Structural, electrical and optical properties of Ga-doped ZnO films on cyclo-olefin polymer substrates

Ga-doped ZnO (GZO) films with a thickness of 100 nm were prepared on cyclo-olefin polymer (COP) and glass substrates at various temperatures below 100 °C by ion plating with direct-current arc discharge. The dependences of the characteristics of GZO films on the substrate temperature Ts were investigated. All the polycrystalline GZO films, which exhibited a high average visible transmittance of greater than 86%, were crystallized with a wurtzite structure oriented along the c-axis. The lowest resistivities of the GZO films were 5.3 × 10^− 4 Ωcm on the glass substrate and 5.9 × 10^− 4 Ωcm on the COP substrate.     

Effect of inserting a buffer layer on the characteristics of transparent conducting impurity-doped ZnO thin films prepared by dc magnetron sputtering

In transparent conducting impurity-doped ZnO thin films prepared on glass substrates by a dc magnetron sputtering (dc-MS) deposition, the obtainable lowest resistivity and the spatial resistivity distribution on the substrate surface were improved by a newly developed MS deposition method. The decrease of obtainable lowest resistivity as well as the improvement of spatial resistivity distribution on the substrate surface in Al- or Ga-doped ZnO (AZO or GZO) thin films were successfully achieved by inserting a very thin buffer layer, prepared using the same MS apparatus with the same target, between the thin film and the glass substrate. The deposition of the buffer layer required a more strongly oxidized target surface than possible to attain during a conventional dc-MS deposition. The optimal thickness of the buffer layer was found to be about 10 nm for both GZO and AZO thin films. The resistivity decrease is mainly attributed to an increase of Hall mobility rather than carrier concentration, resulting from an improvement of crystallinity coming from insertion of the buffer layer. Resistivities of 3 × 10^− 4 and 4 × 10^− 4Ω cm were obtained in 100 nm-thick-GZO and AZO thin films, respectively, incorporating a 10 nm-thick-buffer layer prepared at a substrate temperature around 200 °C.     

Thermally stable, highly conductive, and transparent Ga-doped ZnO thin films

Highly conductive and transparent films of Ga-doped ZnO (GZO) have been prepared by pulsed laser deposition using a ZnO target with Ga₂O₃ dopant of 3 wt.% in content added. Films with resistivity as low as 3.3 × 10^− 4 Ω cm and transmittance above 80% at the wavelength between 400 and 800 nm can be produced on glass substrate at room temperature. It is shown that a stable resistivity for use in oxidation ambient at high temperature can be attained for the films. The electrical and optical properties, as well as the thermal stability of resistivity, of GZO films were comparable to those of undoped ZnO films.     

Deposition of low-resistivity gallium-doped zinc oxide films by low-temperature radio-frequency magnetron sputtering

The transparent and conductive gallium-doped zinc oxide (GZO) film was deposited on 1737F Corning glass using the radio-frequency (RF) magnetron sputtering system with a GZO ceramic target. (The Ga₂O₃ contents are approximately 5 wt. %). In this study, the effect of the sputtering pressure on the structural, optical and electrical properties of GZO films upon the glass or polyester film (PET) substrate was investigated and discussed in detail. The GZO film was grown under a steady RF power of 400 W and a lower substrate temperature from room temperature up to 200 °C. The crystal structure and orientation of GZO thin films were examined by X-ray diffraction. All of the GZO films under various sputtering pressures had strong c-axis (002)-preferred orientation. Optical transparency was high (> 80%) over a wide spectral range from 380 nm to 900 nm. According to the experimental data, the resistivity of a single-layered GZO film was optimized at  8.3 × 10^− 4 Ω cm and significantly influenced by the sputtering pressure. In further research, the sandwich structure of the GZO film/Au metal/GZO film was demonstrated to improve the electrical properties of the single-layered GZO film. The resistivity of the sandwich-structured GZO film was around 2.8 × 10^− 4 Ω cm.     

