Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

Effect of sodium doping on graded Cu(In1−xGax)Se2 thin films prepared by chemical spray pyrolysis

In the present work we have studied the effect of Na on the properties of graded Cu(In_1−xGa_x)Se₂ (CIGS) layer. Graded CIGS structures were prepared by chemical spray pyrolysis at a substrate temperature of 350 °C on soda lime glass. Sodium chloride is used as a dopant along with metal (Cu/In/Ga) chlorides and n, n-dimethyl selenourea precursors. The addition of Na exhibited better crystallinity with chalcopyrite phase and an improvement in preferential orientation along the (112) plane. Energy dispersive analysis of X-rays (line/point mapping) revealed a graded nature of the film and percentage incorporation of Na (0.86 at%). Raman studies showed that the film without sodium doping consists of mixed phase of chalcopyrite and CuAu ordering. Influence of sodium showed a remarkable decrease in electrical resistivity (0.49–0.087 Ω cm) as well as an increase in carrier concentration (3.0×10¹⁸–2.5×10¹⁹ cm⁻³) compared to the un-doped films. As carrier concentration increased after sodium doping, the band gap shifted from 1.32 eV to 1.20 eV. Activation energies for un-doped and Na doped films from modified Arrhenius plot were calculated to be 0.49 eV and 0.20 eV, respectively. Extremely short carrier lifetimes in the CIGS thin films were measured by a novel, non-destructive, noncontact method (transmission modulated photoconductive decay). Minority carrier lifetimes of graded CIGS layers without and with external Na doping are found to be 3.0 and 5.6 ns, respectively.     

Properties of CdTe films brush plated on high temperature substrates

CdTe thin films were brush plated on substrates maintained at temperatures in the range 30–90 °C from the precursors. The films exhibited cubic structure. Optical band gap of 1.45 eV was obtained. XPS measurements indicated the formation of CdTe. AFM studies indicated the formation of fine grains of the order of 50 nm, for the films deposited on room temperature substrates. Hot probe measurements indicated films to be n-type. A mobility in the range of 5–60 cm² V⁻¹ s⁻¹ and a carrier density of 10¹⁵ cm⁻³ was obtained.     

Effects of deposition pressure on the properties of transparent conductive ZnO:Ga films prepared by DC reactive magnetron sputtering

Gallium (Ga)-doped zinc oxide (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. Effects of deposition pressure on the structural, electrical and optical properties of ZnO:Ga films were investigated. X-ray diffraction (XRD) studies show that the films are highly oriented with their crystallographic c-axis perpendicular to the substrate almost independent of the deposition pressure. The morphology of the film is sensitive to the deposition pressure. The transmittance of the ZnO:Ga thin films is over 90% in the visible range and the lowest resistivity of ZnO:Ga films is 4.48×10⁻⁴ Ω cm.     

Low temperature Solution-Processed ZnO film on flexible substrate

Transparent conductive ZnO films were directly deposited on unseeded polyethersulfone (PES) substrates with a spin-spray method using aqueous solution at a low substrate temperature of 85 °C. All ZnO films were crystalline with wurtzite hexagonal structure and impurity phases were not detected. ZnO films deposited without citrate ions in the reaction solution had a rod array structure. In contrast, ZnO films deposited with citrate ions in the reaction solution had a continuous, dense structure. The transmittance of the ZnO films was improved from 11.9% to 85.3% as their structure changed from rod-like to continuous. After UV irradiation, the ZnO films with a continuous, dense structure had a low resistivity of 9.1×10⁻³ Ω cm, high carrier concentration of 2.7×10²⁰ cm⁻³ and mobility of 2.5 cm² V⁻¹ s⁻¹.     

