Ion-beam analysis of CuInSe<Subscript>2</Subscript> solar cells deposited on polyimide foil

CuInSe₂ (CIS) solar cells deposited on polyimide foil by the Solarion company in a web-coater-based process using sputter and evaporation techniques were investigated in the ion beam laboratory LIPSION of the University of Leipzig by means of Rutherford backscattering spectrometry (RBS) and particle-induced X-ray emission (PIXE) using high-energy broad ion beams and microbeams. From these measurements the composition of the absorber and the lateral homogeneity and film thicknesses of the individual layers could be determined on the basis of some reasonable assumptions. For the first time, quantitative depth profiling of the individual elements was performed by microPIXE measurements on a beveled section prepared by ion-beam etching of a CIS solar cell. Within the CIS absorber layer no significant concentration–depth gradients were found for Cu, In, and Se, in contrast with results from secondary neutral mass spectrometry (SNMS) depth profiling, which was applied to the same samples for comparison. Furthermore, both PIXE and SNMS showed the presence of a remarkable amount of Cd from the CdS buffer layer in the underlying absorber.     

Thermische Zersetzung von CuInSe2, LiInSe2 und LiInTe2

The thermal decompositions of CuInSe₂, LiInSe₂ and LiInTe₂ in vacuum at high temperatures were studied by using TG/DTG coupled with mass spectrometry. For CuInSe₂, two steps were found to be significant. Up to 1000 °C Se₂ and In₂Se evaporate, followed later by Cu₂Se. The Li-containing compounds show similar behaviour. However, Li⁺ was already detected during the first step. Obviously, Li₂Se dissociates more readily than Cu₂Se. No Cu⁺ species were detected up to the complete evaporation of CuInSe₂.     

Single‐Step Sulfo‐Selenization Method to Synthesize Cu2ZnSn(SySe1−y)4 Absorbers from Metallic Stack Precursors

Pentenary Cu₂ZnSn(S_ySe_1?y)₄ (kesterite) photovoltaic absorbers are synthesized by a one‐step annealing process from copper‐poor and zinc‐rich precursor metallic stacks prepared by direct‐current magnetron sputtering deposition. Depending on the chalcogen source—mixtures of sulfur and selenium powders, or selenium disulfide—as well as the annealing temperature and pressure, this simple methodology permits the tuning of the absorber composition from sulfur‐rich to selenium‐rich in one single annealing process. The impact of the thermal treatment variables on chalcogenide incorporation is investigated. The effect of the S/(S+Se) compositional ratio on the structural and morphological properties of the as‐grown films, and the optoelectronic parameters of solar cells fabricated using these absorber films is studied. Using this single‐step sulfo‐selenization method, pentenary kesterite‐based devices with conversion efficiencies up to 4.4 % are obtained.     

A crystallographic description of experimentally identified formation reactions of Cu(In,Ga)Se2

This work describes solid-state reactions for the formation of the chalcopyrite compounds CuInSe₂, CuGaSe₂ and Cu(In,Ga)Se₂ on atomic scale. The most important chalcopyrite formation reactions which were identified by the authors by real-time in situ X-ray diffraction in preceding experiments are (A) CuSe+InSe→CuInSe₂, (B) Cu₂Se+2 InSe+Se→2 CuInSe₂ and (C) Cu₂Se+In₂Se₃→2 CuInSe₂. During the selenistaion of a metallic precursor containing gallium a separate fourth reaction occurs: (D) Cu₂Se+Ga₂Se₃→2 CuGaSe₂. The quaternary compound is finally formed by interdiffusion of CuInSe₂ with CuGaSe₂ (E). These five reactions differ in their activation energy and reaction speed. We explain these differences qualitatively by analysing the involved crystal structures for each reaction. It turns out that all reactions involved in the formation of Cu(In,Ga)Se₂ are promoted by epitaxial relations, which facilitates the formation of polycrystalline thin films at temperatures much below those necessary for single crystal growth. Recommendations for the growth of larger grains of Cu(In,Ga)Se₂ containing fewer defects are given.     