Anode material properties of Ga-doped ZnO thin films by pulsed DC magnetron sputtering method for organic light emitting diodes

This study examined the anode material properties of Ga-doped zinc oxide (GZO) thin films deposited by pulsed DC magnetron sputtering along with the device performance of organic light emitting diodes (OLEDs) using GZO as the anode. The structure and electrical properties of the deposited films were examined as a function of the substrate temperature. The electrical properties of the GZO film deposited at 200 °C showed the best properties, such as a low resistivity, high mobility and high work function of 5.3 × 10^− 4Ω cm, 9.9 cm²/Vs and 4.37 eV, respectively. The OLED characteristics with the GZO film deposited under the optimum conditions showed good brightness > 10,000 cd/m². These results suggest that GZO films can be used as the anode in OLEDs, and a lower deposition temperature of 200 °C is suitable for flexible devices.     

Thermally stable transparent conducting and highly infrared reflective Ga-doped ZnO thin films by metal organic chemical vapor deposition

Highly transparent conductive Ga-doped ZnO (GZO) thin films have been prepared on glass substrates by metal organic chemical vapor deposition. The effect of Ga doping on the structural, electrical and optical properties of GZO films has been systematically investigated. Under the optimum Ga doping concentration (∼4.9 at.%), c-axis textured GZO film with the lowest resistivity of 3.6 × 10⁻⁴ Ω cm and high visible transmittance of 90% has been achieved. The film also exhibits low transmittance (<1% at 2500 nm) and high reflectance (>70% at 2500 nm) to the infrared radiation. Furthermore, our developed GZO thin film can well retain the highly transparent conductive performance in oxidation ambient at elevated temperature (up to 500 °C).     

Effect of organic-buffer-layer on electrical property and environmental reliability of Ga-doped ZnO films prepared by RF plasma assisted DC magnetron sputtering on plastic substrate

Ga-doped ZnO (GZO) transparent conductive films have been prepared by RF plasma assisted DC magnetron sputtering under a reductive atmosphere on organic-buffer-layer (OBL) coated polyethylene telephthalate (PET) substrates without intentionally heating substrates. Electrical and optical properties, crystallinity, and environmental reliability of the GZO films have been investigated. The distributional characteristic of resistivity is observed in the GZO film deposited on the OBL-coated PET substrates. The high resistivity at facing the erosion area in the source target is reduced by providing the RF plasma and H₂ gas near the substrate, resulting in a uniform distribution of the sheet resistance. It has been also found that the increase of resistivity by an accelerated aging test performed under a storage condition at 60 °C and at a relative humidity of 95% is suppressed by employing the OBL. The OBL suppresses the formation of cracks, which are induced by the aging test. These facts are thought to contribute to a high environmental reliability of GZO films on PET substrates. Values of resistivity, Hall mobility and carrier concentration are obtained: 5.0-20 × 10⁻³ Ω cm, 4.0 cm²/Vs, and 3.8 × 10²⁰ cm⁻³, respectively. An average transmittance of the GZO film including OBL and PET substrate is 78% in a visible region. The OBL enables to realize the practical use of GZO films on PET sheets.     

Effect of spatial relationship between arc plasma and substrate on the properties of transparent conducting Ga-doped ZnO thin films prepared by vacuum arc plasma evaporation

The effect of the spatial relationship between the arc plasma flow and the substrate surface on the resulting film thickness and electrical properties is investigated in transparent conducting Ga-doped ZnO (GZO) thin films deposited by a vacuum arc plasma evaporation (VAPE) method. It was found that the resulting electrical properties of GZO thin films produced by a VAPE deposition on a fixed substrate were considerably dependent on both the film thickness and the location on the substrate surface, extending from the area nearest the arc plasma source to that at the opposite end of the substrate in a direction parallel to the arc plasma flow; with GZO thin films deposited with various thicknesses in the range from 20 to 200 nm, the films exhibited a thickness dependence of resistivity that was considerably affected by the location on the substrate surface. The variation of resistivity relative to the location on the substrate surface was related to that of carrier concentration, which is mainly attributed to the distribution of the amount of oxygen reaching the substrate surface. In GZO thin films deposited with a thickness of 30-40 nm at a substrate temperature of 250 °C, a resistivity as low as 4 × 10^− 4 Ω cm was obtained in the area of the substrate nearest the arc plasma source.     

