Muonium dynamics in transparent conducting oxides

The motional and electrical properties of positively charged muonium (Mu⁺)$({\mathrm{Mu}}^{+})$ centers in single crystal β-Ga₂O₃$\mathrm{\beta }\mathrm{-}{\mathrm{Ga}}_2{\mathrm{O}}_3$ are investigated via zero field muon spin relaxation (ZF-MuSR). Below room temperature we find two distinct shallow muonium centers with ionization energies of 7 and 16 meV. Above room temperature, at least three different Mu⁺ signals are resolved; two of these are metastable while the third shows characteristics of a stable ground state. As the temperature is elevated, metastable centers undergo several transitions. We obtain the relevant barrier energies associated with these site-change transitions. By 700 K, most muons occupy the mobile ground state, and an activation energy of about 1.65 eV is inferred for Mu⁺ diffusion from the hop rates obtained for this state.     

ZnMgAlO based transparent conducting oxides with modulatable bandgap

ZnMgAlO films with a broad spectral range of optical transmission and high conductivity were prepared by pulsed laser deposition. The optical and electrical properties of ZnMgAlO films could be controlled by adjusting Al and Mg contents. As the Mg content increased from 10 to 30 at.%, the bandgap value could be modulated from 3.78 to 4.66 eV, and the transparent wavelength range was widened within near-UV, visible and near-IR regions. The optimized ZnMgAlO film possesses a wide bandgap of 4.5 eV and a low resistivity of  cm. The broad spectral range of optical transmission and high conductivity maked ZnMgAlO films are of interest as TCO window materials for optoelectronic devices.     

Nuclear quadrupole resonance studies of transparent conducting oxides

We report ^63,65Cu spin–lattice relaxation rates measured by nuclear quadrupole resonance (NQR) in the delafossite compound CuYO₂ and CuYO₂:Ca over a temperature range from 200 to 450 K. CuYO₂:Ca is a prototype transparent oxide exhibiting p-type electrical conductivity. Relaxation rates in CuYO₂:Ca are enhanced by one to two orders of magnitude relative to undoped material, exhibit much stronger temperature dependence, and contain contributions from magnetic and quadrupolar relaxation mechanisms with roughly equal strengths. Relaxation in undoped CuYO₂ is of purely quadrupolar origin and is attributed to interactions with lattice phonons. The main focus of this paper is the magnetic contribution to the relaxation rate in CuYO₂:Ca which is attributed to the hyperfine fields of carriers. It is argued that the dynamics of the hyperfine field are dominated by the hopping rate for carrier transfers between neighboring atoms in the copper planes of the delafossite structure. Comparison of the magnetic relaxation rates with the DC conductivity permits an estimate of the carrier concentration and mobility.     

Temperature dependence of optical absorption for the visible region in transparent conducting oxides

We study theoretically the temperature dependence of the optical-absorption coefficient, for the visible region, in thin films of transparent conducting oxides by using the well-known Varshni approach relative to optical band-gap energy. Zero absorption is considered and an approximate formula for the coefficient of visible absorption is derived when photon energy is near the band-gap energy, that is, when absorption is negligible.     

Dopability, intrinsic conductivity, and nonstoichiometry of transparent conducting oxides

Existing defect models for In(2)O(3) and ZnO are inconclusive about the origin of conductivity, nonstoichiometry, and coloration. We apply systematic corrections to first-principles calculated formation energies Delta H, and validate our theoretical defect model against measured defect and carrier densities. We find that (i) intrinsic acceptors ("electron killers") have a high Delta H explaining high n-dopability, (ii) intrinsic donors ("electron producers") have either a high Delta H or deep levels, and do not cause equilibrium-stable conductivity, (iii) the O vacancy V(O) has a low Delta H leading to O deficiency, and (iv) V(O) has a metastable shallow state, explaining the paradoxical coexistence of coloration and conductivity.     

Room temperature transparent conducting oxides based on zinc oxide thin films

Doped zinc oxide thin films are grown on glass substrate at room temperature under oxygen atmosphere, using pulsed laser deposition (PLD). O₂ pressure below 1 Pa leads to conductive films. A careful characterization of the film stoichiometry and microstructure using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) concludes on a decrease in crystallinity with Al and Ga additions (≤3%). The progressive loss of the (0 0 2) orientation is associated with a variation of the c parameter value as a function of the film thickness and substrate nature. ZnO:Al and ZnO:Ga thin films show a high optical transmittance (>80%) with an increase in band gap from 3.27 eV (pure ZnO) to 3.88 eV and 3.61 eV for Al and Ga doping, respectively. Optical carrier concentration, optical mobility and optical resistivity are deduced from simulation of the optical data.     

