Effect of Cu deficiency on the optical properties and electronic structure of CuIn1−xGaxSe2

Spectroscopic ellipsometry measurements of CuInSe₂ (CIS) and CuIn_1−xGa_xSe₂ (CIGS) over a range of Cu compositions reveal that there are important differences in electronic and optical properties between α-phase CIS/CIGS and Cu-poor CIS/CIGS. We find a reduction in the imaginary part of the dielectric function ?₂ in the spectral region, 1-3 eV. This reduction can be explained in terms of the Cu-3d density of states. An increase in band gap is found for Cu-poor CIS and CIGS due to the reduction in repulsive interaction between Cu-3d and Se-4p states. We also characterize the dielectric functions of polycrystalline thin-film α-phase CuIn_1−xGa_xSe₂ (x=0.18 and 0.36) to determine their optical properties and compare them with similar compositions of bulk polycrystalline CuIn_1−xGa_xSe₂. The experimental results have important implications for understanding the functioning of polycrystalline optoelectronic devices.     

Composition-induced structural modifications in the quaternary CuIn1-xGaxSe2 thin films： bond properties versus Ga content

In this paper the dependence of structural properties of the quaternary CuIn1-xGaxSe2 films with tetragonal structure on the Ga content has been systematically investigated by Raman scattering and x-ray diffraction spectra. The shift of the dominant A1 mode, unlike the lattice constants, does not follow the linear Vegard law with increasing Ga content x, whereas exhibits approximately polynomial change from 174 cm^-1 for CuInSe2 to 185 cm^-1 for CuGaSe2. Such behaviour should be indicative of presence of the asymmetric distribution of Ga and In on a microscopic scale in the films, due to Ga addition. The changes in the tetragonal distortion η lead to a significant variation in the anion displacement parameter U, which should be responsible for the evolution of bond parameters and resultant Raman bands with x.     

Physical properties of electrodeposited CIGS films on crystalline silicon: Application for photovoltaic hetero-junction

P-type CIGS (CuIn_1-xGa_xSe₂) thin films are electro-deposited on a p-type c-Si substrate with a galvanostatic mode to form CIGS(p)/c-Si(p) hetero-junction. The Ga content is varied up to x = 30%. The physical properties of formed CIGS films are characterized by XRD, SEM, EDS and UV–Visible spectroscopy. With x = 30%, we obtain a single chalcopyrite phase of CIGS with a tetragonal crystal structure, a high crystallinity, an orientation toward the (112) direction and a band gap energy of 1.40 eV.AM1.5 J-V performed on the CuI_0.7G_0.3Se₂/c-Si hetero-junction reveals interesting photovoltaic parameters with an efficiency of 3.75%. In addition, using the energy diagram of the hetero-junction calculated with the Anderson model, we show that it could play a dual role when combined to a c-Si cell in a Ag–Al/c-Si(n⁺)/c-Si(p)/CIGS(p)/Al new architecture. Therefore, in addition to its interesting photovoltaic parameters, this hetero-junction can substitute the BSF.     

Bond properties of the chalcopyrite and stannite phases in the Cu–(In,Ga)–Se system

Bond properties of the chalcopyrite and (defect) stannite phases in the Cu–(In,Ga)–Se system are compared in view of the bond overlap population calculated by the molecular orbital calculation of the DV-Xα method. Bond stretching force constant α is estimated for the stannite phases through the bond Ovlp. The Cu–Se and In(Ga)–Se bonds in defect stannite structure are considered to be mechanically weakened by the 2b-site vacancies. We estimate the weakened force constants to be 60–70% of those in the chalcopyrite structure. On the other hand, in In(Ga)-rich stannite, In(Ga)_4d–Se_8i and In(Ga)_2b–Se_8i bonds are estimated to be tighter by 23–25 and 8–9%, respectively, than In(Ga)_4b–Se_8d bond in the chalcopyrite structure. The Γ₁ frequencies of the stannite phases are also calculated using the estimated force constants. Characteristic Raman signals peaked at 160–175 cm⁻¹ observed for the Cu(In_1−xGa_x)₃Se₅ system are explained by the Cu-rich phase for the Cu–In–Se system, and the phase combination of Cu-rich and Ga_2aV_2b types for the Cu–Ga–Se system from these calculations.     