Effect of oxygen pressure of SiOx buffer layer on the electrical properties of GZO film deposited on PET substrate

The present work was made to investigate the effect of oxygen pressure of SiO_x layer on the electrical properties of Ga-doped ZnO (GZO) films deposited on poly-ethylene telephthalate (PET) substrate by utilizing the pulsed-laser deposition at ambient temperature. For this purpose, the SiO_x buffer layers were deposited at various oxygen pressures ranging from 13.3 to 46.7 Pa. With increasing oxygen pressure during the deposition of SiO_x layer as a buffer, the electrical resistivity of GZO/SiO_x/PET films gradually decreased from 7.6 × 10^− 3 to 6.8 × 10^− 4 Ω·cm, due to the enhanced mobility of GZO films. It was mainly due to the grain size of GZO films related to the roughened surface of the SiO_x buffer layers. In addition, the average optical transmittance of GZO/SiO_x/PET films in a visible regime was estimated to be ~ 90% comparable to that of GZO deposited onto a glass substrate.     

Comparative study of resistivity characteristics between transparent conducting AZO and GZO thin films for use at high temperatures

This paper compares in detail the resistivity behavior of transparent conducting Al-doped and Ga-doped ZnO (AZO and GZO) thin films for use in an air environment at high temperatures. AZO and GZO thin films with thicknesses in the range from approximately 30 to 100 nm were prepared on glass substrates at a temperature of 200 °C by rf superimposed dc or conventional dc magnetron sputtering deposition, pulsed laser deposition or vacuum arc plasma evaporation techniques. In heat-resistance tests, the resistivity was measured both before and after heat tests for 30 min in air at a temperature up to 400 °C. The resistivity stability of AZO thin films was found to be always lower than that of GZO thin films prepared with the same thickness under the same deposition conditions, regardless of the deposition technique. However, the resistivity of all AZO and GZO thin films prepared with a thickness above approximately 100 nm was stable when heat tested at a temperature up to approximately 250 °C. It was found that the resistivity stability in both GZO and AZO thin films is dominated by different mechanisms determined by whether the thickness is below or above approximately 50 nm. With thicknesses above approximately 100 nm, the increase in resistivity found in GZO and AZO films after heat testing at a temperature up to 400 °C exhibited different characteristics that resulted from a variation in the behavior of Hall mobility.     

Deposition of Al-doped ZnO films on polyethylene naphthalate substrate with radio frequency magnetron sputtering

100 nm Al-doped ZnO (AZO) thin films were deposited on polyethylene naphthalate (PEN) substrates with radio frequency magnetron sputtering using 2 wt.% Al-doped ZnO target at various deposition conditions including sputtering power, target to substrate distance, working pressure and substrate temperature. When the sputtering power, target to substrate distance and working pressure were decreased, the resistivity was decreased due to the improvement of crystallinity with larger grain size. As the substrate temperature was increased from 25 to 120 °C, AZO films showed lower electrical resistivity and better optical transmittance due to the significant improvement of the crystallinity. 2 wt.% Al-doped ZnO films deposited on glass and PEN substrates at sputtering power of 25 W, target to substrate distance of 6.8 cm, working pressure of 0.4 Pa and substrate temperature of 120 °C showed the lowest resistivity (5.12 × 10^− 3 Ω cm on PEN substrate, 3.85 × 10^− 3 Ω cm on glass substrate) and high average transmittance (> 90% in both substrates). AZO films deposited on PEN substrate showed similar electrical and optical properties like AZO films deposited on glass substrates.     