Properties of fluorine-doped tin oxide films prepared by an improved sol-gel process

Fluorine-doped tin oxide (FTO) films were prepared by an improved sol-gel process, in which FTO films were deposited on glass substrates using evaporation method, with the precursors prepared by the conventional sol-gel method. The coating and sintering processes were combined in the evaporation method, with the advantage of reduced probability of films cracking and simplified preparation process. The effects of F-doping contents and structure of films on properties of films were analyzed. The results showed the performance index (Φ_TC=3.535×10⁻³ Ω⁻¹ cm) of the film was maximum with surface resistance (R_sh) of 14.7 Ω cm⁻¹, average transmittance (T) of 74.4% when F/Sn=14 mol%, the reaction temperature of the sol was 50 °C, and the evaporation temperature was 600 °C in muffle furnace, and the film has densification pyramid morphology and SnO_2−xF_x polycrystalline structure with tetragonal rutile phase. Compared with the commercial FTO films (Φ_TC=3.9×10⁻³ Ω⁻¹ cm, R_sh=27.4 Ω cm⁻¹, T=80%) produced by chemical vapor deposition (CVD) method, the Φ_TC value of FTO films prepared by an improved sol-gel process is close to them, the electrical properties are higher, and the optical properties are lower.     

Effect of electron irradiation on morphological,compositional and electrical properties of nanocluster carbon thin films grown using room temperature based cathodic arc process for large area microelectronics

The influence of 8 MeV electron beam bombardment on room temperature grown nanocluster carbon using cathodic arc process has been studied here. Atomic force microscopy (AFM) study shows that surface roughness varies with varying electron doses. High doses of electrons could causes thermal induce graphitization and morphological changes in the films. Raman spectroscopy analysis reveals that G-peak vary from 1555 cm⁻¹ to 1570 cm⁻¹ and D-peak varying from 1361 cm⁻¹ to 1365 cm⁻¹ indicating the disorderness and presence of both graphitic and diamond-like phases. Room temperature conductivity changes by two to three orders in magnitude. The conductivity in the films could be due to conduction of charge carriers through neighboring islands of conductive chains. Defect states calculated using the differential technique varies from 8 × 10¹⁷cm⁻³ eV⁻¹ to 1.5 × 10¹⁹ cm⁻³ eV⁻¹. Irradiation of nanocluster carbon thin films could be helpful to tune the electrical properties and defect densities of the nanocluster carbon films for various large area, flexible electronic and nano electronic applications.     

Properties of fluorine-doped SnO2 thin films by a green sol–gel method

Fluorine doped tin oxide (FTO) films were fabricated on a glass substrate by a green sol–gel dip-coating process. Non-toxic SnF₂ was used as fluorine source to replace toxic HF or NH₄F. Effect of SnF₂ content, 0–10 mol%, on structure, electrical resistivity, and optical transmittance of the films were investigated using X-ray diffraction, Hall effect measurements, and UV–vis spectra. Structural analysis revealed that the films are polycrystalline with a tetragonal crystal structure. Grain size varies from 43 to 21 nm with increasing fluorine concentration, which in fact critically impacts resultant electrical and optical properties. The 500 °C-annealed FTO film containing 6 mol% SnF₂ shows the lowest electrical resistivity 7.0×10⁻⁴ Ω cm, carrier concentration 1.1×10²¹ cm⁻³, Hall mobility 8.1 cm²V⁻¹ s⁻¹, optical transmittance 90.1% and optical band-gap 3.91 eV. The 6 mol% SnF₂ added film has the highest figure of merit 2.43×10⁻² Ω⁻¹ which is four times higher than that of un-doped FTO films. Because of the promising electrical and optical properties, F-doped thin films prepared by this green process are well-suited for use in all aspects of transparent conducting oxide.     

Effects of RTA temperatures on conductivity and micro-structures of boron-doped silicon nanocrystals in Si-rich oxide thin films

In this work, the B-doped Si rich oxide (SRO) thin films were deposited and then annealed using rapid thermal annealing (RTA) to form SiO₂-matrix silicon nanocrystals (Si NCs). The effects of the RTA temperatures on the structural properties, conduction mechanisms and electrical properties of B-doped SRO thin films (BSF) were investigated systematically using Hall measurements, Fourier transform infrared spectroscopy and Raman spectroscopy. Results showed that the crystalline fraction of annealed BSF increased from 41.3% to 62.8%, the conductivity was increased from 4.48×10⁻³ S/cm to 0.16 s/cm, the carrier concentration was increased from 8.74×10¹⁷ cm⁻³ to 4.9×10¹⁸ cm⁻³ and the carrier mobility was increased from 0.032 cm² V⁻¹ s⁻¹ to 0.2 cm² V⁻¹ s⁻¹ when the RTA temperatures increased from 1050 °C to 1150 °C. In addition, the fluctuation induced tunneling (FIT) theory was applicable to the conduction mechanisms of SiO₂-matrix boron-doped Si-NC thin films.     

