P.M.P. Salomé

A study of ternary Cu2SnS3 and Cu3SnS4 thin films prepared by sulfurizing stacked metal precursors

Thin films of Cu2SnS3 and Cu3SnS4 were grown by sulfurization of dc magnetron sputtered Sn–Cu metallic precursors in a S2 atmosphere. Different maximum sulfurization temperatures were tested which allowed the study of the Cu2SnS3 phase changes. For a temperature of 350 °C the films were composed of tetragonal (I-42m) Cu2SnS3. The films sulfurized at a maximum temperature of 400 °C presented a cubic (F-43m) Cu2SnS3 phase. On increasing the temperature up to 520 °C, the Sn content of the layer decreased and orthorhombic (Pmn21) Cu3SnS4 was formed. The phase identification and structural analysis were performed using x-ray diffraction (XRD) and electron backscattered diffraction (EBSD) analysis. Raman scattering analysis was also performed and a comparison with XRD and EBSD data allowed the assignment of peaks at 336 and 351 cm−1 for tetragonal Cu2SnS3, 303 and 355 cm−1 for cubic Cu2SnS3, and 318, 348 and 295 cm−1 for the Cu3SnS4 phase. Compositional analysis was done using energy dispersive spectroscopy and induced coupled plasma analysis. Scanning electron microscopy was used to study the morphology of the layers. Transmittance and reflectance measurements permitted the estimation of absorbance and band gap. These ternary compounds present a high absorbance value close to 104 cm−1. The estimated band gap energy was 1.35 eV for tetragonal (I-42m) Cu2SnS3, 0.96 eV for cubic (F-43m) Cu2SnS3 and 1.60 eV for orthorhombic (Pmn21) Cu3SnS4. A hot point probe was used for the determination of semiconductor conductivity type. The results show that all the samples are p-type semiconductors. A four-point probe was used to obtain the resistivity of these samples. The resistivities for tetragonal Cu2SnS3, cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4 are 4.59 × 10−2 Ω cm, 1.26 × 10−2 Ω cm, 7.40 × 10−4 Ω cm, respectively.

Inline Cu(In,Ga)Se

In this paper, co-evaporation of Cu(In,Ga)Se2 (CIGS) in an inline single-stage process is used to fabricate solar cell devices with up to 18.6% conversion efficiency using a CdS buffer layer and 18.2% using a Zn1-xSnxOy Cd-free buffer layer. Furthermore, a 15.6-cm2 mini-module, with 16.8% conversion efficiency, has been made with the same layer structure as the CdS baseline cells, showing that the uniformity is excellent. The cell results have been externally verified. The CIGS process is described in detail, and material characterization methods show that the CIGS layer exhibits a linear grading in the [Ga]/([Ga]+[In]) ratio, with an average [Ga]/([Ga]+[In]) value of 0.45. Standard processes for CdS as well as Cd-free alternative buffer layers are evaluated, and descriptions of the baseline process for the preparation of all other steps in the Ångström Solar Center standard solar cell are given.

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The temperature dependence of electrical conductivity and the photoconductivity of polycrystalline Cu2ZnSnS4 were investigated. It was found that at high temperatures the electrical conductivity was dominated by band conduction and nearest-neighbour hopping. However, at lower temperatures, both Mott variable-range hopping (VRH) and Efros?Shklovskii VRH were observed. The analysis of electrical transport showed high doping levels and a large compensation ratio, demonstrating large degree of disorder in Cu2ZnSnS4. Photoconductivity studies showed the presence of a persistent photoconductivity effect with decay time increasing with temperature, due to the presence of random local potential fluctuations in the Cu2ZnSnS4 thin film. These random local potential fluctuations cannot be attributed to grain boundaries but to the large disorder in Cu2ZnSnS4.

Co-evaporation for High-Efficiency Solar Cells and Modules

In this report, we propose an AC response equivalent circuit model to describe the admittance measurements of Cu2ZnSnS4 thin film solar cell grown by sulphurization of stacked metallic precursors. This circuit describes the contact resistances, the back contact, and the heterojunction with two trap levels. The study of the back contact resistance allowed the estimation of a back contact barrier of 246 meV. The analysis of the trap series with varying temperature revealed defect activation energies of 45 meV and 113 meV. The solar cell’s electrical parameters were obtained from the J-V curve: conversion efficiency, 1.21%; fill factor, 50%; open circuit voltage, 360 mV; and short circuit current density, 6.8 mA/cm2.

Hopping conduction and persistent photoconductivity in Cu2ZnSnS4 thin films

Thin film solar cells based on Cu(In,Ga)Se2 as an absorber layer use Mo as the back contact. This metal is widely used in research and in industry but despite this, there are only a few published studies on the properties of Mo. Properties such as low resistivity and good adhesion to soda lime glass are hard to obtain at the same time. These properties are dependent on the deposition conditions and are associated with the overall stress state of the film. In this report, a study of the deposition of a Mo bilayer is carried out by analysing first single and then bilayers. The best properties of the bilayer were achieved when the bottom layer was deposited at 10 ? 10?3?mbar with a thickness of 500?nm and the top layer deposited at 1 ? 10?3?mbar with a thickness of 300?nm. The films deposited under these conditions showed good adhesion and a sheet resistivity lower than 0.8??.

