Impurity induced band-gap narrowing in p-type CuIn1 − xGax(S,Se)2

Green's functions modelling of the impurity induced effects in p-type CuIn_1 − xGa_xS₂ and CuIn_1 − xGa_xSe₂ (x = 0.0, 0.5, and 1.0) reveals that: (i) the critical active acceptor concentration for the metal non-metal transition occurs at N_c ≈ 10¹⁷-10¹⁸ cm^− 3 for impurities with ionization energy of E_A ≈ 30-60 meV. (ii) For acceptor concentrations N_A > N_c, the hole gas of the metallic phase affects the band-edge energies and narrows the energy gap E_g = E_g⁰ − ΔE_g. The energy shift of the valence-band maximum ΔE_v1 is roughly twice as large as the shift of the conduction-band minimum ΔE_c1. (iii) ΔE_v1 depends strongly on the non-parabolicity of the valence bands. (iv) Sulfur based compounds and Ga-rich alloys have the largest shifts of their band edges. (v) A high active acceptor concentrations of N_A = 10²⁰ cm^− 3 implies a band-gap narrowing in the order of ΔE_g ≈ 0.2 eV, thus E_g = E_g⁰ − 0.2 eV, and an optical band gap of E_g^opt ≈ E_g⁰ − 0.1 eV.     

Preparation and characterization of CuIn1 − xGaxSe2 − ySy thin film solar cells by rapid thermal processing

This paper describes the synthesis and characterization of CuIn_1 − xGa_xSe_2 − yS_y (CIGSeS) thin-film solar cells prepared by rapid thermal processing (RTP). An efficiency of 12.78% has been achieved on ~ 2 µm thick absorber. Materials characterization of these films was done by SEM, EDS, XRD, and AES. J-V curves were obtained at different temperatures. It was found that the open circuit voltage increases as temperature decreases while the short circuit current stays constant. Dependence of the open circuit voltage and fill factor on temperature has been estimated. Bandgap value calculated from the intercept of the linear extrapolation was 1.1-1.2 eV. Capacitance-voltage analysis gave a carrier density of 4.0 × 10¹⁵ cm^− 3.     

Parameterization of CuIn1−xGaxSe2 (x = 0, 0.5, and 1) energy bands

Parameterization of the electronic band structure of CuIn_1−xGa_xSe₂ (x = 0, 0.5, and 1) demonstrates that the energy dispersions of the three uppermost valence bands [E_j(k); j = v1, v2, and v3] are strongly anisotropic and non-parabolic even very close to the Γ-point valence-band maximum E_v1(0). Also the lowest conduction band E_c1(k) is anisotropic and non-parabolic for energies ~ 0.05 eV above the band-gap energy. Since the electrical conductivity depends directly on the energy dispersion, future electron and hole transport simulations of CuIn_1−xGa_xSe₂ need to go beyond the parabolic approximation of the bands. We therefore present a parameterization of the energy bands, the k-dependency of the effective electron and hole masses m_j(k), and also an average energy-dependent approximation of the masses m_j(E).     

Towards an electronic model for CuIn1 − xGaxSe2 solar cells

We model some aspects of highly efficient CuIn_1 − xGa_xSe₂ solar cells with x ≈ 0.3 as well as wide band gap cells with x = 1 and ask for the dominant recombination mechanism which limits the V_oc of these devices. For CuIn_1 − xGa_xSe₂ solar cells with x ≈ 0.3, interface recombination combined with Fermi-level pinning is a possible but unlikely recombination mechanism. We argue that these cells are rather limited by recombination in the quasi-neutral region (QNR) including the back contact. Using the expression for the QNR recombination rate we calculate the derivative of the collection function in the absorber at the space charge region edge which is in reasonable agreement with the experiment. It turns out that the diffusion length must approximate the absorber thickness. Based on this information, we draw a band diagram for a CuIn_1 − xGa_xSe₂ solar cells with x ≈ 0.3 and plot the simulated collection function. For cells with x = 1 (Cu-poor CuGaSe₂), the experimental activation energy of the recombination rate mostly equals the absorber band gap, i.e. E_a ≈ E_g,a = 1.67 eV. As the experimental interface band gap is smaller than E_a, interface recombination must be ruled out. Thus, the carrier lifetime in the Cu-poor CuGaSe₂ absorber should be so small that bulk recombination is more efficient than interface recombination. From this consideration, we postulate an electron lifetime value of 10⁻¹² s for CuGaSe₂.     