Post-annealing effect on the reactively sputter-grown CIGS thin films and its influence to solar cell performance

Using a reactive co-sputtering from Cu_0.6Ga_0.4 and Cu_0.4In_0.6 alloy targets, we prepared CuIn_1−xGa_xSe₂ (CIGS) thin films on Mo/soda-lime glass (SLG) in association with a thermal cracker for elemental atomic Se radicals. The film growth was performed at 500 °C for 90 min. To achieve the composition ratio of CIGS absorber layer, Cu_0.6Ga_0.4 target was set at RF power of 50 W, 60 W, 70 W, and 80 W while keeping at 100 W for Cu_0.4In_0.6 alloy target. Post-annealing was done for all the CIGS films at 550 °C for 30 min. The composition ratio of [Cu]/[In + Ga] and [Ga]/[In + Ga] was increased with RF power but showed no change after post-annealing. X-ray diffraction analysis revealed all the samples has grown dominantly in the [112] crystal orientation. We found the Cu_2−xSe and (InGa)_2−xSe₃ defect phase both at the surface and in the bulk, and developed with post-annealing. From the devices fabricated in the structure of grid/ITO/i-ZnO/CdS/CIGS/Mo/soda-lime glass (SLG), the external quantum efficiency (EQE) was observed to improve in the wavelength, λ ≥ 550 nm in the samples treated with annealing. In the current–voltage (J–V) measurements, the solar cell showed the best performance of FF = 54.1%, V_oc = 0.48 V, J_sc = 33.1 mA/cm² and η = 8.5% in the sample with [Cu]/[In + Ga] = 0.84 that improved largely from η = 4.6% for the solar cell with an as-grown CIGS films.     

Material and device properties of Cu(In,Ga)Se2 absorber films prepared by thermal reaction of InSe/Cu/GaSe alloys to elemental Se vapor

The aim of this work was to study the influence of selenization temperature on the morphological and structural properties of CuIn_1−xGa_xSe₂ (CIGS) polycrystalline thin films prepared by a two-step method. The compound and metallic precursors were deposited sequentially using GaSe, InSe and Cu sources by thermal evaporation. These identical InSe/Cu/GaSe precursors are then selenized with Se vapor in a vacuum system. All the CIGS films showed chalcopyrite structure and presence of secondary phases observed at low temperatures. High temperature treatment led to better crystalline and an increase in grain size. Solar cell devices are fabricated and J–V measurements performed under AM1.5 global solar spectra conditions at 25 °C are presented.     

Nd:YAG laser ablation characteristics of thin CIGS solar cell films

This work reports that the ablation characteristics of thin CuIn_1?x Ga _x Se₂ (CIGS) solar cell film differ significantly with elemental composition and laser pulse energy. From in situ shadowgraphs measured during Nd:YAG laser (1,064 nm) irradiation of CIGS films and crater morphologies, it was found that strong surface evaporation is dominant for low Ga concentration films of which band gap is well below the photon energy. As the band gap of CIGS film becomes close to or over the laser photon energy due to increased Ga content, surface absorption diminishes and at low laser energy, laser heating of the film plays an important role. It is demonstrated that for the CIGS films with Ga/(Ga + In) ratio being approximately over 0.2, the laser irradiation leads to solid phase removal of the film due to thermomechanical fracture at low laser energy but to ablative evaporation at elevated energy.     

Microstructure,dielectric, and piezoelectric properties of 0.38Bi(Gax Sc1–x )O3–0.62PbTiO3 high temperature piezoelectric ceramics

0.38Bi(Ga_x Sc_1–x )O₃–0.62PbTiO₃ (BGSPTx) ceramics have been prepared by using the conventional mixed oxide method. X‐ray diffraction analysis revealed that BGSPTx has a pure perovskite structure, and the crystal symmetry of BGSPTx changed from rhombohedral to tetragonal with increasing Ga content (x). The Curie temperature (T_C) of BGSPTx ceramics is in the range of 448–467 °C for different x. The ferroelectric phase transition of BGSPTx was found to be of the first order type according to the Curie–Weiss law. For x = 0.125, BGSPTx ceramics show enhanced piezoelectric properties: piezoelectric constant d₃₃ = 420 pC/N and d₃₁ = –142 pC/N, planar and thickness electromechanical coupling factors k_p = 56.27% and k_t = 56.00%, respectively. The high‐T_C of BGSPTx coupled with its excellent piezoelectric properties suggests those future high‐temperature applications. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectromicroscopic investigation of (NH4)2S treated polycrystalline Cu(In1−xGax)Se2

