Comparison of the dye-sensitized solar cells performances based on transparent conductive ITO and FTO

We investigated dye-sensitized solar cell (DSSC) performances with regard to transparent conducting oxide substrates: indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO). The DSSCs were in a standard configuration: a photoelectrode of TiO₂ nanoparticles (9 nm size, anatase phase) deposited on transparent and electrically conductive substrates, counter electrodes of Pt-coated glass, ruthenium 535 dye, and AN50 iodolyte electrolyte (Solaronix). The cells manufactured from ITO (FTO) had an open circuit voltage of 705 (763) mV and short-circuit current of 7.87 (34.3) mA/cm². A direct correlation was found between transparent conductive film resistivity and cell efficiency. Resistivities of 52 Ω/sq for ITO substrates and 8.5 Ω/sq for FTO led to major differences in internal global efficiency: from 2.24% for ITO to 9.6% for FTO.     

Properties of multilayer transparent conducting oxide films

Multilayered transparent conducting oxide (TCO) film structures have been designed and fabricated to achieve both high conductivity and high transmittance in the visible spectrum. Double-layered TCO structures consisting of Sn-doped CdO and Sn-doped CdIn₂O₄, Cd-rich Cd₂SnO₄, or Ga-doped ZnO are discussed. By optimizing the thickness of the individual layers and the doping levels within those layers, an effective conductivity of 20 600 S/cm and an average transmittance larger than 85% in the 400-700 nm range have been achieved for films epitaxially grown on MgO substrates. Bi-layer films consisting of Sn-doped CdO and Ga-doped ZnO have also been deposited on plastic substrates at room temperature with resistivities of ∼1×10⁻⁴ Ω cm and an average transmittance of 80-85% in the visible range. These properties are attractive for future TCO applications.     

Preparation of fluorine-doped tin oxide (SnO2:F) film on polyethylene terephthalate (PET) substrate

Fluorine-doped tin oxide (FTO), one of the most popular transparent conductive oxide (TCO) materials, coated on glass has been used in various applications including many new-generation solar cells. However, there is a lack of reporting when it comes to FTO coated on flexible transparent substrate. For this paper, spray pyrolysis technique was used to have FTO firstly coated on to a brass substrate, which was then dissolved away after cementing an upper flexible transparent polyethylene terephthalate (PET) substrate, finally leaving high quality FTO film on PET substrate. Their structural, electrical, optical and flexible properties were investigated. The lowest resistivity was 7.6 × 10^− 4 Ω cm, which is as good as conventional FTO deposited on glass. Their fold ability could be significantly improved to transcend commercial ITO/PET only by increasing the pretreating time of the brass substrate.     

Low-indium content bilayer transparent conducting oxide thin films as effective anodes in organic photovoltaic cells

Bilayer In-doped CdO/Sn-doped In₂O₃ (CIO/ITO) transparent conducting oxide (TCO) thin films were prepared by depositing thin ITO films by ion-assisted deposition on CIO films grown by metal-organic chemical vapor deposition. The optical, electrical, and microstructural properties of these bilayer TCO films were investigated in detail. A low sheet resistance of ~ 4.9 Ω/□ is achieved for the CIO/ITO (170/40 nm) bilayers without annealing. With a significantly lower In content (20 vs. ~ 93 at.%) and a much higher conductivity (> 12,000 vs. 3000-5000 S/cm) than commercial ITO, these bilayer films were investigated as anodes in bulk-heterojunction organic photovoltaic (OPV) devices having a poly(2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene) + [6,6]-phenyl C₆₁ butyric acid methyl ester active layer. Device performance metrics in every way comparable to those of devices fabricated on commercial ITO are achieved, demonstrating that CIO/ITO bilayers are promising low-In content, highly conductive and transparent electrode candidates for OPV cells.     