Origin of defects in CuIn1 − xGaxSe2 solar cells with varied Ga content

A series of CuIn_1 − xGa_xSe₂ solar cells with varied Ga content (0 ≤ x ≤ 1) was prepared using a three-stage co-evaporation process. The grain sizes of these devices vary with gallium content, exhibiting a maximum for approximately x = 0.2, which does not coincide with the maximum of the solar conversion efficiency observed between 0.34 < x < 0.37 for these devices.Admittance spectroscopy and drive-level capacitance profiling measurements were performed yielding a defect level with an activation energy of E_a = 0.1 eV which is independent of the amount of Ga and the grain size respectively. This defect closely resembles the N1 defect level reported in the literature. Only for relatively high Ga contents (x > 0.7) an additional defect appears. An equivalent circuit model describing a parallel connection of bulk and grain boundary capacitors allows us to conclude that the detected shallow defect is not predominantly located at the grain boundaries.     

Development of ZnSexTe1 − x p-type contacts for high efficiency tandem structures

With a band gap of 1.7 eV CdSe is a near-ideal top cell for a tandem solar cell using CuIn_xGa_1 − xSe₂ (CIGS) as the bottom cell. We and others have demonstrated that CdSe has excellent electronic properties that should result in efficiencies of 18%. The primary obstacle to meeting that objective is low Voc due to not having an effective p-contact. We have made some progress in this regard with ZnSe and ZnTe, but each has limitations that limit Voc below the needed 1+ V. ZnSe is not easily doped p-type, and ZnTe's valence band is not as low as desired. In our recent work we have been combining the two binaries to try to get around these limitations. Films are deposited using conventional co-evaporation to be consistent with manufacturing constraints for solar cells. In one approach we are forming the ternary ZnSe_xTe_1 − x. While giving up a bit of ZnSe's favorable valence band location, we hope to enhance dopability. One of the difficulties that we encountered was maintaining stoichiometry for our targeted Te/Se ratio of 1.0. Such films are typically Zn-rich and not dopable. We found deposition techniques that allow access to stoichiometric films with the desired ratio and have measured modest conductivity. We are also investigating superlattice structures as another way of combining the properties of the binaries. This approach avoids competition between the group VI elements during deposition allowing more control over stoichiometry. However, an added difficulty is posed by the activated N dopant environment in the chamber in that it enhances loss of Te during deposition. The superlattice approach provides means of compensation and is producing stoichiometric films, but conductivity is not yet evident.     

Study of GeYSi1 − Y:H films deposited by low frequency plasma

In this work, we report a study of the optical properties measured through spectral transmission and spectroscopic ellipsometry in Ge:H and Ge_YSi_1 − Y:H (Y ≈ 0.97) films deposited by low frequency (LF) PE CVD with hydrogen (H) dilution. The dilution was varied in the range of R = 20 to 80. It was observed that H-dilution influences in a different way on the interface and bulk optical properties, which also depend on incorporation of silicon. The films with low band tail characterized by its Urbach energy, E_U, and defect absorption, α_D, have been obtained in Ge:H films for R = 50 with E_U = 0.040 eV and α_D = 2 × 10³ cm^− 1 (hν ≈ 1.04 eV), and in Ge_YSi_1 − Y:H films for R=75 with E_U = 0.030 eV and α_D = 5 × 10² cm^− 1 (hν ≈ 1.04 eV).     

CuIn1 − xGaxSe2 photovoltaic devices for tandem solar cell application

CuIn_1 − xGa_xSe₂ (CIGS) solar cells show a good spectral response in a wide range of the solar spectrum and the bandgap of CIGS can be adjusted from 1.0 eV to 1.7 eV by increasing the gallium-to-indium ratio of the absorber. While the bandgaps of Ga-rich CIGS or CGS devices make them suitable for top or intermediate cells, the In rich CIGS or CIS devices are well suited to be used as bottom cells in tandem solar cells. The photocurrent can be adapted to the desired value for current matching in tandem cells by changing the composition of CIGS which influences the absorption characteristics. Therefore, CIGS layers with different [Ga]/[In + Ga] ratios were grown on Mo and ZnO:Al coated glass substrates. The grain size, composition of the layers, and morphology strongly depend on the Ga content. Layers with Ga rich composition exhibit smaller grain size and poor photovoltaic performance. The current densities of CIGS solar cells on ZnO:Al/glass varied from 29 mA cm^− 2 to 13 mA cm^− 2 depending on the Ga content, and 13.5% efficient cells were achieved using a low temperature process (450 °C). However, Ga-rich solar cells exhibit lower transmission than dye sensitized solar cells (DSC). Prospects of tandem solar cells combining a DSC with CIGS are presented.     