Device-grade polycrystalline thin-film Cu(In_1−xGa_x)Se₂ was treated with (NH₄)₂S at 60°C to determine the resulting microscopic surface composition/morphology. Scanning electron microscopy was used to evaluate the resultant macroscopic surface morphology. Modification of the surface and grain boundary chemistry of the Cu(In_1−xGa_x)Se₂ polycrystalline films was investigated with scanning photoemission spectromicroscopy. The submicrometer lateral resolution of this technique allows us to directly characterize not only the surface chemistry of the treated films on the submicron scale, but also to probe the grain boundary chemistry. Chemical maps depicting the distribution of chemical species on the surface and at grain boundaries were obtained by monitoring the S 2p, Se 3d, In 4d/Ga 3d and Cu 3d (valence band) photoelectrons while scanning the sample. Background maps were also acquired of each of the peak energies to separate chemical contrast from topographic contrast. Results show that S has been incorporated at the surface, possibly creating a wider bandgap Cu(In_1−xGa_x)(Se_1−yS_y)₂ surface layer, and along the grain boundaries. The purpose of this investigation is to find an environmentally safe replacement for the toxic CdS overlayer commonly used for heterojunction devices without sacrificing overall device performance and reliability.     

Structural, thermal and optical studies of mechanical alloyed Ga40Se60 mixture

A mixture of elemental Ga and Se with the nominal composition Ga₄₀Se₆₀ was submitted to the Mechanical alloying technique and their structural, thermal and optical properties were followed by X-ray diffraction, differential thermal analysis, photoacoustic spectroscopy, UV-VIS‐NIR absorbance spectroscopy and Raman spectroscopy techniques. After 10 h of milling the X-ray pattern showed monoclinic Ga₂Se₃ phase nucleation, which is in the nanometric form, and also a minority amorphous phase. The DSC results showed exothermic reactions between 430 and 720 K attributed to amorphous-crystalline phase transition and structural relaxation of Ga₂Se₃ phase. Based on this a small amount of the as-milled sample was annealed at 723 K. Its XRD pattern showed evidences of grain growth, reduction of the interfacial component, as well as, disappearance of the amorphous phase. The annealing process induced thermal diffusivity increasing, while the optical band gap energy and Raman profile remained practically unchanged.     

Effect of Ga incorporation on valence band splitting of OVC CuIn3Se5 thin films

Polycrystalline thin films of CuIn_2.95Ga_0.05Se₅ produced by the incorporation of Ga into the ordered vacancy compound CuIn₃Se₅ by a two-stage vacuum evaporation process were structurally, compositionally and optically characterized using X-ray diffraction, energy dispersive analysis of X-rays and optical absorbance measurements. From the X-ray diffraction data of the films, the structural parameters like lattice constants, tetragonal deformation, bond lengths and anion displacement were evaluated and their effect on the optical behavior of films was discussed. The Hopfields quasi-cubic model adapted for chalcopyrites with tetragonal deformation was used to elucidate the crystal field and spin orbital splitting parameters in the uppermost valence band of the compound, using the three energy gaps 1.649, 1.718 and 1.92 eV corresponding to the threefold absorption in the fundamental absorption region of the optical spectra of these films. The percentage contributions of Se p and Cu d orbitals to p-d hybridization in this compound were calculated using linear hybridization of orbitals model and the effects of p-d hybridization on the band gaps were studied.     

Deposition of quaternary sputtered CIGS nanorods via glancing angle deposition

Nanostructured materials have become an attractive alternative to their thin film and bulk counterparts in photovoltaic and photoconductivity research. This is mainly attributed to their superior optical and electrical properties. Light trapping in vertically aligned nanostructures results in high optical absorption and provides enhanced carrier collection by utilizing a fully depleted p–n‐junction between the anode and cathode via an isolated ”capping” construction. The combination of these two features can potentially lead to the development of high efficiency nanostructured devices including solar cells, photodiodes, and photodetectors. Optical absorption proper ties of nanorod arrays of CuIn_x Ga_1–xSe₂ (CIGS), a p‐type semiconductor with a wide band gap ranging from 1.0 eV to 1.7 eV, are compared to their thin film counterpart. Utilizing an RF sputtering system, a quaternary target, and glancing angle deposition (GLAD) technique, vertical arrays of CIGS nanorods were fabricated while conventional films were fabricated by normal incidence deposition. Scanning electron microscopy (SEM) images indicated a successful growth of CIGS nanorods. Optical absorption was found to be strongly altered by the presence of the nanorod structures through spectroscopic reflectometry. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Structural properties of CuInSe2 films prepared by selenization of metallic precursors on MoNx film substrates

