Electrical and optical studies of Ga-doped ZnO thin films

Nanostructure Ga-doped zinc oxide (GZO) thin films with highly (0 0 2) preferred orientation were fabricated on glass substrates, using radio frequency magnetron sputtering with an GZO ceramic target (The Ga₂O₃ contents was about 3 wt%) and different deposition conditions. The structural features, surface morphology and electrical and optical properties of the GZO thin films were studied, in terms of the deposition parameters. A Grey-based Taguchi method was used to determine the optimal deposition parameters for GZO thin films by considering multiple performance characteristics. The response graph and table for each level of the deposition parameters forms the Grey relational grade and the optimal levels of the deposition parameters were chosen. The experimental results show that the process pressure and the thickness make the most significant contribution to the overall performance. In the confirmation runs, Grey relational analysis showed that the improvement in deposition rate is 14.2 %, the improvement in electrical resistivity 38.1 % and the improvement in optical transmittance is 1.2 %. Annealing in a vacuum further improved the crystalline quality and optoelectronic performances of the GZO thin films.     

Effect of Thickness on the Properties of Ga-doped Nano-ZnO Thin Films Prepared by RF Magnetron Sputtering

Nano transparent conductive oxide (TCO) Ga-doped ZnO (GZO) thin films with thickness from 260 nm to 620 nm were prepared on glass substrates by RF magnetron sputtering from a powder target with 3 at.% Ga₂O₃. The substrate temperature was kept at 300 °C. The effect of thickness on the structural, electrical, and optical properties of GZO thin films was investigated. It shows that the nano-GZO films are dense and flat, and have polycrystalline structure with preferentially in the (002) orientation. With the increase of thickness, the crystallinity and the grain sizes of the films are improved, meanwhile the carrier concentration increases and the lowest resistivity of 3.685×10⁻³ Ω cm occurs in the 620 nm thick GZO film. The average optical transmittance of all the films is over 80% in the visible range. Decreasing the thickness, the optical transmission of the films increase, and the absorption edge shifts to shorter wavelength, which means the optical band gap is broadened.     

Low indium content In–Zn–O system towards transparent conductive films: structure,properties and comparison with AZO and GZO

In this work, low content indium doped zinc oxide (IZO) thin films were deposited on glass substrates by RF magnetron sputtering using IZO ceramic targets with the In₂O₃ doping content of 2, 6, and 10 wt%, respectively. The influences of In₂O₃ doping content and substrate temperature on the structure and morphology, electrical and optical properties, and environmental stability of IZO thin films were investigated. It was found that the 6 wt% doped IZO thin film deposited at 150?°C exhibited the best crystal quality and the lowest resistivity of 9.87?×?10^?4 Ω cm. The corresponding Hall mobility and carrier densities were 9.20 cm² V^?1 s^?1 and 6.90?×?10²⁰ cm^?3, respectively. Compared with 2 wt% Al₂O₃ doped ZnO and 5 wt% Ga₂O₃ doped ZnO thin films, IZO thin film with the In₂O₃ doping content of 6 wt% featured the lowest surface roughness of 1.3 nm. It also showed the smallest degradation with the sheet resistance increased only about 4.4% at a temperature of 121?°C, a relative humidity of 97% for 30 h. IZO thin film with 6 wt% In₂O₃ doping also showed the smallest deterioration with the sheet resistance increased only about 2.8 times after heating at 500?°C for 30 min in air. The results suggested that low indium content doped ZnO thin films might meet practical requirement in environmental stability needed optoelectronic devices.     

A study on the electrical and optical characteristics of IGZO films

The electrical and optical properties of InGaZnO (IGZO) thin films were studied in the research. It was found that all the films deposited at room temperature exhibit amorphous structures. A better film quality was obtained at a lower pressure with sputtering ambiance. The RF power toward the IZO target was constant at 125 W; the RF power toward the Ga₂O₃ target varied from 0 to 70 W. A best IGZO film with corresponding resistivity, carrier concentration, and mobility is 7.94 × 10^?4 Ω-cm, 1.68 × 10²⁰ cm^?3, and 47 cm²/V-s, respectively. Due to the doping of gallium in the IGZO film, it led to a lower resistivity than that of the IZO film. A blue shift effect of the film was also observed in the doping of gallium to the IGZO film. The H₂ plasma effects toward the IGZO were also observed.     