Detection of trace impurities in Cu(In, Ga)Se2 thin film solar cells by laser ablation ICP-MS

CIGS solar cells (CIGS: CuInSe₂, doped with gallium) on flexible glass fibre substrates were investigated to determine a possible migration of compounds from the substrate through the back contact layer into the absorber layer. We employed laser ablation ICP-MS to perform depth profile analysis as this technique combines ease of sample preparation with high sensitivity and moderate depth resolution. Careful optimization of the fluence and repetition rate of the laser system was necessary to ensure sufficient depth resolution in order to be able to relate the transient signals to the different layers. The results show that apart from sodium and small amounts of titanium no elements have migrated into the absorber layer. This was confirmed by micro-PIXE measurements on cross sections of the cell.     

Electrodeposition of CuInSe<Subscript>2</Subscript> films onto a molybdenum electrode

Joint reduction of Cu(II), Se(IV), and In(III) ions at a molybdenum electrode from a solution based of sulfosalicylic acid solution was studied. The optimal range of potentials for deposition of the CuInSe₂ compound was chosen. The composition of the films obtained was confirmed by X-ray phase and electron microprobe analyses.     

CHALCOGENIDE PHOTOVOLTAIC SOLAR CELLS OF SPECIAL INTEREST

Abstract

A brief review is given of those semiconducting selenides and tellurides that appear suitable for the absorber layer of a photovoltaic solar cell, with energy gaps in the range 1 to 2 eV. Furthermore, to obtain a lower cost cell, the semiconductor is also required to be used in the form of a thin polycrystalline film, necessitating a high optical absorption coefficient in the material. At the present time the two best chalcogenides meeting these requirements are the compounds CuInSe ₂ and CdTe, both of which have been used in polycrystalline thin film structures with CdS, as the window layer, yielding conversion efficiencies of over 10%. They have also demonstrated very good chemical stability.     

Polyol-mediated synthesis of Cu2ZnSn(S,Se)4 kesterite nanoparticles and their use in thin-film solar cells

Cu₂ZnSnS₄ kesterite nanoparticles (CZTS) with a particle diameter of 10–20 nm are prepared by a polyol-mediated synthesis with diethylene glycol as the liquid phase. The polyol – a high-boiling multidentate alcohol − allows controlling the particle size and agglomeration as well as preparing readily crystalline nanoparticles. The as-prepared kesterite nanoparticles exhibit an overall composition of Cu_1.56Zn_1.29Sn_1.16S_4.59 and a band gap of 1.37 eV. As a first test, thin-film solar cells are manufactured after layer deposition of the as-prepared CZTS nanoparticles and conversion to Cu₂ZnSn(S,Se)₄ (CZTSSe) via gas-phase selenization. The volume increase of about 15% due to the CZTS-to-CZTSSe conversion supports the formation of a dense layer, reduces the interparticulate surfaces and leads to a reduction of the band gap to 1.14 eV. The chemical composition of the as-prepared CZTS nanoparticles and of the deposited CZTSSe thin film prior and after selenization are studied in detail by energy-dispersive X-ray spectroscopy, Raman spectroscopy and X-ray fluorescence analysis. All these methods confirm the intended copper-poor and zinc-/tin-rich CZTS/CZTSSe composition. The resulting thin-film solar cells show an open-circuit voltage of 247.3 mV, a short-circuit current density of 21.3 mA/cm², a fill factor of 41.1% and a power-conversion efficiency of 2.2%.     