Low temperature processing of hybrid nanoparticulate Indium Tin Oxide (ITO) polymer layers and application in large scale lighting devices

We report on transparent conductive indium tin oxide (In₂O₃:Sn; ITO) nanoparticle films processed at a low temperature of 130 °C for the application in lighting devices using spin coating and doctor blading techniques. Major emphasis is put on the beneficial application of the particular transparent electrode material for the fabrication of patterned large area electroluminescence lamps. In order to improve film properties like adhesion and conductivity, hybrid nanoparticle-polymer blends out of ITO particles and organic film-forming agent polyvinylpyrrolidone (PVP) and the organofunctional coupling agent 3-methacryloxypropyltrimethoxysilane (MPTS) have been developed. The layers were cured by UV-irradiation, which was also used for lateral structuring of the transparent, conductive electrode. Additional low-temperature heat treatment (T = 130 °C) in air and forming gas improved the electronic properties. While pure ITO nanoparticulate layers processed at 130 °C exhibited conductance of up to 3.1 Ω^− 1 cm^− 1, the nanocomposite coatings showed a conductance of up to 9.8 Ω^− 1 cm^− 1. Corresponding layers with a sheet resistance of 750 Ω/□ were applied in electroluminescent lamps.     

Recent progress in transparent oxide semiconductors: Materials and device application

This paper reviews our recent research progress on new transparent conductive oxide (TCO) materials and electronic and optoelectronic devices based on these materials. First, described are the materials including p-type materials, deep-UV transparent TCO(β-Ga₂O₃), epitaxially grown ITO with atomically flat surface, transparent electrochromic oxide (NbO₂F), amorphous TCOs, and nanoporous semiconductor 12CaO · 7Al₂O₃. Second, presented are TCO-based electronic/optoelectronic devices realized to date, UV/blue LED and UV-sensors based on transparent pn junction and high performance transparent TFT using n-type TCO as an n-channel. Finally, unique optoelectronic properties (p-type degenerate conduction, transfer doping of carriers, RT-stable exciton, and large optical nonlinearity) originating from 2D-electronic nature in p-type layered oxychalcogenides are summarized along with the fabrication method of epitaxial thin films of these materials.     

Low-temperature processing of transparent conductive indium tin oxide nanocomposites using polyvinyl derivatives

We report on the influence of additives on the electrical, optical, morphological and mechanical properties of transparent conductive indium tin oxide (In₂O₃:Sn; ITO) nanoparticle films by the use of polymers as matrix material. Key issues to fabricate layers suitable for use in electronic device applications are presented. Polyvinyl derivatives polyvinyl acetate, polyvinyl alcohol (PVA) and polyvinyl butyral were applied and their suitability to form transparent conductive ITO nanocomposite coatings at a maximum process temperature of 130 °C was investigated. A low-temperature treatment with UV-light has been developed to provide the possibility of curing ITO thin films deposited on substrates which do not withstand high process temperatures. Compared to best pure ITO layers (0.2 Ω^− 1 cm^− 1), the ITO-PVA nanocomposite coatings show a conductance value of 4.1 Ω^− 1 cm^− 1 and 5.9 Ω^− 1 cm^− 1 after reducing in forming gas. Sheet resistance of ca. 1200 Ω/□ with coexistent transmittance of 85% at 550 nm for a layer thickness of about 1.45 μm was achieved. The conductance enhancement is a consequence of nanoparticulate ITO network densification due to the acting shrinkage forces caused by the polymer matrix during film drying and additionally UV-induced crosslinking of PVA.     

Comparative study of ITO and FTO thin films grown by spray pyrolysis

Tin doped indium oxide (ITO) and fluorine doped tin oxide (FTO) thin films have been prepared by one step spray pyrolysis. Both film types grown at 400 °C present a single phase, ITO has cubic structure and preferred orientation (4 0 0) while FTO exhibits a tetragonal structure. Scanning electron micrographs showed homogeneous surfaces with average grain size around 257 and 190 nm for ITO and FTO respectively.The optical properties have been studied in several ITO and FTO samples by transmittance and reflectance measurements. The transmittance in the visible zone is higher in ITO than in FTO layers with a comparable thickness, while the reflectance in the infrared zone is higher in FTO in comparison with ITO. The best electrical resistivity values, deduced from optical measurements, were 8 × 10⁻⁴ and 6 × 10⁻⁴ Ω cm for ITO (6% of Sn) and FTO (2.5% of F) respectively. The figure of merit reached a maximum value of 2.15 × 10⁻³ Ω⁻¹ for ITO higher than 0.55 × 10⁻³ Ω⁻¹ for FTO.     

