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.     

High mobility transparent conducting oxides for thin film solar cells

A special class of transparent conducting oxides (TCO) with high mobility of > 65 cm² V^− 1 s^− 1 allows film resistivity in the low 10^− 4 Ω cm range and a high transparency of > 80% over a wide spectrum, from 300 nm to beyond 1500 nm. This exceptional coincidence of desirable optical and electrical properties provides opportunities to improve the performance of opto-electronic devices and opens possibilities for new applications. Strategies to attain high mobility (HM) TCO materials as well as the current status of such materials based on indium and cadmium containing oxides are presented. Various concepts used to understand the underlying mechanisms for high mobility in HMTCO films are discussed. Examples of HMTCO layers used as transparent electrodes in thin film solar cells are used to illustrate possible improvements in solar cell performance. Finally, challenges and prospects for further development of HMTCO materials are discussed.     

Characterization of transparent conducting oxide thin films deposited on ceramic substrates

In this work, we investigate the optical and electrical properties of various transparent conductive oxide (TCO) thin films deposited on insulating ceramics for emerging optoelectronic applications. Thin films investigated include indium tin oxide (ITO), ruthenium oxide (RuO₂), and iridium oxide (IrO₂) on Al₂O₃ ceramic substrates. The conducting films have been deposited by various techniques including RF magnetron sputtering and low-cost spray pyrolysis. The morphological characteristics of the films were carried out using high magnification optical microscopy and atomic force microscopy (AFM). Optical and electrical characterization was carried out by optical absorbance/transmittance, van der Pauw, current-voltage (I-V), and Hall effect measurements. The results are presented in this paper.     

Studies of key technologies for large area CdTe thin film solar cells

The structure and main manufacturing technologies of CdTe film solar cells of large area are reviewed. Among the technologies, some have been developed for application in a pilot manufacturing line. The high resistant SnO₂ (HRT) thin films have been fabricated by PECVD. The effects of annealing on the structure and properties have been studied. A surface etching process of CdTe in low temperature and lower concentration of nitric acid has been developed. The Cd_1 − xZn_xTe ternary compound films have been studied. In order to improve the back contact layer, Cd_0.4Zn_0.6Te layer with 1.8 eV band gap as a substitute for ZnTe layer is introduced in CdTe cells. The effects of the technologies on performance of CdTe cells and feasibility of application in the modules are discussed.     

Substitution of transparent conducting oxide thin films for indium tin oxide transparent electrode applications

The present status and prospects for further development of reduced or indium-free transparent conducting oxide (TCO) materials for use in practical thin-film transparent electrode applications such as liquid crystal displays are presented in this paper: reduced-indium TCO materials such as ZnO-In₂O₃, In₂O₃-SnO₂ and Zn-In-Sn-O multicomponent oxides and indium-free materials such as Al- and Ga-doped ZnO (AZO and GZO). In particular, AZO thin films, with source materials that are inexpensive and non-toxic, are the best candidates. The current problems associated with substituting AZO or GZO for ITO, besides their stability in oxidizing environments as well as the non-uniform distribution of resistivity resulting from dc magnetron sputtering deposition, can be resolved. Current developments associated with overcoming the remaining problems are also presented: newly developed AZO thin-film deposition techniques that reduce resistivity as well as improve the resistivity distribution uniformity using high-rate dc magnetron sputtering depositions incorporating radio frequency power. In addition, stability tests of resistivity in TCO thin films evaluated in air at 90% relative humidity and 60 °C have demonstrated that sufficiently moisture-resistant AZO thin films can be produced at a substrate temperature below 200 °C when the film thickness was approximately 200 nm. However, improving the stability of AZO and GZO films with a thickness below 100 nm remains a problem.     