Influence of the substrate temperature on the optical and electrical properties of Ga-doped ZnO thin films fabricated by pulsed laser deposition

Ga-doped (5 wt%) zinc oxide (GZO) thin films were fabricated on corning 1737 substrates at a fixed oxygen pressure of 200 mTorr at various substrate temperatures (100–300 °C) by using pulsed laser deposition (PLD) in order to investigate the microstructure, optical, and electrical properties of the GZO thin films. It was observed that all the thin films exhibit c-axis orientation and exhibit only a (002) diffraction peak. The GZO thin film, which was fabricated at 200 mTorr and 300 °C, showed the highest (002) orientation, and the full width at half maximum (FWHM) of the (002) diffraction peak was 0.38°. The position of the XRD peak shifted to a higher angle with increase in the substrate temperature. The optical transmittance in the visible region was greater than 85%. The Burstein-Moss effect, which causes a shift toward a high photon energy level, was observed. The electrical property indicated that the highest carrier concentration (2.33 × 10²¹ cm⁻³) and the lowest resistivity (3.72 × 10⁻⁴ Ωcm) were obtained in the GZO thin film fabricated at 200 mTorr and 300 °C.     

High density plasma treatment of polyimide substrate to improve structural and electrical properties of Ga-doped ZnO films

We investigated the effects of a high density O₂ plasma treatment on the structural and electrical properties of sputter-deposited GZO films. The GZO films were deposited on polyimide substrate without substrate heating by RF magnetron sputtering from a ZnO target mixed with 5 wt.% Ga₂O₃. Prior to the GZO film growth, we treated a polyimide substrate with highly dense inductively coupled oxygen plasma. The optical transmittance of the GZO film, about 80%, was maintained regardless of the plasma pre-treatment. However, the resistivity of the film was strongly influenced by the plasma pre-treatment. The resistivity of the GZO film decreased from 1.02 × 10^− 2 Ω cm without an O₂ plasma pre-treatment to 1.89 × 10^− 3 Ω cm with an O₂ plasma pre-treatment.     

Effect of the substrate temperature on the properties of Ga-doped ZnO films for photovoltaic cell applications deposited by a pulsed DC magnetron sputtering with a rotating cylindrical target

Effect of substrate temperature on the properties of Ga-doped ZnO (GZO) films was investigated by pulsed DC magnetron sputtering with a rotating cylindrical target with an aim to establish suitable process conditions for their photovoltaic (PV) cell applications. Without formation of undesirable secondary oxide phases such as Ga₂O₃ and ZnGa₂O₄, the GZO film having mixed orientation at lower deposition temperature evolved into the c-axis oriented one with increasing deposition temperature to 230 °C, which accompanied morphological evolution to vertically oriented dense columnar structure and improved doping efficiency. Correlated with this, crater-like surface texturing was possible only on the sample deposited at 230 °C. Electrical resistivity and diffuse surface reflectance over the spectral range of 200-1200 nm of this GZO film after surface texturing were 8.73 × 10⁻⁴ Ω cm and 3.32%, respectively, indicating that the film has application potential as anti-reflection coating and front electrode of PV cells. Morphological features, surface texturing behavior, electrical and optical properties of the GZO films in this study suggest that this novel technique would be applicable to the fabrication of anti-reflection coating and front electrode of PV cells only when substrate temperature is sufficiently high.     

Effect of Ga doping on micro/structural, electrical and optical properties of pulsed laser deposited ZnO thin films

Undoped and Ga doped ZnO thin films (1% GZO, 3% GZO and 5% GZO) were grown on c-Al₂O₃ substrates using the 1, 3 and 5 at. wt.% Ga doped ZnO targets by pulsed laser deposition. X-ray diffraction studies revealed that highly c-axis oriented, single phase, undoped and Ga doped ZnO thin films with wurtzite structure were deposited. Micro-Raman scattering analysis showed that Ga doping introduces defects in the host lattice. The E₂^High mode of ZnO in Ga doped ZnO thin film was observed to shift to higher wavenumber indicating the presence of residual compressive stress. Appearance of the normally Raman inactive B₁ modes (B₁^Low, 2B₁^Low and B₁^High) due to breaking of local translational symmetry, also indicated that defects were introduced into the host lattice due to Ga incorporation. Band gap of the Ga doped ZnO thin films was observed to shift to higher energy with the increase in doping concentration and is explicated by the Burstein-Moss effect. Electrical resistivity measurements of the undoped and GZO thin films in the temperature range 50 to 300 K revealed the metal to semiconductor transition for 3 and 5% GZO thin films.     