ITO thin films prepared by a microwave heating

ITO thin films were prepared by irradiating 2.45 GHz of microwave with an output power of 700 W using a commercial kitchen microwave oven. A substrate temperature went up and down rapidly between 100 and 650 °C in a minute by a dielectric loss of SnO₂ layer pre-deposited on a glass substrate. We found that the electrical and optical properties of films were affected by the atmosphere in a microwave irradiation, while the sintering was completed within a few minutes. Although the electrical resistivity was not reduced below 5.0 × 10^− 4 Ω·cm in this study, the results lead to the possibility of a practical rapid synthesis of ITO transparent conducting oxide films.     

Structural, electrical and bending properties of transparent conductive Ga-doped ZnO films on polymer substrates

We investigated the characteristics of highly transparent conductive Ga-doped ZnO (GZO) polycrystalline films of 100 nm thickness deposited on glass and polymer substrates. GZO films were deposited by ion plating with dc-arc discharge. We developed multiple-deposition method to obtain various deposition process temperatures lower than 100 °C. Cross-sectional SEM images show that all the GZO films have columnar structure. Analysis of data obtained by XRD measurements shows that all the GZO films with wurtzite structure exhibit highly (002) orientation perpendicular to the substrate. The resistivity of the GZO films deposited on polyester and glass substrates were 5.0 × 10^-4 Ω · cm. The mechanical bending properties of the GZO films were investigated by comparing the sheet resistance determined before and after a bending test with various bending diameters. For the bending diameter of more than 30 mm, all the GZO films exhibited excellent bending properties with no change in sheet resistance. For the bending diameter of less than 20 mm, we found the sheet resistance affected by the bending. We demonstrated that our multiple-deposition method to achieve different controllable polyester substrate temperatures is highly suitable for improving the bending properties of GZO films.     

Effect of the [Al/Zn] ratio in the starting solution and deposition temperature on the physical properties of sprayed ZnO:Al thin films

Aluminum-doped zinc oxide thin films (ZnO:Al) were deposited on sodocalcic glass substrates by the chemical spray technique, using zinc acetate and aluminum pentanedionate as precursors. The effect of the [Al/Zn] ratio in the starting solution, as well as the substrate temperature, on the physical characteristic of ZnO:Al thin films was analyzed. We have found that the addition of Al to the starting solution decreases the electrical resistivity of the films until a minimum value, located between 2 and 3 at.%; a further increase in the [Al/Zn] ratio leads to an increase in the resistivity. A similar resistivity tendency with the substrate temperature was encountered, namely, as the substrate temperature is increased, a minimum value of around 475 °C in almost all the cases, was obtained. At higher deposition temperatures the film resistivity suffers an increase. After a vacuum-thermal treatment, performed at 400 °C for 1 h, the films showed a resistivity decrease about one order of magnitude, reaching a minimum value, for the films deposited at 475 °C, of 4.3 × 10^− 3 Ω cm.The film morphology is strongly affected by the [Al/Zn] ratio in the starting solution. X-ray analysis shows a (002) preferential growth in all the films. As the substrate temperature increases it is observed a slight increase in the transmittance as well as a shift in the band gap of the ZnO:Al thin films.     

Half wave rectification of inorganic/organic heterojunction diode at the frequency of 1 kHz

An inorganic/organic vertical heterojunction diode has been demonstrated with p-type Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) deposited by spin coating on n-type Ga-doped ZnO (GZO) thin films. Transparent conducting GZO thin films are deposited on glass substrate by rf-magnetron sputtering. Electrical properties of GZO thin films are investigated depending on the processing temperatures. The resistivity, mobility and carrier concentration of the GZO thin films deposited at processing temperatures of 500 °C are measured to be about 3.6 × 10⁻⁴ Ω cm, 23.8 cm²/Vs and 7.1 × 10²⁰ cm³, respectively. The root mean square surface roughness of the GZO thin films is calculated to be ~ 0.9 nm using atomic force microscopy. Current-voltage characteristics of the n-GZO/p-PEDOT:PSS heterojunction diode present rectifying operation. Half wave rectification is observed with the maximum output voltage of 1.85 V at 1 kHz. Low turn-on voltage of about 1.3 V is obtained and the ideality factor of the n-GZO/p-PEDOT:PSS diode is derived to be about 1.8.     