A study on phase transformation of SnOx thin films prepared by reactive magnetron sputtering

In the paper, SnO_x thin films were deposited by reactive magnetron sputtering from a tin target in O₂ containing working gas. The evolution from Sn-containing SnO to tetravalent SnO₂ films was investigated. The films could be classified into three groups according to their optical band gaps, which are E_g<2.5 eV, E_g=3.0–3.3 eV and E_g>3.7 eV. The electric measurements show that high conductivity can be obtained much easier in SnO₂ than in SnO films. A high electron mobility of 15.7 cm² V⁻¹ s⁻¹, a carrier concentration of 1.43×10²⁰ cm⁻³ and a resistivity of 2.8×10⁻³ Ω cm have been achieved in amorphous SnO₂ films. Films with the optical band gap of 3.0–3.3 eV remain amorphous though the substrate temperature is as high as 300 °C, which implies that °btaining high mobility in p-type SnO is more challenging in contrast to n-type SnO₂ films.     

Substrate temperature effect on structural,optical and electrical properties of vacuum evaporated SnO2 thin films

Tin oxide (SnO₂) thin films were deposited on glass substrates by thermal evaporation at different substrate temperatures. Increasing substrate temperature (T_s) from 250 to 450 °C reduced resistivity of SnO₂ thin films from 18×10⁻⁴ to 4×10⁻⁴▒ Ω ▒cm. Further increase of temperature up to 550 °C had no effect on the resistivity. For films prepared at 450 °C, high transparency (91.5%) over the visible wavelength region of spectrum was obtained. Refractive index and porosity of the layers were also calculated. A direct band gap at different substrate temperatures is in the range of 3.55−3.77 eV. X-ray diffraction (XRD) results suggested that all films were amorphous in structure at lower substrate temperatures, while crystalline SnO₂ films were obtained at higher temperatures. Scanning electron microscopy images showed that the grain size and crystallinity of films depend on the substrate temperature. SnO₂ films prepared at 550 °C have a very smooth surface with an RMS roughness of 0.38 nm.     

Ultraviolet-assisted annealing for low-temperature solution-processed p-type gallium tin oxide (GTO) transparent semiconductor thin films

Solution-processed p-type gallium tin oxide (GTO) transparent semiconductor thin films were prepared at a low temperature of 300 °C using ultraviolet (UV)-assisted annealing instead of conventional high-temperature annealing (> 500 °C). We report the effects of UV irradiation time on the structural, optical, and electrical properties of sol-gel derived GTO thin films and a comparison study of the physical properties of UV-assisted annealed (UVA) and conventional thermally annealed (CTA) GTO thin films. The Ga doping content was fixed at 15 at% in the precursor solution ([Ga]/[Sn]+[Ga] = 15%). After a spin-coating and preheating procedure was performed two times, the dried sol-gel films were heated on a hotplate at 300 °C under UV light irradiation for 1–4 h. Each UVA GTO thin film had a dense microstructure and flat free surface and exhibited an average optical transmittance approaching 85.0%. The level of crystallinity, crystallite size, and hole concentration density of the GTO thin films increased with increasing UV irradiation time. In this study, the UVA 4 h thin film samples exhibited the highest hole concentration (9.87 × 10¹⁷ cm⁻³) and the lowest resistivity (1.8 Ω cm) and had a hole mobility of 5.1 cm²/Vs.     

In0.75Ga0.25As channel layers with record mobility exceeding 12,000 cm2/Vs for use in high-κ dielectric NMOSFETs

In_0.75Ga_0.25As channel layers with a record mobility exceeding 12,000 cm²/Vs for use in high-κ dielectric NMOSFETs have been fabricated. The device structures which have been grown by molecular beam epitaxy on 3″ semi-insulating InP substrate comprise a 10 nm strained In_0.75Ga_0.25As channel layer and a high-κ oxide based dielectric layer (κ ≅ 20). Electron mobilities of 12,033 and 7,042 cm²/Vs have been measured for sheet carrier concentrations n_s of 2.5 × 10¹² and 6 × 10¹² cm⁻², respectively.     