Electrochemical performance of grown layer of Ni(OH)2 on nickel foam and treatment with phosphide and selenide for efficient water splitting

Active nanocomposites synthesized by the electrochemical approach play a vital role in energy generation, conversion, and storage technologies. Recently, scientists began to explore the use of earth-rich transition metal-based materials to replace precious metal-based catalysts. Transition metals (TMs) based nickel (Ni) and their pnictides compounds such as phosphides and selenides exhibit good activity for hydrogen evaluation reaction (HER) and the entire water electrolysis process. In this study, we first prepared Ni(OH)₂ and grown its layer on Ni foam (NF) and treated it with selenide (Se) and phosphide (P) then nickel-based selenide-phosphide catalyst (Ni–P–Se) was prepared by simultaneous selenization and phosphidation process for the first time. The as-obtained composite was then analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), elemental mapping and transmission electron microscope (TEM) means to study the composition, structure, and micro-morphology of materials. Furthermore, we also observed electrocatalytic water splitting activity using electrochemical cell. The results of electrochemical tests depicted that the selenization and phosphidation treatments significantly enhanced the electrocatalytic HER activity of the starting materials. The overpotentials required for Ni–P–Se to reach 10 ?mA ?cm^?2 and 100 ?mA ?cm^?2 were only 242 ?mV and 282 ?mV. The Tafel slope of Ni–P–Se is 151 ?mV dec^?1, which is lower than that of nickel phosphide, selenide, and hydroxide indicating that selenide-phosphide enhances the HER reaction kinetics of the material, which in turn increases hydrogen output rate as compared with previous studies.     

Scrutinizing the facile growth of β-Ag2Se fine films

Silver selenide thin film is one of the best candidates for thermoelectric devices. In the previous report, we demonstrated that high-performanced [201] oriented β-Ag₂Se thin films can be prepared by direct metal surface element reaction (DMSER) solution selenization in a really short time at room temperature. However, the underlying mechanism of the fast reaction process were not discussed in depth. Herein, based on hard soft acid base (HASB) theory and strong oxidation, we further explored the possible reaction mechanism of the in-situ growth of β-Ag₂Se thin films as the function of the reaction time. The time-dependent experimental results showed that the formation of the β-Ag₂Se on elemental Ag precursor (∼690 nm thick) in Se/Na₂S precursor solution is in a growth driven mode with no obvious orientation or growth rate selections to the elemental Ag precursors. Our investigations provide a prerequisite for the further preparation of thermoelectric materials with excellent properties.     

Trigonal pyramidal CuInSe2 nanocryastals derived by a new method for photovoltaic applications

Copper indium selenide (CuInSe₂) nanocrystals with trigonal pyramidal shape are synthesized by a two-step process for photovoltaic applications. Structural, morphological and optical properties of the as-synthesized CuInSe₂ nanocrystals are characterized by using powder X-ray diffraction analysis, transmission electron microscopy, X-ray photoelectron spectroscopy and UV-Vis absorption spectroscopy. Results indicate that the monodispersed nanocrystals show a single phase polycrystalline and the size of the trigonal pyramid is in the range of 10-12 nm, and the average composition ratio of the Cu/In/Se is measured to be 1.0:1.2:2.0. It is also investigated that the size and morphology of the CuInSe₂ nanocrystals can be tuned through a manipulation of the reaction time. Under an illumination of the simulated AM 1.5, the as-fabricated hybrid solar cell based on the P3HT/CuInSe₂ nanocrystals blends exhibits a promising open circuit voltage (V_oc) of 0.42 V and its energy conversion efficiency is as 3 times as that of the solar cell fabricated by only the naked P3HT polymer.     

Dynamic analysis on metal selenide electrodeposition

Based on the basic principles of kinetics and some reasonable assumptions about the electrodeposition process, a dynamic model for metal selenide electrodeposition (kink site selected model) was constructed. This model is of universal significance in realizing the compositional prediction and dynamic behavior analysis of deposited films for different main salt concentration ratios and was applied to the ternary Cu–In–Se system. For CuInSe₂ electrodeposition, in the Cu–Se system, the co-deposition of Cu and Se can be carried out within a large range of main salt concentration ratio; in the Cu–In system, the mole fraction of Cu in deposited thin films is always higher than that of Cu²⁺ in electrolyte, while in the In–Se system, the co-deposition of In and Se can be achieved only when the In³⁺ concentration is much higher than the H₂SeO₃ concentration. As for the compositional estimation of CuInSe₂, the predictive results of our dynamic model agree well with the experimental data. It is then found that by correcting the difference of kink site selectivity constants caused by the change of deposition potential, the error of the predictive results can be reduced.     