Substitution mechanism of Ga for Zn site depending on deposition temperature for transparent conducting oxides

High quality transparent conductive gallium-doped zinc oxide (GZO) thin films were deposited on glass substrates using rf-magnetron sputtering system at the temperature ranging from room temperature (RT) to 500 °C. The temperature-dependence of Ga doping effect on the structural, optical and electrical properties in ZnO has been investigated. For the GZO thin films deposited at over 200 °C, (103) orientation was strongly observed by X-ray diffraction analysis, which is attributed to the substitution of Ga elements into Zn site. X-ray photoelectron spectroscopy measurements have confirmed that oxygen vacancies were generated at the temperature higher than 300 °C. This might be due to the effective substitution of Ga³⁺ for Zn site at higher temperature. It was also found that the optical band gap increases with deposition temperature. The optical transmittance of GZO thin films was above 87% in the visible region. The GZO thin films grown at 500 °C showed a low electrical resistivity of 4.50 × 10^?4 Ω cm, a carrier concentration of 6.38 × 10²⁰ cm^?3 and a carrier mobility of 21.69 cm²/V.     

Electronic structure of transparent oxides with the Tran-Blaha modified Becke-Johnson potential

We present electronic band structures of transparent oxides calculated using the Tran-Blaha modified Becke-Johnson (TB-mBJ) potential. We studied the basic n-type conducting binary oxides In(2)O(3), ZnO, CdO and SnO(2) along with the p-type conducting ternary oxides delafossite CuXO(2) (X=Al, Ga, In) and spinel ZnX(2)O(4) (X=Co, Rh, Ir). The results are presented for calculated band gaps and effective electron masses. We discuss the improvements in the band gap determination using TB-mBJ compared to the standard generalized gradient approximation (GGA) in density functional theory (DFT) and also compare the electronic band structure with available results from the quasiparticle GW method. It is shown that the calculated band gaps compare well with the experimental and GW results, although the electron effective mass is generally overestimated.     

SrZrO3-based proton conducting materials with La additions

The behaviour of La-containing strontium zirconate based ceramics is revised. La additions contribute to improve the sinterability of these materials, but transport properties are also affected. Sr_1−xLa_xZrO_3+δ show some unusual changes in transport properties when samples are exposed to H₂-containing atmospheres and then reoxidized. Nevertheless, the transport properties of (Sr,La)(Zr,Y)O_3−δ, are still mainly dependent on Y additions, at least for cases when the fraction of Y exceeds the fraction of La. In addition, lanthanum causes significant changes in lattice parameters. A combination of conductivity measurements in different atmospheres, ion blocking experiments, and emf measurements has been used to demonstrate that electron hole conductivity increases with temperature, and the protonic contribution drops. The transport properties at temperatures lower than about 800 °C might be affected by structural changes. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Materials design of p-type transparent conducting oxides of delafossite CuAlO2 by super-cell FLAPW method

We propose a new crystal growth method and a new valence control method to fabricate a low-resistive p-type and transparent conducting oxides of Delafossite CuAlO₂ based on ab initio electronic structure calculation using a super-cell FLAPW method. We propose a Cu-vacancy-acceptor doping method by decreasing a Cu-vapor pressure in order to increase a Cu-vacancy concentration. We also propose the Mg- or Be-impurity doping method at the Al-site using the thermal non-equilibrium crystal-growth method with extreme conditions in MBE or MOCVD by decreasing an Al-vapor pressure and avoiding the Mg- or Be-atom doping at the Cu-site by increasing a Cu-vapor pressure.     

General model for the functional dependence of defect concentration on oxygen potential in mixed conducting oxides

To understand and engineer applications for mixed conducting oxides, it is desirable to have explicit, analytical expressions for the functional dependence of defect concentration and transport properties on the partial pressure of the external gas phase. To fulfill this need, general expressions are derived for the functional dependence of defect concentration on the oxygen partial pressure () for the mixed ionic electronic conductors. The model presented in this paper differs from expressions obtained using the popular Brouwer approach because they are continuous across multiple Brouwer regions.

Alternative transparent conducting electrode materials for flexible optoelectronic devices

Transparent Conductive Electrode (TCE) is an essential part of the optoelectronic and display devices such as Liquid Crystal Displays (LCDs), Solar Cells, Light Emitting Diodes (LEDs), Organic Light Emitting Diodes (OLEDs) and touch screens. Indium Tin Oxide (ITO) is a commonly used TCE in these devices because of its high transparency and low sheet resistance. However, scarcity of indium and brittle nature of ITO limit its use in future flexible electronics. In order to develop flexible optoelectronic devices with improved performance, there is a requirement of replacing the ITO with a better alternate TCE. In this work, several alternative TCEs including transparent conductive oxides, carbon nanotubes, conducting polymers, metal nanowires, graphene and composites of these materials are studied with their properties such as sheet resistance, transparency and flexibility. The advantage and current challenges of these materials are also presented in this work.     