Structural,optical and magnetic properties of Cr doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> powders and thin films

The (In_1?xCr_x)₂O₃ powders as well as thin films of x = 0.03, 0.05 and 0.07 were synthesized using a solid state reaction and an electron beam evaporation technique (on glass substrate), respectively. The influence of Cr doping concentration on structural, optical and magnetic properties of the In₂O₃ samples was systematically studied. The X-ray diffraction results confirmed that all the Cr doped In₂O₃ samples exist cubic structure of In₂O₃ without any secondary phases presence. The chemical composition analyses showed that all the Cr doped In₂O₃ compounds were nearly stoichiometric. The X-ray photoelectron spectroscopy analysis of the Cr doped In₂O₃ thin films showed an increase of oxygen vacancies with Cr concentration and the existence of Cr as Cr³⁺ state in the host In₂O₃ lattice. A small blue shift in the optical band gap was observed in the powder compounds, when the dopant concentration increased from x = 0.03 to x = 0.07. In thin films, the band gap found to increase from 3.63 to 3.74 eV, with an increase of Cr concentration. The magnetic measurements show that the undoped In₂O₃ bulk powder sample has the diamagnetic property at room temperature. And a trace of paramagnetism was observed in Cr doped In₂O₃ powders. However (In_1?xCr_x)₂O₃ thin films (x = 0.00, 0.03, 0.05 and 0.07) samples shows soft ferromagnetism. The observed ferromagnetism in thin films are attributed to oxygen vacancies created during film prepared in vacuum conditions. The ferromagnetic exchange interactions are established between metal cations via free electrons trapped in oxygen vacancies (F-centers).     

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.     

Dependence of the resistivity and the transmittance of sputter-deposited Ga-doped ZnO films on oxygen partial pressure and sputtering temperature

Ga-doped ZnO (GZO) thin films were prepared by rf magnetron sputtering and dependence of the electrical resistivity and the transmittance of the GZO films on the oxygen partial pressure (R = the O₂/Ar gas flow ratio) and the substrate temperature were investigated. The resistivity of the GZO film decreases first and then increases with an increase in the substrate temperature (T). A minimum resistivity obtained with a substrate temperature of 300 °C is 3.3 × 10⁻⁴ Ωcm. The resistivity nearly does not change with R for R < 0.25. The decrease in the resistivity for R < 0.25 is attributed to enhancement in crystallinity, whereas the increase in the resistivity for R > 0.25 to precipitation of gallium oxides at grain boundaries. Optical transmittance of the GZO films is enhanced by increasing R up to 0.75. This enhancement in the transmittance is due to a decrease in oxygen vacancy concentration and a decrease in surface roughness with R.     

Optical and hall properties of Al-doped ZnO thin films fabricated by pulsed laser deposition with various substrate temperatures

The 3 wt% Al-doped zinc oxide (AZO) thin films were fabricated on quartz substrates at a fixed oxygen pressure of 200 mTorr with various substrate temperatures (room temp. ～500 °C) by using pulsed laser deposition in order to investigate the microstructure, optical, and electrical properties of AZO thin films. All thin films were shown to be c-axis oriented, exhibiting only a (002) diffraction peak. The AZO thin film, fabricated at 200 mTorr and 400 °C, showed the highest (002) orientation and the full width at half maximum (FWHM) of the (002) diffraction peak was 0.42°. The c-axis lattice constant decreased with increasing substrate temperature. The electrical property indicated that the highest carrier concentration (1.27 × 10²¹ cm^?3) and the lowest resistivity (6.72 × 10^?4 Ωcm) were obtained in the AZO thin film fabricated at 200 mTorr and 400 °C. The optical transmittance in the visible region was higher than 80 %. The Burstein-Moss effect, which shifts to a high photon energy, was observed.     