Structural and optical properties of rock-salt Cd1 − xZnxO thin films prepared by thermal decomposition of electrodeposited Cd1 − xZnxO2

Cd_1 − xZn_xO nanocrystalline thin films with rock-salt structure were obtained through thermal decomposition of Cd_1 − xZn_xO₂ (x = 0, 0.37, 0.57, 1) thin films which were electrodeposited from aqueous solution at room temperature. X-ray diffraction results showed that the Zn ions were incorporated into rock salt-structure of CdO and the crystal lattice parameters decreased with the increase of Zn contents. The bandgaps of the Cd_1 − xZn_xO thin films were obtained from optical transmission and were 2.40, 2.51, 2.63 and 3.25 eV, respectively.     

Band alignment of Cd(1 − x)ZnxS produced by spray pyrolysis method

Cd_(1 − x)Zn_xS thin films have been grown on glass substrates by the spray pyrolysis method using CdCl₂ (0.05 M), ZnCl₂ (0.05 M) and H₂NCSNH₂ (0.05 M) solutions and a substrate temperature of 260 °C. The energy band gap, which depends on the mole fraction × in the spray solution used for preparing the Cd_(1 − x)Zn_xS thin films, was determined. The energy band gaps of CdS and ZnS were determined from absorbance measurements in the visible range as 2.445 eV and 3.75 eV, respectively, using Tauc theory. On the other hand, the values calculated using Elliott-Toyozawa theory were 2.486 eV and 3.87 eV, respectively. The exciton binding energies of Cd_0.8Zn_0.2S and ZnS determined using Elliott-Toyozawa theory were 38 meV and 40 meV, respectively. X-ray diffraction results showed that the Cd_(1 − x)Zn_xS thin films formed were polycrystalline with hexagonal grain structure. Atomic force microscopy studies showed that the surface roughness of the Cd_(1 − x)Zn_xS thin films was about 50 nm. Grain sizes of the Cd_(1 − x)Zn_xS thin films varied between 100 and 760 nm.     

Unusual changes observed in the photoluminescence of annealed InxGa1 − xN/GaN quantum wells explained

In_xGa_1 − xN/GaN heterostructures and quantum wells (QWs) are particularly important in the application of III-V nitride materials for light emitting diodes and laser diodes. The photoluminescence (PL) emissions from In_xGa_1 − xN/GaN QW structures have been reported, where, for successive annealing operations, the PL peak suffers a primary red shift, followed by a blue shift. The observed phenomenon remains unexplained because of its complexity. This paper is intended towards a proper explanation of the observed experimental results through suitable quantum mechanical models and computations, whether the band gap of InN is 1.95 eV or 0.7 eV.     

One-step synthesis and double emission (Ca1 + x − yEuy)Ga2S4 + x phosphor for white LEDs

(Ca_{1 + x − y}Eu_y)Ga₂S_4 + x phosphors have been synthesized one step by solid state reaction. The photoluminescence excitation and emission spectra of phosphors have been studied; the influence of host composition and Eu²⁺ concentration on emission spectra has also been investigated. The emission spectrum consists of yellow emission at 550 nm and red emission at 650 nm. It also indicates that the excitation spectrum is a broadband and can be well matched with the emission of GaN chip. Combined these phosphors with 460 nm-emitting GaN chips, White LEDs have been fabricated. Their electroluminescence spectra have been measured under 20 mA forward-bias current. Their CIE chromaticity coordinates and color temperature indicate that (Ca_{1 + x − y}Eu_y)Ga₂S_4 + x phosphors are promising phosphors for GaN-based white LEDs.     