Fabrication of high-performance fluorine doped-tin oxide film using flame-assisted spray deposition

A high-performance fluorine-doped tin oxide (FTO) film was fabricated by flame-assisted spray deposition method. By varying the NH₄F doping concentration, the optimal concentration was established as 8 at.%. X-ray diffractograms confirmed that the as-grown FTO film was tetragonal SnO₂. In addition, the FTO film was comprised of nano-sized grains ranging from 40 to 50 nm. The heat-treated FTO film exhibited a sheet resistance of 21.8 Ω/? with an average transmittance of 81.9% in the visible region (λ = 400-800 nm). The figures of merit shows that the prepared FTO film can be used for highly efficient dye-sensitized solar cells electrodes.     

The characteristics of chemical and heat stability properties of chromium-vanadium-aluminum co-doped zinc oxide films for dye-sensitized solar cells

Transparent conducting oxide thin films are used as front contact material for dye-sensitized solar cells. This study investigated the effects of chromium (Cr) and vanadium (V) contents on the chemical and heat stability properties of aluminum-doped zinc oxide (AZO) thin films using pulsed direct current magnetic sputtering on Corning 1737F glass substrates. The experimental results show that Cr and V doping is useful for improving the chemical and thermal stability of AZO films. The energy gap for AZO thin films is between 3.65 and 3.69 eV. The resistivity of the AZO:Cr:V thin film was 4.23 × 10^-4 Ω cm at a Cr/V ratio of 0.30/0.23 wt.%, deposition power of 150 W, working distance of 5.5 cm, substrate temperature of 473 K, working pressure of 0.4 Pa, and frequency of 10 kHz. This value is lesser than (and therefore superior to) the resistivity of SnO₂:F (FTO) films (6.5 × 10^-4 Ω cm), but greater than that of SnO₂:In (ITO) thin films (1.2 × 10^-4 Ω cm). The resistivity increased by about 0.27% after electrolyte etching, which is similar to the 0.16% increase observed for the ITO thin film. After a thermal cycle test at 673 K, the resistivity of the AZO:Cr:V film increased to 5.42 × 10^-4 Ω cm, which is better than the resistivity of the ITO and FTO films after the same thermal cycle.     

CdTe solar cell with industrial Al:ZnO on soda-lime glass

One avenue to enhance CdTe cell performance is to improve the optical transmission of the transparent conductive oxide (TCO)/window layer stack. In this paper, we examine soda-lime float glass coated with an Al-doped ZnO layer and a buffer layer. The possible advantages of using a ZnO-based TCO include reduced surface roughness, improved transparency, and an integrated buffer layer that can be optimized for use in a CdTe PV device. Device processing was modified to address the chemical and thermal differences between the ZnO-based TCO stack produced by Saint-Gobain and the TCOs previously used at the National Renewable Energy Laboratory (NREL). These process modifications produced ~ 8% efficiency for devices without a buffer layer. Incorporation of buffer layers has already produced devices with ~ 11% and > 12% efficiency for CdTe deposition temperatures of 570° and 500°C, respectively.     

Fabrication of transparent conductive films with a sandwich structure composed of ITO/Cu/ITO

New transparent conductive films that had a sandwich structure composed of ITO/Cu/ITO multilayer films were prepared by a conventional RF and DC magnetron sputtering process on a polycarbonate substrate without intentional substrate heating. The thickness of each layer in the ITO/Cu/ITO films was kept constant at 50 nm/5 nm/45 nm. The optoelectrical and structural properties of the films were compared with conventional ITO single-layer films and ITO/Cu/ITO multilayered films. Although both films had identical thickness, 100 nm, the ITO/Cu/ITO films showed a lower resistivity, 3.5 × 10⁻⁴ Ω cm. In optical transmittance measurements, however, the ITO single-layer films showed a higher transmittance of 74% in the wavelength range of 300-800 nm. XRD spectra showed that both the ITO and ITO/Cu/ITO films were amorphous. The figure of merit, φ_TC, reached a maximum of 5.2 × 10⁻⁴ Ω⁻¹ for the ITO/Cu/ITO films, which was higher than the φ_TC of the ITO films (1.6 × 10⁻⁴ Ω⁻¹). The φ_TC results suggested that ITO/Cu/ITO films had better optoelectrical properties than conventional ITO single-layer films.     