Synthesis and characterization of Sn1Mg1−xO2 thin films fabricated by aero-sole assisted chemical vapor deposition

In order to achieve high conductivity and transmittance of transparent conducting oxide, Mg doped SnO₂ (Mg_xSn_1?xO₂) thin films have been fabricated and characterized to investigate their structural and optical properties. The Mg_xSn_1?xO₂ thin films have been deposited on glass substrate using aero-sole assisted chemical vapor deposition. The molar concentration of Mg contents was changed from 0 to 8 %. The confirmation of tetragonal structure and particle size (32–87 nm) of thin films was analyzed by X-ray diffraction. The surface roughness has been found to decrease with the increase of the dopant concentration as investigated by atomic force microscopy. The optical transmission increased from 54 to 78 % and the band gap of pure SnO₂ has been found to be 3.75 eV while it rises up to 3.88 eV with increasing Mg doping. The sheet resistance (R_s) of undoped SnO₂ is maximum which become lowest at 4 % Mg doped SnO₂.     

Influence of post-deposition annealing on the microstructure and properties of Ga2O3:Mn thin films deposited by RF planar magnetron sputtering

Thin films of Ga₂O₃:Mn have been deposited on silicon (100) substrates without intentional heating by radio frequency (RF) planar magnetron sputtering from a Mn-doped Ga₂O₃ target in an oxygen-argon mixture atmosphere. Microstructure and properties of the deposited Ga₂O₃:Mn films were systematically investigated as a function of the post-deposition annealing temperature in the range between 500 °C and 1200 °C. X-ray diffraction (XRD) measurements showed that the as-deposited Ga₂O₃:Mn films were of an amorphous structure in nature. The Ga₂O₃:Mn films became crystalline by the post-deposition annealing above 800 °C and the crystallinity of the films was continuously improved up to the annealing temperature of 1200 °C. It was shown that the annealed Ga₂O₃:Mn films possessed a monoclinic β-Ga₂O₃ phase having a textured structure with (400) and (?401) crystallographic planes oriented preferentially parallel to the substrate surface. The lattice parameters of the monoclinic β-Ga₂O₃ phase in the 1200 °C annealed Ga₂O₃:Mn films were measured to be a = 12.152 Å, b = 3.043 Å, and c = 5.785 Å.     

Characterization of hexagonal ɛ-Ga1.8Sn0.2O3 thin films for solar-blind ultraviolet applications

Ga_1.8Sn_0.2O₃ thin films were deposited on c-plane Al₂O₃ (0001) substrates by laser molecular beam epitaxy technology. Well crystallized (002) oriented ɛ-phase Ga_1.8Sn_0.2O₃ thin films were obtained at the substrate temperature above 750 °C and the oxygen partial pressure more than 5 × 10⁻³ Pa. The band-gap slightly shrinks with Sn⁴⁺ ions incorporated into Ga³⁺ sites, showing an excellent solar-blind ultraviolet (UV) characteristic. The conductivity of hexagonal ɛ-Ga_1.8Sn_0.2O₃ films is very low in the dark, and permitting the design and fabrication of solar-blind photodetector. The photodetector exhibits obvious photo-response under 254 nm UV light irradiation, and it increases in photocurrent with both the rise of applied bias and optical input power. The results suggest that ɛ-Ga_1.8Sn_0.2O₃ thin film is a promising candidate for using in solar-blind photodetectors.     

Influence of Ag concentration on the structure,optical and electrical properties of SnS<Subscript>2</Subscript>:Ag thin films prepared by spray pyrolysis deposition

Ag-doped tin-sulfide thin films were deposited with in spray pyrolysis method at T = 425 °C on soda lime glass substrates. The effects of Ag doping were investigated on the structural, optical, and electrical properties of thin films. Double deionized water was used as a precursor solution in which tin chloride (SnCl₄5H₂O) and thiourea (CS(NH₃)₂) in addition to silver acetate (AgC₂H₃O₂) were dissolved. All in all resulted to preparation of SnS₂:Ag thin films with \(\frac{{\left[ {\text{Ag}} \right]}}{{\left[ {\text{Sn}} \right]}}\% = 0, \,1, \,2, \,3\, {\text{and}} \,4\,{\text{at}}.\%\). The (001) plane is the preferred orientation of the SnS₂ phase which is analyzed by X-ray diffraction (XRD). The intensity of mentioned peak has an increasing trend, generally, with increasing Ag doping concentration. Thin films have spherical grains as is shown in SEM images. Increasing doping concentration from 1 to 4%, causes decrease in: single-crystal grains from 14.68 to 6.31 nm, optical band gap from 2.75 to 2.62 eV, carrier concentration from 3.11 × 10¹⁷ to 2.58 × 10¹⁷ cm^?3, and Hall mobility from 1.81 to 0.13 cm²/v s, as well as increase in: average grain size, generally, from 70 to 79 nm and electrical resistance from 11.11 to 181.26 Ω cm, respectively. The majority carriers are electrons for these films as is concluded from Hall Effect measurements.     