ZnxCd1 − xS as a heterojunction partner for CuIn1 − xGaxS2 thin film solar cells

Zinc cadmium sulfide (Zn_xCd_1 − xS) heterojunction partner layer prepared with chemical bath deposition (CBD) has exhibited better blue photon response and higher current densities due to its higher bandgap than that of conventional cadmium sulfide (CdS) layer for CuIn_1 − xGa_xS₂ (CIGS2) solar cells. CIGS2/Zn_xCd_1 − xS devices have also shown higher open circuit voltage, V_oc indicating improved junction properties. A conduction band offset has been observed by J-V curves at various temperatures indicating that still higher V_oc can be obtained by optimizing the conduction band offset. This contribution discusses the effect of variation of parameters such as concentration of compounds, pH of solution and deposition time during CBD on device properties and composition and crystallinity of film. Efficiencies comparable to CIGS2/CdS devices have been achieved for CIGS2/Zn_xCd_1 − xS devices.     

CuIn1 − xAlxSe2 thin films obtained by selenization of evaporated metallic precursor layers

CuIn_1 − xAl_xSe₂ (CIAS) thin films were grown by a two stage process. Cu, In and Al layers were sequentially evaporated and subsequently heated with elemental selenium in a quasi-closed graphite box. Different x values (0 ≤ x ≤ 0.6) were obtained by varying the Al and In precursor layers thicknesses. Selenization conditions such as Se amount provided during the selenization process were adjusted in order to optimize the film properties. Polycrystalline CuIn_1 − xAl_xSe₂ thin films with chalcopyrite structure were obtained. Referred to CuInSe₂ thin films the lattice parameters, the (112) orientation and the average crystallite size decreased and the band gap energy increased with increasing Al content. To optimize structural properties of the CIAS films a higher Se amount was required as the x value increased. The incorporation of Al changed the thin film morphology towards smaller grain sizes and less compact structures.     

A comparative study of the properties of thermally evaporated CuIn2n + 1S3n + 2 (n = 0, 1, 2 and 3) thin films

CuInS₂, CuIn₃S₅, CuIn₅S₈ and CuIn₇S₁₁ compounds were synthesized by the horizontal Bridgman method using high-purity copper, indium and sulphur elements. Crushed powders of these ingots were used as raw materials for the vacuum thermal evaporation. So, CuIn_2n + 1S_3n + 2 (n = 0, 1, 2, and 3) thin films were deposited by single source vacuum thermal evaporation onto glass substrates heated at 150 °C. The structural, compositional, morphological, electrical and optical properties of the deposited films were studied using X-ray diffraction (XRD), energy dispersive X-ray, atomic force microscopy and optical measurement techniques. XRD results revealed that all the films are polycrystalline. However, CuInS₂ and CuIn₃S₅ films had a chalcopyrite structure with preferred orientation along 112 while CuIn₅S₈ and CuIn₇S₁₁ films exhibit a spinel structure with preferred orientation along 311. The absorption coefficients of the all CuIn_2n + 1S_3n + 2 films are in the range of 10⁻⁴ and 10⁻⁵ cm⁻¹. The direct optical band gaps of CuIn_2n + 1S_3n + 2 layers are found to be 1.56, 1.78, 1.75 and 1.30 eV for n = 0, 1, 2, and 3, respectively. CuIn₃S₅ and CuIn₅S₈ films are p type with electrical resistivities of 4 and 12 Ω cm whereas CuInS₂ and CuIn₇S₁₁ are highly compensated with resistivities of 1470 and 1176 Ω cm, respectively.     

Pechini sol-gel deposition and luminescent properties of SrLa1−xRExGa3O7 (RE = Eu, Tb) phosphor films

SrLa_1−xRE_xGa₃O₇ (RE = Eu³⁺, Tb³⁺) phosphor films were deposited on quartz glass substrates by a simple Pechini sol-gel method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy, field-emission scanning electron microscopy, photoluminescence spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 700 °C and crystallized fully at 900 °C. The results of FT-IR spectra were in agreement with those of XRD. Uniform and crack-free films annealed at 900 °C were obtained with average grain size of 80 nm, root mean square roughness of 46 nm and thickness of 130 nm. The RE ions showed their characteristic emission in crystalline SrLa_1−xRE_xGa₃O₇ films, i.e., Eu³⁺⁵D₀-⁷F_J (J = 0, 1, 2, 3, 4), Tb³⁺⁵D₄-⁷F_J (J = 6, 5, 4, 3) emissions, respectively. The optimum concentrations (x) of Eu³⁺ and Tb³⁺ were determined to be 50, and 80 mol% in SrLa_1−xRE_xGa₃O₇ films, respectively.     