Properties of Ce-doped ITO films deposited on polymer substrate by DC magnetron sputtering

Ce-doped indium tin oxide (ITO:Ce) films were deposited on flexible polyimide substrates by DC magnetron sputtering using ITO targets containing various CeO₂ contents (CeO₂ : 0, 0.5, 3.0, 4.0, 6.0 wt.%) at room temperature and post-annealed at 200 °C. The crystallinity of the ITO films decreased with increasing Ce content, and it led to a decrease in surface roughness. In addition, a relatively small change in resistance in dynamic stress mode was obtained for ITO:Ce films even after the annealing at high temperature (200 °C). The minimum resistivity of the amorphous ITO:Ce films was 3.96 × 10^− 4 Ωcm, which was deposited using a 3.0 wt.% CeO₂ doped ITO target. The amorphous ITO:Ce films not only have comparable electrical properties to the polycrystalline films but also have a crystallization temperature > 200 °C. In addition, the amorphous ITO:Ce film showed stable mechanical properties in the bended state.     

Sputtering deposition of amorphous cadmium stannate as transparent conducting oxide

In this work we studied deposition conditions by RF sputtering of ternary oxides of Cd and Sn, starting from Cd₂SnO₄ target and varying substrate temperature, sputtering power and deposition gas (from inert Ar to oxidizing 50% Ar-50% O₂ atmosphere). The aim of this study was to obtain thin films for use as Transparent Conducting Oxide (TCO). TCOs are oxides that couples low sheet resistance and high transparency that find application in many fields like solar cells, light emitting diodes and transparent thin film transistors.Thin films functional properties were characterised by means of sheet resistance and transmittance measurements in the visible region, and film composition and structure were investigated by total reflection X ray fluorescence and glancing incidence X ray diffraction. Morphology was studied by Atomic Force Microscopy and Scanning Electron Microscope and showed very smooth surface suitable for solar cells application. Composition and phase analysis allowed us to discuss possible correlation of film structure with functional properties. Deposition in inert atmosphere at 400 °C substrate temperature was selected for its low sheet resistance and high transparency that are comparable to the ones of commercial TCOs like indium tin oxide or SnO₂: F. The thin film obtained in these conditions was amorphous, and it crystallized into CdSnO₃ ilmenite phase when annealed at 700 °C; segregation of Sn₃O₄ was also observed. Since sheet resistance of thin films increases after annealing treatments, amorphous thin film was selected for future applications.     

Electrical and optical properties of indium tin oxide films prepared on plastic substrates by radio frequency magnetron sputtering

The influence of deposition power, thickness and oxygen gas flow rate on electrical and optical properties of indium tin oxide (ITO) films deposited on flexible, transparent substrates, such as polycarbonate (PC) and metallocene cyclo-olefin copolymers (mCOC), at room temperature was studied. The ITO films were prepared by radio frequency magnetron sputtering with the target made by sintering a mixture of 90 wt.% of indium oxide (In₂O₃) and 10 wt.% of tin oxide (SnO₂). The results show that (1) average transmission in the visible range (400-700 nm) was about 85%-90%, and (2) ITO films deposited on glass, PC and mCOC at 100 W without supplying additional oxygen gas had optimum resistivity of 6.35 × 10⁻⁴ Ω-cm, 5.86 × 10⁻⁴ Ω-cm and 6.72 × 10⁻⁴ Ω-cm, respectively. In terms of both electrical and optical properties of indium tin oxide films, the optimum thickness was observed to be 150-300 nm.     