Enhancing charge transport in copper phthalocyanine thin film by elevating pressure of deposition chamber

Copper phthalocyanine (CuPc)-based thin film transistors were fabricated using CuPc films grown under different deposition pressure (P_dep) (ranging from 1.8 × 10⁻⁴ Pa to 1.0 × 10⁻¹ Pa). The transistor performance highly depended on P_dep. A field-effect mobility of 2.1 × 10⁻² cm²/(V s) was achieved under 1.0 × 10⁻¹ Pa. Detailed investigations revealed that P_dep modulates the molecular packing and orientation of the organic films grown on a SiO₂/Si substrate and influences the charge transport. Furthermore, from a device physics point of view, contact resistance of the fabricated transistors decreased when P_dep increased, which was beneficial in reducing energy consumption.     

Effect of doping concentration on the properties of bismuth doped tin sulfide thin films prepared by spray pyrolysis

Bismuth doped tin sulfide (SnS:Bi) thin films were deposited onto glass substrates by the spray pyrolysis technique at the substrate temperature of 350 °C. The effect of doping concentration [Bi/Sn] on their structural, optical and electrical properties was investigated as a function of bismuth doping between 0 and 8 at%. The XRD results showed that the films were polycrystalline SnS with orthorhombic structure and the crystallites in the films were oriented along (111) direction. Atomic force microscopy revealed that the particle size and surface roughness of the films increased due to Bi-doping. Optical analysis exhibited the band gap value of 1.40 eV for SnS:Bi (6 at%) which was lower than the band gap value for 0 at% of Bi (1.60 eV). The film has low resistivity of 4.788×10⁻¹ Ω-cm and higher carrier concentration of 3.625×10¹⁸ cm⁻³ was obtained at a doping ratio of 6 at%.     

Electrochemical growth of tin(II) oxide films: Application in photocatalytic degradation of methylene blue

We have investigated the semiconducting and photoelectrochemical properties of SnO films grown potentiostatically on tin substrate. The oxide is characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy. The anodic process corresponds to the formation of SnO·nH₂O pre-passive layer that is removed upon increasing potential due to surface etching at the metal/oxide interface. SnO films deposited for long durations (>50 mn) are uniform and well adhered; they thicken up to ~50 nm by diffusion-controlled process and the growth follows a direct logarithmic law. The thickness is determined by coulometry and the X-ray diffraction indicates the tetragonal SnO phase (SG: P4/mmm) with a crystallite size of 32 nm. The Mott–Schottky plot is characteristic of n type conductivity with an electrons density of 5.72×10¹⁸ cm⁻³, a flat band potential of −0.09 V_SCE and a depletion width of ~10 nm. The valence band, located at 5.91 eV below, vacuum is made up of hybridized O²⁻:2p Sn²⁺:5s while the conduction band (4.45 eV) derives from Sn²⁺:5p orbital. The electrochemical impedance spectroscopy (EIS) measured in the range (10⁻²–10⁵ Hz) shows the contribution of the bulk and grain boundaries. The energy band diagram predicts the photodegradation of methylene blue on SnO films. 67% of the initial concentration (10 mg L⁻¹) disappears after 3 h of exposure to visible light (9 mW cm⁻²) with a quantum yield of 0.072.     

Growth of Zn doped Cu(In, Ga)Se2 thin films by RF sputtering for solar cell applications

Cu(In, Ga)Se₂ (CIGS) surface was modified with Zn doping using a magnetron sputtering method. CuInGa:Zn precursor films targeting a CuIn_0.7Ga_0.3Se₂ stoichiometry with increasing Zn content from 0 to 0.8 at% were prepared onto Mo-coated glass substrates via co-sputtering of Cu–Ga alloy, In and Zn targets. The CuInGa:Zn precursors were then selenized with solid Se pellets. The structures and morphologies of grown Zn doped CIGS films were found to depend on the Zn content. At zinc doping level ranging between 0.2 and 0.6 at%, the Zn doping improved the crystallinity and surface morphology of CIGS films. Compared with the performance of the non-doped CIGS cell, the fabricated CIGS solar cell displayed a relative efficiency enhancement of 9–22% and the maximum enhancement was obtained at a Zn content of 0.4 at%.     