Calorimetric and optical study of amorphous Se85 − xTe15Bix glassy alloy

Bulk samples of Se_85 − xTe₁₅Bi_x (where x = 0, 1, 2, 3, 4, 5) glassy alloys are obtained by melt quenching technique. Differential scanning calorimetric (DSC) technique has been applied to determine the thermal properties of Se-rich Se_85 − xTe₁₅Bi_x glassy alloys in the glass transition and crystallization regions at four heating rates (5, 10, 15, 20 K min^− 1). The glass transition temperature (T_g) and peak crystallization temperature(T_p) are found to shift to a higher temperature with increasing heating rate. With Bi addition, the value of (T_g)increases. (T_p) is found to increase as Bi is introduced to the Se-Te host, however further increase in Bi concentration is responsible for the reduction of. Thin film of bulk samples are deposited on glass substrate using thermal evaporation technique under vacuum for optical characterization. Optical band gap is estimated using Tauc's extrapolation and is found to decrease from 1.46 to 1.24 eV with the Bi addition.     

Structural and optical properties of polycrystalline CdSexTe1−x (0 ≤ x ≤ 0.4) thin films

CdSe_xTe_1−x (0 ≤ x ≤ 0.4) ternary thin films have been deposited on quartz substrates at room temperature by a single source thermal evaporation. X-ray diffraction patterns and transmission electron microscope micrographs of these films showed that the films were of polycrystalline texture over the whole range studied and exhibit predominant cubic (zinc blende) structure with strong preferential orientation of the crystallites along (1 1 1) direction. Linear variation of the lattice constant with mole fraction x is observed obeying Vegard's law. The dependence of the optical constants, the refractive index n and extinction coefficient k, of the films on the mole fraction x was studied in the spectral range of 400-2500 nm. The normal dispersion of the refractive index of the films could be described using the Wemple-DiDomenco single-oscillator model. CdSe_xTe_1−x thin films of different composition have two direct and indirect transitions corresponding to energy gaps and . The variation in either or with x indicates that this system belongs to the amalgamation type. The variation follows a subquadratic dependence and the bowing parameters were found to be 0.36 and 0.48 eV for the direct, and indirect energy gaps, respectively. Direct linear variation of the ratio N/m^* with x is observed.     

Effect of GaAs substrate misorientation on InxGa1 − xAs crystalline quality and photovoltaic performance

This paper presents the quality of In_xGa_1 − xAs (0 < x < 0.2) layers grown on GaAs substrate with different miscut angle (2° and 15°) by metal organic chemical vapor deposition. The crystalline quality of In_xGa_1 − xAs layers was found to strongly depend on indium content and substrate misorientation. The In_0.16Ga_0.84As solar cells with PN structure were grown on a 2°- and 15°-off GaAs substrates. It was found that the photovoltaic performance of In_0.16Ga_0.84As solar cell grown on 2°-off GaAs substrate was better than that of In_0.16Ga_0.84As grown on a 15°-off GaAs substrate, because the In_xGa_1 − xAs films grown on 15°-off GaAs substrate shows a highly strain relaxation in active layer of solar cell, which causes the high dislocation density at the initial active layer/In_xGa_1 − xAs graded layer interface.     

Formation of CuIn1 − xAlxSe2 thin films studied by Raman scattering

CuIn_1 − xAl_xSe₂ (CIAS) thin films (x = 0.06, 0.18, 0.39, 0.64, 0.80 and 1) with thicknesses of approximately 1 μm were formed by the selenization of sputtered Cu―In―Al precursors and studied via X-ray diffraction, inductively coupled plasma mass spectrometry and micro-Raman spectroscopy at room temperature. Precursor films selenized at 300, 350, 400, 450, 500 and 550 °C were examined via Raman spectroscopy in the range 50-500 cm^− 1 with resolution of 0.3 cm^− 1. Sequential formation of In_xSe_y, Cu_2 − xSe, CuInSe₂ (CIS) and CIAS phases was observed as the selenization temperature was increased. Conversion of CIS to CIAS was initiated at 500 °C. For all CuIn_1 − xAl_xSe₂ products, the A₁ phonon frequency varied nonlinearly with respect to the aluminum composition parameter x in the range 172 cm^− 1 to 186 cm^− 1.