Factorial design preparation of transparent conducting oxide thin films

Transparent and conducting properties of Cd₂SnO₄ films deposited onto glass substrates by the dip coating technique have been obtained using a 2⁴ factorial design. All films were well adhered onto their substrates, presented porous morphology and inverse spinel structure. Statistical factorial design analysis showed that only substrate withdrawal rate and precursor solution concentration had significant effects on average transmission of the films. Cumulative probability graphs of factorial design model coefficients showed that none of the factor levels have significant effects on resistivity. However the films presented significantly higher resistivities using low withdrawal rates and low concentration levels. This indicates resistivity is a more complex function of the factor variables than transmission. From the factorial design experiments and statistical analysis of their results a highest average transmission of 88% and lowest resistivity of 2.43 × 10^− 4 Ω m were found.     

Humid environment stability of low pressure chemical vapor deposited boron doped zinc oxide used as transparent electrodes in thin film silicon solar cells

The stability in humid environment of low pressure chemical vapor deposited boron doped zinc oxide (LPCVD ZnO:B) used as transparent conductive oxide in thin film silicon solar cells is investigated. Damp heat treatment (exposure to humid and hot atmosphere) induces a degradation of the electrical properties of unprotected LPCVD ZnO:B layers. By combining analyses of the electrical and optical properties of the films, we are able to attribute this behavior to an increase of electron grain boundary scattering. This is in contrast to the intragrain scattering mechanisms, which are not affected by damp heat exposure. The ZnO stability is enhanced for heavily doped films due to easier tunneling through potential barrier at grain boundaries.     

Development of thickness measurement program for transparent conducting oxide thin films

The gallium doped zinc oxide has been one of the candidates for the transparent conducting oxide thin film electrode. It is not suitable to use a conventional light interference method to measure the thickness of the gallium doped zinc oxide thin film because the refractive index and extinction coefficient of the thin film is unknown during the optimization of the deposition conditions. In this paper, we report on the details of the film thickness program which uses the measured optical and electric properties and relationship between the plasma frequency and the optical constant of the film. The obtained film thickness of the prepared gallium doped zinc oxide thin film using the program was comparable with thicknesses measured by a cross-sectional analysis of the atomic force microscopy and the surface profiler. Moreover, the optical constant of refractive index and extinction coefficient of the film could also be estimated.     

Ultrathin Al-doped transparent conducting zinc oxide films fabricated by pulsed laser deposition

Al-doped transparent conducting zinc oxide (AZO) films, approximately 20-110 nm-thick, were deposited on glass substrates at substrate temperatures between 200 and 300 °C by pulsed laser deposition (PLD) using an ArF excimer laser (λ = 193 nm). When fabricated at a substrate temperature of 260 °C, a 40-nm-thick AZO film showed a low resistivity of 2.61 × 10^− 4 Ω·cm, carrier concentration of 8.64 × 10²⁰ cm^− 3, and Hall mobility of 27.7 cm²/V·s. Furthermore, for an ultrathin 20-nm-thick film, a resistivity of 3.91 × 10^− 4 Ω·cm, carrier concentration of 7.14 × 10²⁰ cm^− 3, and Hall mobility of 22.4 cm²/V·s were obtained. X-ray diffraction (XRD) spectra, obtained by the θ-2θ method, of the AZO films grown at a substrate temperature of 260 °C showed that the diffraction peak of the ZnO (0002) plane increased as the film thickness increased from 20 to 110 nm. The full-width-at-half-maximum (FWHM) values were 0.5500°, 0.3845°, and 0.2979° for film thicknesses of 20, 40, and 110 nm, respectively. For these films, the values of the average transmittance in visible light wavelengths (400-700 nm) were 95.1%, 94.2%, and 96.6%, respectively. Field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM) observations showed that even the 20-nm-thick films did not show island structures. In addition, exfoliated areas or vacant and void spaces were not observed for any of the films.     