Mechanism of a microwave-assisted polyol synthesis of nanosize CuInSe2 particles and their optical and photoelectric properties

Mechanism of the reaction in which CuInSe₂ nanoparticles are formed in synthesis by the microwaveassisted polyol method was studied. The morphology and optical properties of thin layers (films) produced from the synthesized CuInSe₂ nanoparticles and the morphology and photoelectric properties of composite films based on CuInSe₂ and [6,6]phenyl C61 butyric acid methyl ester were examined. It is shown that CuInSe₂ nanoparticles can be used to form a photo-absorbing layer in composite organo-inorganic solar cells.     

Metal Precursor Influence on Performance of CuIn1-xGaxSe2 Films

CuIn_1-xGa_xSe₂ (CIGS) films were prepared by a two-stage method, in which Cu-In-Ga metallic precursors were firstly deposited on unheated Mo-coated soda lime glass substrates by direct current sputtering CuGa (20%Ga) and radio frequency sputtering In targets inan Ar atmosphere, followed by selenization at 520 oC for 40 min in Se vapor. By adjust-ing the sputtering thickness ratio of surface CuGa (20%Ga) and bottom CuGa (20%Ga) alloy layers in metal precursor, different CIGS thin films were fabricated. Through X-ray diffraction spectra, Raman spectra, local energy dispersive spectrometer, planar- and cross-sectional views of scanning electron microscopy measurements, it revealed that the CIGS thin films from selenization of metal precursor with CuGa:In:CuGa thickness ratio of 7:20:3 (sample-2-se) was of chalcopyrite structure with the preferred (112) orientation, and the grains sizes ranged from 0.5 μm to 2 μm, and sample-2-se had no binary compound phase of In-Se and order defect compound phase. Consequently, the results of illuminated current-voltage curve and quantum efficiency measurements showed that the CIGS film device made from sample-2-se had relative higher photo-electric conversion efficiency (3.59%) and good spectrum response.     

Electrochemical growth of CuInSe<Subscript>2</Subscript> thin film on different substrates from alkaline medium. Characterization of the films

The simultaneous electrodeposition of the system Cu–In–Se was investigated. The study was carried out at pH 8.5 using diethylentriamine as complexing agent for the Cu⁺² ion. The synthesis of CuInSe₂ semiconductor thin films was carried out by electrodeposition on different substrates [indium–tin oxide (ITO) on glass, aluminum and type 304 steel]. The simultaneous codeposition of the Cu, In, and Se was achieved by constant potential electrolysis technique in aqueous solutions containing the elements that conform this material. The deposits of CuInSe₂ were about 4 μm thick, which is thick enough for the photovoltaic effect to take place. The as-deposited films were characterized by atomic emission spectroscopy with inductive coupling plasm (AES-ICP) and scanning electronic microscopy (SEM). Annealed films were characterized X-ray diffraction, optical NIR spectroscopy, and photoelectrochemical studies The films were obtained with a well-defined composition, very close to the expected one. Homogeneous deposit with chalcopyrite structure was produced. A In₂O₃ phase was also observed. Annealing of the film improved the crystallinity of the films. Good photo response, an appropriate absorption coefficient, and a band gap of 1.09 eV were obtained.     

Electrodeposition of CuInSe2 films by an alternating double-potentiostatic method using nearly neutral electrolytes

One step electrodeposition with an alternating double-potentiostatic(DPSED) program was used to prepare CuInSe₂ thin films in nearly neutral aqueous electrolytes with sodium citrate complex. Linear sweep voltammetry(LSV) was measured to probe voltammetric properties of electrolytes with respect to Cu, In and Se individual precursor and their mixed solutions. Compositional and structural characteristics of the as-deposited and annealed films at 400 °C in Ar atmosphere for 0.5 h were analyzed by XRD and XPS. The results showed that reduction of Cu²⁺ to Cu⁺ at one potential point of ?800 mV and subsequently formation of CuIn alloy as well as metal In and amorphous Se at the other potential point of ?1400 mV were responsible for synthesis of CISe chalcopyrite. Composition self-regulation made DPSED films have three elements co-deposition and more uniform element distribution, which promoted chalcopyrite CISe formation.     