Research on the structural and optical stability of Ga2O3 films deposited by electron beam evaporation

Ga₂O₃ films were deposited on c-plane sapphire substrates using electron beam evaporation method with subsequent annealing in oxygen ambient for different time interval. The effect of annealing treatment on the microstructures and optical characteristics of Ga₂O₃ films were systematically investigated by X-ray diffraction, atomic force microscope, photoluminescence (PL) spectra and optical transmittance spectra, respectively. The results indicated that Ga₂O₃ films showed a stronger preferred orientation after annealing for 30, 60 and 90 min at 1,000 °C. The diffraction peaks $(\bar{6}01)$ and (403) of the annealed Ga₂O₃ films increased first and then decreased. We discussed the influence of annealing time interval on the grain sizes and surface morphologies properties of Ga₂O₃ films. The PL spectra measured at room temperature revealed blue, green and red emissions. Intense green luminescence was obtained from the sample annealed for 60 and 90 min. The crystalline quality of Ga₂O₃ film was markedly improved after annealing, which caused the intensity of blue peak (~430 nm) and green peak (~513 nm) increasing noticeably. The origin of these emissions was discussed. All annealed Ga₂O₃ films exhibited a steep absorption edge in deep ultraviolet region, and presented over 70 % transmittance in the visual light region.     

Investigation of dual ion beam sputtered transparent conductive Ga-doped ZnO films

Ga-doped ZnO (GZO) transparent conducting films were deposited on sapphire (0001) substrates using dual ion beam sputtering deposition system. The impact of growth temperature on the structural, morphological, elemental, optical, and electrical properties was thoroughly investigated and reported. X-ray diffraction measurements explicitly confirmed that all GZO films had (002) preferred crystal orientation. The film deposited at 400 °C exhibited the narrowest full-width at half-maximum value of 0.24° for (002) crystalline plane and the lowest room temperature electrical resistivity of 4.11 × 10^?3 Ω cm. The Raman spectra demonstrated the vibrational modes at 576 and 650–670 cm^?1, associated with native oxygen vacancies and elemental Ga doping in ZnO lattice, respectively. All doped films showed an overall transmittance of above 95 % in the visible spectra. A correlation between structural, optical, elemental, and electrical properties with GZO growth temperature was established.     

Growth and characterizations of dual ion beam sputtered CIGS thin films for photovoltaic applications

The growth of CIGS thin films on soda-lime glass substrates at different substrate temperatures by dual ion beam sputtering system in a single-step route from a single quaternary sputtering target with the composition of Cu (In_0.70 Ga_0.30) Se₂ was reported. The effects of the substrate temperature on structural, optical, morphological and electrical properties of CIGS films were investigated. Stoichiometry of one such film was investigated by X-ray photoelectron spectroscopy. All CIGS films had demonstrated a strong (112) orientation located at 2θ ~26.70^o, which indicated the chalcopyrite structure of films. The value of full-width at half-maximum of (112) peak was reduced from 0.58° to 0.19° and crystallite size was enlarged from 14.98 to 43.05 nm as growth temperature was increased from 100 to 400 °C. However, atomic force microscope results showed a smooth and uniform surface at lower growth temperature and the surface roughness was observed to increase with increasing growth temperature. Hall measurements exhibited the minimum film resistivity of 0.09 Ω cm with a hole concentration of 2.42 × 10¹⁸ cm^?3 and mobility of 28.60 cm² V^?1 s^?1 for CIGS film grown at 100 °C. Film absorption coefficient was found to enhance nominally from 1 × 10⁵ to 2.3 × 10⁵ cm^?1 with increasing growth temperature from 100 to 400 °C.