Effect of process parameters on the growth and properties of impurity-doped zinc oxide transparent conducting thin films by RF magnetron sputtering

Zinc oxide transparent conducting thin films co-doped with aluminum and ruthenium were grown on polyethylene terephthalate substrates at room temperature using RF magnetron sputtering. The crystal growth and physical properties of the films were investigated with respect to the variation of discharge power density from 1.5 to 6.1 W/cm² and sputtering pressure from 0.13 to 2.0 Pa. X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) showed that the films grown with 3.6 W/cm² power density and sputtering pressure of 0.4 Pa had the best crystallinity and larger pyramid-like grains. The optimized electrical resistivity had a lowest measured value of about 9 × 10⁻⁴ Ω cm. The low carrier mobilities of the films (3-8.9 cm² V⁻¹ s⁻¹) have been discussed in terms of what is believed to be the dominant effect of ionized impurity scattering, but in addition chemisorption of oxygen on the film surface and effect of grain boundaries are also thought to be significant. The transmittances of the films in the visible range are greater than 80%, while the optical band gaps are in the order of 3.337-3.382 eV.     

Hydrogen-radical durability of TiO2 thin films for protecting transparent conducting oxide for Si thin film solar cells

Hydrogen-radical durability of TiO₂ thin films has been investigated under conditions for preparing Si thin film solar cells by catalytic chemical vapor deposition method. It is found that the composition and the optical transmittance of TiO₂ films are almost the same before and after hydrogen-radical exposures with a filament temperature at approximately 1700 °C and a H₂ pressure of approximately 133 Pa. The durability of TiO₂ film has also been observed even under the condition with higher hydrogen-radical density under a filament temperature at approximately 1900 °C, in which SnO₂ and ZnO are easily deoxidized. The application of TiO₂ film as a protecting material of transparent conducting oxide film for Si thin film solar cells are discussed by the hydrogen-radical durability and fundamental properties of TiO₂ thin film.     

Electrical and optical properties of Zn-In-Sn-O transparent conducting thin films

Indium tin oxide (ITO) is one of the widely used transparent conductive oxides (TCO) for application as transparent electrode in thin film silicon solar cells or thin film transistors owing to its low resistivity and high transparency. Nevertheless, indium is a scarce and expensive element and ITO films require high deposition temperature to achieve good electrical and optical properties. On the other hand, although not competing as ITO, doped Zinc Oxide (ZnO) is a promising and cheaper alternative. Therefore, our strategy has been to deposit ITO and ZnO multicomponent thin films at room temperature by radiofrequency (RF) magnetron co-sputtering in order to achieve TCOs with reduced indium content. Thin films of the quaternary system Zn-In-Sn-O (ZITO) with improved electrical and optical properties have been achieved.The samples were deposited by applying different RF powers to ZnO target while keeping a constant RF power to ITO target. This led to ZITO films with zinc content ratio varying between 0 and 67%. The optical, electrical and morphological properties have been thoroughly studied. The film composition was analysed by X-ray Photoelectron Spectroscopy. The films with 17% zinc content ratio showed the lowest resistivity (6.6 × 10^− 4 Ω cm) and the highest transmittance (above 80% in the visible range). Though X-ray Diffraction studies showed amorphous nature for the films, using High Resolution Transmission Electron Microscopy we found that the microstructure of the films consisted of nanometric crystals embedded in a compact amorphous matrix. The effect of post deposition annealing on the films in both reducing and oxidizing atmospheres were studied. The changes were found to strongly depend on the zinc content ratio in the films.     

Natively textured surface aluminum-doped zinc oxide transparent conductive layers for thin film solar cells via pulsed direct-current reactive magnetron sputtering

Natively textured surface aluminum-doped zinc oxide (ZnO:Al) layers for thin film solar cells were directly deposited without any surface treatments via pulsed direct-current reactive magnetron sputtering on glass substrates. Such an in-situ texturing method for sputtered ZnO:Al thin films has the advantages of efficiently reducing production costs and dramatically saving time in photovoltaic industrial processing. High purity metallic Zn-Al (purity: 99.999%, Al 2.0 wt.%) target and oxygen (purity: 99.999%) were used as source materials. During the reactive sputtering process, the oxygen gas flow rate was controlled using plasma emission monitoring. The performance of the textured surface ZnO:Al transparent conductive oxides (TCOs) thin films can be modified by changing the number of deposition rounds (i.e. thin-film thicknesses). The initially milky ZnO:Al TCO thin films deposited at a substrate temperature of ~ 553 K exhibit rough crater-like surface morphology with high transparencies (T ~ 80-85% in visible range) and excellent electrical properties (ρ ~ 3.4 × 10^− 4 Ω cm). Finally, the textured-surface ZnO:Al TCO thin films were preliminarily applied in pin-type silicon thin film solar cells.     