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.     

New transparent conductive films: FTO coated ITO

New transparent conductive films, fluorine doped tin oxide (FTO) films coated on indium-tin-oxide (ITO) films, were developed. These transparent conductive films were prepared by the spray pyrolysis deposition method at a substrate temperature of 350 °C in ITO and 400 °C in FTO. For ITO deposition, an ethanol solution of indium(III) chloride, InCl₃·4H₂O, and tin(II) chloride, SnCl₂·2H₂O [Sn/(In+Sn), 5 at.%] was sprayed on a Corning #7059 glass substrate (100×100×1.1 mm³). After the deposition, FTO films were consecutively deposited for protecting oxidation of ITO films. FTO deposition was carried out by an ethanol solution of tin(IV) chloride, SnCl₄·5H₂O within the saturated water solution of NH₄F. These new transparent conductive films achieved the lowest resistivity of 1.4×10⁻⁴ Ω cm and the optical transmittance of more than 80% in the visible range of the spectrum. The electrical resistance of these new transparent conductive films increased by less than 10% even when exposed to high temperatures of 300-600 °C for 1 h in the air.     

Low resistivity transparent conducting CdO thin films deposited by DC reactive magnetron sputtering at room temperature

Transparent conducting cadmium oxide (CdO) films were deposited on PET (polyethylene terephthalate) substrate by DC reactive magnetron sputtering at room temperature. All the films deposited at room temperature were polycrystalline in rock-salt structure. Dependences of the physical properties of the CdO films on the oxygen partial pressure were systematically studied. The films deposited at low oxygen flow rate were (200) oriented, while the films deposited at an oxygen flow rate greater than 20 sccm were (111) oriented. The average grain size of the CdO films decreased as the oxygen flow rate increases as determined by XRD and SEM. The Hall effect measurement showed that CdO films have high concentration, low resistivity, and high mobility. Both the mobility and the concentration of the carrier decreased with the increase of the oxygen flow rate. A minimum sheet resistance of 36.1 Ω/□, or a lowest resistivity of 5.44 × 10^− 4 Ω cm (6.21 × 10²⁰/cm³, μ = 19.2 cm²/Vs) was obtained for films deposited at an oxygen flow rate of 10 sccm.     

Towards ultra-thin CdTe solar cells using MOCVD

A study was made on very thin CdTe absorber < 1 µm layers to investigate limitations in CdTe collection efficiency. Metal organic chemical vapour deposition (MOCVD) was used to deposit cadmium sulfide (CdS), cadmium zinc sulfide (Cd_0.9Zn_0.1S) and cadmium telluride (CdTe). Improvements in photon collection in the blue, where the absorption length is shorter, have been achieved using a wider band gap Cd_0.9Zn_0.1S ternary alloy to replace CdS as the window layer. Solar cell capacitance simulator (SCAPS) modelling software [M. Burgelman, P. Nollet, S. Degrave, Thin Solid Films, 361-362 (2000) 527-532] has been used to calculate device parameters as a function of the absorber layer thickness (controlled by in situ using laser reflectometry). One feature of the MOCVD grown devices is the apparent absence of pin-holes, demonstrated by growth of an ultra-thin absorber (200 nm) with conversion efficiency of nearly 4%.     

Enhanced characterization of ITO films deposited on PET by RF superimposed DC magnetron sputtering

Tin-doped indium oxide (ITO) films were deposited on polyethylene terephthalate substrates by RF superimposed DC magnetron sputtering using an ITO target composed of In₂O₃ (90 wt.%):SnO₂ (10 wt.%). The total sputtering power was maintained at 70 W and the power ratio of RF/(RF + DC) was varied from 0 to 100% in steps of 25%. The discharge voltage and deposition rate decreased with increasing RF/(RF + DC) power ratio. The ITO film deposited at a 50% RF portion of the total power showed the lowest resistivity (3.18 × 10^− 4 Ωcm), high transmittance (87.5%) and relatively good mechanical durability, which was evaluated using bending and scratch tests.