion, and Cauchy pressure indicate that ternary chalcopyrite semiconductor CuAlS2 is ductile against pressure. Meanwhile, the analysis of the electronic structures reveals that the states near the valence band top are derived from Cu 3d and S 3p orbitals, and the lowest conduction band is composed of Al 3p and S 3p orbitals. We expect that the findings predicted the physical properties of this compound will promote future experimental studies on CuAlS2.

First-principles study on crystal structures and bulk modulus of CuInX2 (X = S, Se, S-Se) solar cell absorber

Chalcopyrite semiconductors are widely used as absorbers in thin film solar cells, especially flexible solar cells, due to their high power conversion efficiency. They also have interesting mechanical properties, making them promising materials for flexible, light, and thin solar cells. In this work, we report the first-principle calculations of the lattice constant and bulk modulus for CuInS2, CuInSe2, and CuIn(S,Se)2 absorber solar materials. All calculations are performed using plane wave as implemented in the Quantum ESPRESSO software package in the framework of density functional theory using PBE-GGA approximations and ultrasoft pseudopotentials. The calculated lattice constant correlates well with the available experimental study. The energy-volume and pressure-volume relations are described using the third order of Birch-Murnaghan’s equation of state to calculate the bulk modulus of the absorber solar material, which is associated to the hardness of a material under particular conditions. The values of bulk modulus obtained for CuInS2 and CuInSe2 are in good agreement with available theoretical results, except for CuIn(S,Se)2, which have been calculated and reported for the first time.

Investigations of physical properties of lithium-based chalcopyrite semiconductors: non-toxic materials for photovoltaic applications

The ab-initio calculations have been executed for structural, electronic and optical properties of LiAlTe2, LiGaTe2 and LiInTe2 chalcopyrite structured solids and these calculations are grounded on the principle of density functional theory employed into the full potential augmented plane wave method. The computed lattice constants oscillating from a = 6.257 Å to 6.450 Å and c = 12.044 Å to 12.256 Å for LiXTe2 (X=Al, Ga and In) and also these values consistent with experimentally existed lattice constants. From the study of electronic band-gap, it confirms that these compounds are good semiconductors with direct band-gaps from 2.22 eV, 1.48 eV and 1.61 eV for LiXTe2 (X=Al, Ga and In). The result of optical properties confirms that these chalcopyrite semiconductors can be the fortunate compounds for the photovoltaic applications.

First-principles study for physical properties and stability of Li based chalcopyrite semiconductors: Reliable for green energy sources

In this research study, we have been performed the first principles calculation for physical properties likewise structural, electronic, optical and mechanical properties of the lithium gallium chalcopyrites LiGaX2 (X= S, Se). We have used two exchange correlation potentials one is full potential augmented plane wave method (FP-LAPW) and second is pseudo-potential method. The reported lattice parameters in this work ranging from a = b = 5.28 Å to 5.82 Å and c = 10.11 Å to 11.25 Å and found that these materials have direct band-gap 4.41 eV for LiGaS2 and 2.90 eV for LiGaSe2­. Refractive indexes n(ω) is 2.1 and 2.3 respectively for these compounds. The study of optical and elastic properties for these materials ensures that these show the anisotropic behaviour and ductile in nature.

Size-dependent radiative recombination characteristics of isolated CuInS2 nanocrystals

Ternary chalcopyrite semiconductor nanocrystals of the I–III–VI2 type are potential nontoxic alternatives to Cd- and Pb-based chalcogenide nanocrystals, which can be adopted for light emission and photovoltaic applications. Most I–III–VI2 nanocrystals exhibit luminescence originated from defect-related recombination, which is characterized by a broad spectrum with a large Stokes shift regardless of the size-dependent spectral shift due to the quantum size effect. However, the origin of the luminescence in I–III–VI2 nanocrystals is still under debate, and deeper investigations of the carrier recombination processes are necessary to gain further understanding of the luminescence mechanisms. For this purpose, we investigated the temperature dependence of the luminescence properties of CuInS2 nanocrystals down to cryogenic temperatures to suppress the nonradiative recombination. The intrinsic luminescence properties of the isolated CuInS2 nanocrystals were successfully evaluated by eliminating the influence of the interactions among the nanocrystals, which is different from previous studies on nanocrystal aggregates. Both the thermal quenching behavior and the temperature dependence of the carrier recombination rate could be satisfactorily described using a simple model that assumes a thermally activated nonradiative recombination. The radiative recombination rates of the CuInS2 nanocrystals were found to be 106–107 s−1, and a characteristic cubic dependence of the radiative recombination rate on the nanocrystal diameter was found.