Stability of nano-thick transparent conducting oxide films for use in a moist environment

The stability of nano-thick transparent conducting oxide thin films in a high humidity environment was investigated. The stability of ITO and impurity-doped ZnO thin films prepared with a thickness in the range from approximately 20 to 100 nm on glass substrates at a temperature below 200 °C by a pulsed laser deposition was evaluated in air at a relative humidity of 90% and a temperature of 60 °C. The resistivity of all Al- and Ga-doped ZnO thin films tested was found to increase markedly with test time, whereas that of ITO remained relatively stable; the stability (resistivity increase) of the doped ZnO thin films was considerably affected by film thickness but was relatively independent of the deposition substrate temperature. In particular, doped ZnO thin films with a thickness below approximately 50 nm were very unstable under the test conditions. The resistivity increase of doped ZnO films is mainly attributed to the grain boundary scattering resulting from the adsorption of oxygen on the grain boundary.     

Preparation of SnO2 thin films at low temperatures with H2 gas by the hot-wire CVD method

H₂ additional effect for crystallization of SnO₂ films prepared by the hot-wire CVD method was investigated. The crystallization of SnO₂ films starts at 170 °C. The selectivity enhancement of the solar cell substrate will contribute to reduce the cost of silicon thin film solar cells. The atomic hydrogen assisted nano-crystallization exists for the depositions of SnO₂ films by the hot-wire CVD method. Furthermore, the addition of H₂ gas improved the electrical conductivity up to 5.3 × 10⁰ S/cm. However, these effects are limited in the deposition condition of a small amount of hydrogen. Addition of much higher hydrogen concentration starts an etching effect of oxygen atoms.     

银基透明导电多层膜界面研究进展

由于具有较低的电阻率和成本、较好的机械加工性能、设计上的灵活性,可室温沉积等优点,银基透明导电多层膜已广泛应用于低辐射膜、强电磁屏蔽、低功耗光电子器件特别是柔性电子器件等领域.但由于材料自身的性质与制备条件的差异性,实际制备的金属/电介质(或半导体)透明导电多层膜界面处往往存在表面等离子体共振、界面导电电子散射、膜层脱...     

Photoelectron spectroscopy investigation of thin metal films employed as top contacts in transparent organic solar cells

The performance of transparent metal top contacts in organic solar cells can strongly be improved by employing surfactant layers. We use scanning electron microscopy to investigate the change in morphology upon insertion of an Al surfactant layer between 4,7-diphenyl-1,10-phenanthroline (BPhen) and a silver top contact. UV photoelectron spectroscopy measurements show the changes in energetic alignments at different steps of the organic/metal interface formation. Furthermore, using X-ray photoelectron spectroscopy depth profiling, we compare the differing intermixing processes happening within the two samples. Thereby, we can show that Al binds to BPhen molecules, acting as surfactant for subsequently deposited Ag layers, while Ag without any Al surfactant layer penetrates into and intermixes with the BPhen layer.     

Heat generation properties of Ga doped ZnO thin films prepared by rf-magnetron sputtering for transparent heaters

Ga doped ZnO (GZO) thin films were prepared by rf-magnetron sputtering on glass substrate for window heater applications. Electrical and optical properties of these films were analyzed in order to investigate on substrate temperature and rf power dependencies. High quality GZO films with a resistivity of 1.30 × 10^− 4 Ω cm and a transparency above 90% in the visible range were able to be formed. GZO films have been patterned on glass substrate as a line heater. This GZO line heater showed the rapid heat radiation property from room temperature to 90 °C for 22 s at the applied voltage of 42 V. These results could provide a possibility to use GZO as effective transparent heaters.