Thickness-dependent optoelectronic properties of CuCr0.93Mg0.07O2 thin films deposited by reactive magnetron sputtering

CuCr_0.93Mg_0.07O₂ thin films were successfully deposited by DC reactive magnetron sputtering at 1123 K from metallic targets. The influence of film thickness on the structural and optoelectronic properties of the films was investigated. X-ray diffraction (XRD) results revealed that all the films had a delafossite structure with no other phases. The optical and electrical properties were investigated by UV–VIS spectrophotometer and Hall measurement, respectively. It was found that the optoelectronic properties exhibited a thickness-dependent behavior. The optical band gap and the average transmittance of the films showed a monotonous decrease with respect to the increase in thickness. The average transmittance in the visible region decreased from 67% to 47% as the thickness increased from ~70 nm to ~280 nm. Simultaneously, the conductivity of the films fell from 1.40 S∙cm⁻¹ to 0.27 S∙cm⁻¹. According to Haacke's figure of merit (FOM), a film with a maximum FOM value of about 1.72×10⁻⁷ Ω⁻¹ can be achieved when the thickness is about 70 nm (σ≈ 1.40 S·cm⁻¹ and T_av. ≈67%).     

Effect of the film thickness on the crystal structure and ferroelectric properties of (Hf0.5Zr0.5)O2 thin films deposited on various substrates

In this work, the effect of the film thickness on the crystal structure and ferroelectric properties of (Hf_0.5Zr_0.5)O₂ thin films was investigated. The thin films were deposited on (111) Pt-coated SiO₂, Si, and CaF₂ substrates with thermal expansion coefficients of 0.47, 4.5, and 22×10⁻⁶/°C, respectively. From the X-ray diffraction measurements, it was found that the (Hf_0.5Zr_0.5)O₂ thin films deposited on the SiO₂ and CaF₂ substrates experienced in-plane tensile and compressive strains, respectively, in comparison with the films deposited on the Si substrates. For films deposited on all three substrates, the volume fraction of the monoclinic phase increased with increasing film thickness, with the SiO₂ substrate having the lowest monoclinic phase volume fraction at all film thicknesses tested. The grain size of the films, which is an important factor for the formation of the ferroelectric phase, remained almost constant at about 10 nm in diameter regardless of the film thickness and type of substrate utilized. Ferroelectricity was observed for the 17 nm-thick films deposited on SiO₂ and Si substrates, and the maximum remanent polarization (P_r) value of 9.3 µC/cm² was obtained for films deposited on the SiO₂ substrate. In contrast, ferroelectricity with P_r=4.4 µC/cm² was observed only for film on SiO₂ substrate in case of 55 nm-thick films. These results suggest that the films under in-plane tensile strain results in the larger ferroelectricity for 17 nm-thick films and have a ferroelectricity up to 55 nm-thick films.     

Evaporated iron disulfide thin films with sulfurated annealing treatments

FeS₂ thin films were grown on a glass substrate using a physical vapor deposition technique at room temperature. Subsequently, the thin films were annealed in two different atmospheres: vacuum and vacuum-sulfur. In the vacuum-sulfur atmosphere a graphite box was used as sulfur container and the films were sulfurated successfully at 200–350 ºC. It was found that annealing in a vacuum-sulfur atmosphere was indispensable in order to obtain polycrystalline FeS₂ thin films. The polycrystalline nature and pure phase were determined by XRD and Raman techniques and the electrical properties by the Hall effect. Using the sulfurating technique, the n-type semiconductor was prepared at 200–350 °C and a p-type at 500 °C. The carrier concentrations were between 1.19×10²⁰ and 2.1×10²⁰ cm⁻³. The mobility was 9.96–5.25 cm² V⁻¹ s⁻¹ and the resistivity was 6.31×10⁻² to 1.089×10⁻² Ω cm. The results obtained from EDS showed that the films prepared in the vacuum-sulfur atmosphere were close to stoichiometric and that the indirect band gap varied between 1.03 and 0.945 eV.