Admittance spectroscopy of Cu2ZnSnS4 based thin film solar cells

In this work, tin selenide thin films (SnSex) were grown on soda lime glass substrates by selenization of dc magnetron sputtered Sn metallic precursors. Selenization was performed at maximum temperatures in the range 300 °C to 570 °C. The thickness and the composition of the films were analysed using step profilometry and energy dispersive spectroscopy, respectively. The films were structurally and optically investigated by X-ray diffraction, Raman spectroscopy and optical transmittance and reflectance measurements. X-Ray diffraction patterns suggest that for temperatures between 300 °C and 470 °C, the films are composed of the hexagonal-SnSe2 phase. By increasing the temperature, the films selenized at maximum temperatures of 530 °C and 570 °C show orthorhombic-SnSe as the dominant phase with a preferential crystal orientation along the (400) crystallographic plane. Raman scattering analysis allowed the assignment of peaks at 119 cm−1 and 185 cm−1 to the hexagonal-SnSe2 phase and those at 108 cm−1, 130 cm−1 and 150 cm−1 to the orthorhombic-SnSe phase. All samples presented traces of condensed amorphous Se with a characteristic Raman peak located at 255 cm−1. From optical measurements, the estimated band gap energies for hexagonal-SnSe2 were close to 0.9 eV and 1.7 eV for indirect forbidden and direct transitions, respectively. The samples with the dominant orthorhombic-SnSe phase presented estimated band gap energies of 0.95 eV and 1.15 eV for indirect allowed and direct allowed transitions, respectively.

Mo bilayer for thin film photovoltaics revisited

Recently, Cu(In,Ga)Se2 (CIGS) solar cells have achieved 21% world-record efficiency, partly due to the introduction of a postdeposition potassium treatment to improve the front interface of CIGS absorber layers. However, as high-efficiency CIGS solar cells essentially require long diffusion lengths, the highly recombinative rear of these devices also deserves attention. In this paper, an Al2O3 rear surface passivation layer with nanosized local point contacts is studied to reduce recombination at the standard Mo/CIGS rear interface. First, passivation layers with well-controlled grids of nanosized point openings are established by use of electron beam lithography. Next, rear-passivated CIGS solar cells with 240-nm-thick absorber layers are fabricated as study devices. These cells show an increase in open-circuit voltage (+57 mV), short-circuit current (+3.8 mA/cm2), and fill factor [9.5% (abs.)], compared with corresponding unpassivated reference cells, mainly due to improvements in rear surface passivation and rear internal reflection. Finally, solar cell capacitance simulator (SCAPS) modeling is used to calculate the effect of reduced back contact recombination on high-efficiency solar cells with standard absorber layer thickness. The modeling shows that up to 50-mV increase in open-circuit voltage is anticipated.

Thermodynamic pathway for the formation of SnSe and SnSe2 polycrystalline thin films by selenization of metal precursors

Highly efficient Cu(In,Ga)(S,Se)2 photovoltaic thin film solar cells often have a compositional variation of Ga to In in the absorber layer, here described as a Ga-profile. In this work we have stu ...

Introduction of Si PERC Rear Contacting Designto Boost Efficiency of Cu(In,Ga)Se2 Solar Cells

In this paper, Cu(In,Ga)Se2 (CIGS) thin-film solar cells are prepared on nominally alkali-free glass substrates using an in-line CIGS growth process. As compared with, for example, borosilicate glass or quartz, the glass is engineered to have similar thermal expansion coefficient as soda-lime glass (SLG) but with alkali content close to zero. Na is incorporated in the CIGS material using an ex-situ deposited NaF precursor layer evaporated onto the Mo back contact. Several thicknesses of the NaF layer were tested. The results show that there is a process window, between 15 and 22.5 nm NaF, where the solar cell conversion efficiency is comparable with or exceeding that of SLG references. The effect of an NaF layer that is too thin on the solar cell parameters was mainly lowering the open-circuit voltage, which points to a lower effective dopant concentration in the CIGS layer and is also consistent with presented C - V measurements and modeling results. For excessively thick NaF layers, delamination of the CIGS layer occurred. Additional measurements, such as scanning electron microscopy (SEM), secondary ion mass spectrometry, capacitance-voltage analysis (C - V), time-resolved photoluminescence (TRPL), external quantum efficiency (EQE), current-voltage analysis (J-V), and modeling, are presented, and the results are discussed.

Optimizing Ga-profiles for highly efficient Cu(In,Ga)Se2 thin film solar cells in simple and complex defect models

Na plays an important role in the electrical performance of Cu(In,Ga)Se 2 (CIGS) thin-film solar cells. Traditionally, Na has been introduced during the growth of CIGS by thermal diffusion from the soda-lime glass (SLG) substrate; however, better control of the amount of Na is needed to have a more precise control of growth conditions. The introduction of Na into CIGS was studied in three different ways: from the SLG, from a NaF precursor, and from a Na-doped Mo (MoNa) back contact. The most successful approaches were obtained by using the conventional SLG and the NaF precursor. Different growth temperatures of CIGS were tested in an attempt to diffuse more Na from the MoNa layer.