电沉积-退火工艺制备铜铟硒太阳能电池薄膜及表征

CuInSe₂ (CIS) films with good crystalline quality were synthesized by electrodeposition followed by annealing in Se vapor at 530 oC. The morphology, composition, crystal structure, optical and electrical properties of the CIS films were investigated by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, Raman spectroscopy, UV-VIS-NIR spectroscopy, and admittance spectroscopy. The results revealed that the annealed CIS films had chalcopyrite structure and consisted of relatively large grains in the range of 500-1000 nm and single grain of films extend usually through the whole film thickness. The band gap of CIS films was 0.98 eV and carrier concentration was in the order of 10¹⁶ cm^-3 after etching the Cu-Se compounds on the film surface. Solar cells with the structure of AZO/i-ZnO/CdS/CIS/Mo/glass were fabricated. Current density vs. voltage test under standard reported condition showed the solar cells with an area of 0.2 cm² had a conversion efficiency of 0.96%. The underlying physics was also discussed.     

Enhancement in as-grown CuInSe2 film microstructure by a three potential pulsed electrodeposition method

P-type copper indium diselenide (CuInSe₂) films have been prepared onto ITO substrates by an electrodeposition method, that sequentially applies potential pulses at the deposition potential of each element Cu, Se and In, and then step it back in cyclically to induce the solid state reaction between the elements. Two electrolyte concentrations as well as three different pulse durations were assessed. The resulting films were compared with those deposited at fixed electrode potentials. As-grown films are nanocrystalline and have an E_g ～ 0.95 eV. Raman spectroscopy shows that Se and Cu–Se contents decrease while pulse duration increases and electrolyte concentration decreases. Cu–Se phases are even absent for films grown at the low electrolyte concentration. These results represent a great improvement in the film phase purity reducing the need of post-deposition treatments.     

A Directed Route to Colloidal Nanoparticle Synthesis of the Copper Selenophosphate Cu3PSe4

The first colloidal nanoparticle synthesis of the copper selenophosphate Cu₃PSe₄, a promising new material for photovoltaics, is reported. Because the formation of binary copper selenide impurities seemed to form more readily, two approaches were developed to install phosphorus bonds directly: 1) the synthesis of molecular P₄Se₃ and subsequent reaction with a copper precursor, (P‐Se)+Cu, and 2) the synthesis of copper phosphide, Cu₃P, nanoparticles and subsequent reaction with a selenium precursor, (Cu‐P)+Se. The isolation and purification of Cu₃P nanoparticles and subsequent selenization yielded phase‐pure Cu₃PSe₄. Solvent effects and Se precursor reactivities were elucidated and were key to understanding the final reaction conditions.     

Synthesis of WOn‐WX2 (n=2.7, 2.9; X=S,Se) Heterostructures for Highly Efficient Green Quantum Dot Light‐Emitting Diodes

Preparation of two‐dimensional (2D) heterostructures is important not only fundamentally, but also technologically for applications in electronics and optoelectronics. Herein, we report a facile colloidal method for the synthesis of WO_n ‐WX₂ (n =2.7, 2.9; X=S, Se) heterostructures by sulfurization or selenization of WO_n nanomaterials. The WO_n ‐WX₂ heterostructures are composed of WO_2.9 nanoparticles (NPs) or WO_2.7 nanowires (NWs) grown together with single‐ or few‐layer WX₂ nanosheets (NSs). As a proof‐of‐concept application, the WO_n ‐WX₂ heterostructures are used as the anode interfacial buffer layer for green quantum dot light‐emitting diodes (QLEDs). The QLED prepared with WO_2.9 NP‐WSe₂ NS heterostructures achieves external quantum efficiency (EQE) of 8.53 %. To our knowledge, this is the highest efficiency in the reported green QLEDs using inorganic materials as the hole injection layer.