The aim of this work was to study the effect of MoN_x film substrates on the structural properties of CuInSe₂ films prepared by selenization of metallic Cu-In alloy precursors. MoN_x films were prepared by reactive dc-magnetron sputtering. All the CuInSe₂ films exhibit single phase chalcopyrite structure with (1 1 2) preferred orientation, which can be explained by the reduction of lattice mismatch between CuInSe₂ and MoN_x. The bulk composition of selenized CuInSe₂ films are near stoichiometric, but the surface composition analysis suggests Cu deficiency on surface area. Furthermore, ordered defect compound, CuIn₂Se_3.5 is found on the surface of CuInSe₂ films. The results will be helpful for fabricating Cd-free ZnO buffer layer CuInSe₂ and Cu(In_1−xGa_x)Se₂ based thin film solar cells.     

等离子体活化硒对电沉积Cu-In-Ga金属预制层硒化的影响

使用等离子体活化硒源对电沉积制备的Cu-In-Ga金属预制层进行了硒化处理时, 发现等离子体功率对Cu(In_1-xGa_x)Se₂(CIGS)晶粒的生长有重要影响, 当等离子体功率为75 W时, 制备出单一Cu(In_0.7Ga_0.3)Se₂相的CIGS薄膜. 通过对不同衬底温度的等离子体活化硒源硒化的CIGS 薄膜进行了研究与分析, 并与普通硒化后的薄膜进行对比, 发现高活性硒在低温下会促进Ga-Se二元相的生成, 从而有利于Cu(In_0.7Ga_0.3)Se₂单相的生长. 对等离子体硒化后的CIGS薄膜进行了电池制备, 发现单相CIGS薄膜没有显著提高电池性能. 通过优化工艺, 所制备的CIGS电池效率达到了9.4%. 关键词： 0.7Ga_0.3)Se₂')" href="#">Cu(In_0.7Ga_0.3)Se₂ 电沉积 Cu-In-Ga金属预制层 等离子体活化硒     

The influence of annealing temperature and tellurium (Te) on electrical and dielectrical properties of Al/p-CIGSeTe/Mo Schottky diodes

p-CuIn_0.7Ga_0.3(Se_(1?x)Te_x)₂ type thin films were synthesized by thermal evaporation method on Mo coated glass substrates. To obtain Al/CuIn_0.7Ga_0.3(Se_(1?x)Te_x)₂/Mo Schottky diode structure for two compositions of x = 0.0 and 0.6, Al metal was evaporated on upper surface of CuIn_0.7Ga_0.3(Se_(1?x)Te_x)₂ as a front contact. Al/p-CuIn_0.7Ga_0.3(Se_(1?x)Te_x)₂/Mo structures were annealed temperature range from 150 °C to 300 °C for 10 min under vacuum. The electrical and dielectrical properties of Al/p-CuIn_0.7Ga_0.3(Se_(1?x)Te_x)₂ (CIGSeTe) Schottky barrier diodes (SBD) have been investigated. Capacitance–Voltage (C–V) characteristics, Conductance–Voltage (G/w–V) characteristics and interface state density were studied in order to obtain electrical and dielectrical parameters. The effects of interface state density (N_ss), series resistance (R_s), the dielectric constant (?′), dielectric loss (?″), dielectric loss tangent (tan δ), ac electrical conductivity (σ_ac) and carrier doping densities were calculated from the C–V and G/w–V measurements and plotted as a function of annealing temperature. It was observed that the values of carrier doping density N_A for annealing temperature at 150 °C decreased from 2.83 × 10⁺¹⁵ cm^?3 to 2.87 × 10⁺¹⁴ cm^?3 with increasing Te content from x = 0.0 to 0.6. The series resistance for x = 0.0 found to be between 10 and 75 Ω and between 50 and 230 Ω for x = 0.6 in the range of annealing temperature at 150–300 °C.     