Organic acid-based wet etching behaviors of Ga-doped ZnO films sputter-deposited at different substrate temperatures

150 nm thick Ga-doped ZnO (GZO) thin films were sputter-deposited at different substrate temperatures of 200 °C and room temperature (RT). Different degrees of crystallinity, electrical resistivities, and surface topologies resulted between these as-deposited GZO films. Weak organic acid-based etchants such as citric and formic acids with the identical concentration of 0.02 M were chosen for line-patterning of GZO films, and their etching results were found to be strongly dependent on the crystallinity of as-deposited GZO films. The GZO films deposited at 200 °C and RT exhibited a desirable etch profile such as a steep sidewall angle and a straight pattern line by 0.02 M formic and citric acids, respectively. The etch rate, etch profile, and activation energy for 200 °C- and RT-GZO films with organic acids used are compared, and the distinct etching mechanisms between 200 °C- and RT-GZO films are suggested.     

Conductive Ga doped ZnO/Cu/Ga doped ZnO thin films prepared by magnetron sputtering at room temperature for flexible electronics

Ga doped ZnO(GZO)/Cu/GZO multilayers were deposited by magnetron sputtering on polycarbonate substrates at room temperature. We investigated the structural, electrical, and optical properties of multilayers at various thicknesses of Cu and GZO layers. The lowest resistivity value of 3.3 × 10^− 5 Ω cm with a carrier concentration of 2.9 × 10²² cm^− 3 was obtained at the optimum Cu (10 nm) and GZO (10 nm) layer thickness. The highest value of figure of merit φ_TC is 2.68 × 10^− 3 Ω^− 1 for the GZO (10 nm)/Cu(10 nm)/GZO(10 nm) multilayer. The highest average near infrared reflectivity in the wavelength range 1000-2500 nm is as high as 70% for the GZO(10 nm)/Cu(10 nm)/GZO(10 nm) multilayer.     

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.     

Effects of the O2 flow rate and post-deposition thermal annealing on the optical absorption spectra of Ga-doped ZnO films

The optical absorption spectra of polycrystalline Ga-doped ZnO (GZO) thin films deposited by ion plating with direct current arc discharge have been studied. The GZO films that were deficient in oxygen showed absorption in the visible wavelength range. The intensity of the absorption band decreased with increasing O₂ flow rate during the deposition. Post-deposition thermal annealing in air and in a N₂ gas atmosphere also decreased the intensity of the absorption band. The intensity of the absorption band showed a slight correlation with carrier concentrations in the GZO films. The absorption intensity decreased with the decrease of the carrier concentration and diminished at a carrier concentration of around 7 × 10²⁰ cm^− 3. The contribution of carriers from native donors to transport in GZO films is discussed.     

Microstructural and optical properties of Ga-doped ZnO semiconductor thin films prepared by sol-gel process

Transparent thin films of Ga-doped ZnO (GZO), with Ga dopant levels that varied from 0 to 7 at.%, were deposited onto alkali-free glass substrates by a sol-gel process. Each spin-coated film was preheated at 300 °C for 10 min, and then annealed at 500 °C for 1 h under air ambiance. The effects of Ga dopant concentrations on crystallinity levels, microstructures, optical properties, and electrical resistivities of these ZnO thin films were systematically investigated. Photoluminescence spectra of GZO thin films were examined at room temperature. XRD results revealed that the undoped ZnO thin films exhibited a preferred orientation along the (002) plane and that the ZnO thin films doped with Ga showed degraded crystallinity. Experimental results also showed that Ga doping of ZnO thin films could markedly decrease surface roughness, improve transparency in the visible range, and produce finer microstructures than those of undoped ZnO thin films. The most promising films for transparent thin film transistor (TTFT) application produced in this study, were the 3 and 5 at.% Ga-doped ZnO thin films, both of which exhibited an average transmittance of 90.6% and an RMS roughness value of about 2.0 nm.