Magnetic properties of R2Fe17−xGax (R=Y and Gd) compounds

The magnetic properties of Y₂Fe_17−xGa_x for 3≤x≤7 and Gd₂Fe_17−xGa_x for 5≤x≤7 have been investigated using ⁵⁷Fe Mössbauer spectroscopy. These compounds have the rhombohedral Th₂Zn₁₇ structure. X-ray diffraction analysis of aligned powders shows that the easy direction of magnetization is parallel to the c-axis in Y₂Fe₁₀Ga₇ and Gd₂Fe₁₀Ga₇ and is perpendicular to the c-axis in Y₂Fe₁₄Ga₃, Y₂Fe₁₂Ga₅, Gd₂Fe₁₂Ga₅ and Gd₂Fe₁₁Ga₆. Mössbauer studies indicate that those samples are ordered ferromagnetically. The ⁵⁷Fe hyperfine field decreases with increasing Ga content. This decrease results from the decreased magnetic exchange interactions resulting from Ga substitution. The average isomer shift, δ, for R₂Fe_17−xGa_x (R=Y and Gd) at room temperature is positive and the magnitude of δ increases with increasing Ga content.     

The effect of Na on the electronic properties of Cu(In,Ga)Se2 thin films: A local‐probe study

We investigated the effect of Na incorporation on the electronic properties of polycrystalline CuIn_0.7Ga_0.3Se₂ thin films using scanning tunneling microscopy and spectroscopy. The tunneling spectra indicate a reduced in‐gap density of states at grain boundaries and reveal a downward band‐bending in Na‐rich grain boundaries with respect to the adjacent grains, in agreement with our conductive atomic force microscopy data. It thus appears that Na passivates deep‐level defects at grain boundaries and induces a downward band‐bending there. Moreover, we provide evidence that Na passivates mainly Cu vacancy related defects. We suggest that the grain‐boundary passivation, which reduces the recombination rate of photogenerated carriers, is at least of major importance in the well known Na‐induced improvement in the efficiency of the corresponding solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Piezoresistivity in GaAs/InxGa1–xAs/AlAs superlattice structures

We report on a strong piezoresistive effect in GaAs/ In_x Ga_1–x As/AlAs superlattice structures fabricated on a GaAs‐base cantilever. The measurements of the piezoresistive properties were performed for tensile strains by static pressure experiments. The maximum gauge factor (GF) for the GaAs/In_x Ga_1–x As/AlAs epilayer can be estimated to 200, which is higher than the value of the gauge factor reported for Si transducers. Our results demonstrate a higher potential of GaAs/In_x Ga_1–x As/AlAs superlattice structures for the development of piezoresistive sensors. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Features of the Percolation Scheme of Vibrational Spectrum Reconstruction in the Ga1 – xAl x P Alloy

Specific features of the properties of Ga–P lattice vibrations have been investigated using the percolation model of a mixed Ga_{1 – x}Al _x P crystal (alloy) with zero lattice mismatch between binary components of the alloy. In contrast to other two-mode alloy systems, in Ga_{1 – x}Al _x P a percolation splitting of δ ~ 13 cm^–1 is observed for the low-frequency mode of GaP-like vibrations. An additional GaP mode (one of the percolation doublet components) split from the fundamental mode is observed for the GaP-rich alloy, which coincides in frequency with the gap corresponding to the zero density of one-phonon states of the GaP crystal. The vibrational spectrum of impurity Al in the GaP crystal has been calculated using the theory of crystal lattice dynamics. Upon substitution of lighter Al for the Ga atom, the calculated spectrum includes, along with the local mode, a singularity near the gap with the zero density of phonon states of the GaP crystal, which coincides with the mode observed experimentally at a frequency of 378 cm^–1 in the Ga_{1 – x}Al _x P (x < 0.4) alloy.

     

Se-Ga23Se phase equilibria: a regular associated solution model for the Ga-Se liquid

Se vapor pressures were measured by the dew point method for the binary system Ga_1·xSe_x, 0.60 < x < 1.00 (Ga₂Se₃-Se), between 700 and 1050°C. The Se vapor pressure was found to decrease rapidly near x = 60 atomic% Se. The T-X and P-X liquidus curves are thermodymanically modelled by a regular associated solution model for the liquid phase, with the associate, Ga₂Se₃. The best fit to the data was obtained with 4000 cal/mole of Ga₂Se₃ for the regular solution interaction parameter and 0.10 for the degree of dissociation in the stoichiometric liquid (x = 0.60).