Bipolar resistance switching in the fully transparent BaSnO_3-based memory device

The fully transparent indium-tin-oxide/BaSnO3/F-doped SnO2 devices that show a stable bipolar resistance switching effect are successfully fabricated. In addition to the transmittance being above 87% for visible light, an initial forming process is unnecessary for the production of transparent memory. Fittings to the current-voltage curves reveal the interfacial conduction in the devices. The first-principles calculation indicates that the oxygen vacancies in cubic BaSnO3 will form the defective energy level below the bottom of conduction band. The field-induced resistance change can be explained based on the change of the interracial Schottky barrier, due to the migration of oxygen vacancies in the vicinity of the interface. This work presents a candidate material BaSnO3 for the application of resistive random access memory to transparent electronics.     

Sb掺杂SrTio3透明导电薄膜的光电子能谱研究

用X射线光电子能谱和同步辐射光电子能谱研究了Sb掺杂的钙钛矿型氧化物SrTi1-xSbxO3(x=0.05,0.10,0.15,0.20)薄膜的电子结构.薄膜由紫外脉冲激光淀积在SrTiO3(001)单晶衬底上.该薄膜系列在可见光波段透明,透过率均超过90%.其导电性与掺杂浓度有关,当Sb掺杂浓度x=0.05时,薄膜显示金属型导电性.X射线光电子能谱和同步辐射光电子能谱研究结果表明,Sb掺杂在母化合物SrTiO3的禁带内引入了浅杂质能级和深杂质能级.浅杂质能级上的退局域化电子离化到导带中会产生一定的传导电 关键词： 光电子能谱 光学透过率 脉冲激光沉积薄膜     

Electromechanical properties of graphene transparent conducting films for flexible electronics

We report a systematic study of the electromechanical properties of graphene films for flexible transparent conducting electrodes. The flexibility of graphene films, which were grown using a chemical vapor deposition (CVD) method and transfer process on polyethylene terephthalate (PET) substrates, was investigated using a lab-made inner/outer bending, twisting and stretching test system. The electromechanical properties as a function of the change of bending radius, twisting angle and strain distance were evaluated by measuring the change in resistance. The change in resistance during the inner bending test was less than 8% even when the bending radius was 3 mm. Additionally, the results of the inner bending fatigue test showed a constant resistance throughout 2000 bending cycles. However, in the outer bending test, the resistance increased substantially when the bending radius was smaller than 10 mm. Therefore, we can expect that more cracks form between the grains of graphene during the outer bending test. The twistability and stretchability of the graphene film were also investigated. Both twisting and stretching tests show gradually increasing resistances according to the twisting angle and stretching distance. These results provide useful information regarding the electromechanical properties of graphene transparent conducting films for the development of flexible electronics.     

Direct-write pulsed laser processed silver nanowire networks for transparent conducting electrodes

Metal nanowire networks are promising alternatives for transparent conducting layers in flexible electronics. However, the inverse relationship between transparency and conductivity limits their viability in many critical applications. In this work, we demonstrate a direct-write refining technique in which a solution-processed nanowire network, deposited by spin coating, is exposed to monochromatic UV pulsed laser processing near a plasmonic resonance. Our results exhibit a 75?% reduction in surface resistance along with marginal improvements in optical transparency. The local nature of the laser technique enables direct-write or large area processing on a variety of substrates including flexible, and organic materials.     

Mechanical reliability of transparent conducting IZTO film electrodes for flexible panel displays

The mechanical reliability of transparent In-Zn-Sn-O (IZTO) films grown using pulsed DC magnetron sputtering with a single oxide alloyed ceramic target on a transparent polyimide (PI) substrate at room temperature is investigated. All IZTO films deposited at room temperature have an amorphous structure. However, their optical and electrical properties change depending on the oxygen partial pressure applied during depositing process. At an oxygen partial pressure of 3%, the films exhibit a resistivity of 8.3 × 10⁻⁴ Ω cm and an optical transmittance of 86%. Outer bending tests show that the critical bending radius decreases from 10 mm to 7.5 mm when the oxygen partial pressure increases from 1% to 3%. In the inner bending test, the critical bending radius is independent of oxygen partial pressure at 3.5 mm, indicating excellent film flexibility. In the dynamic fatigue test, the electrical resistance of the films reduces by less than 1% for more than 2000 bending cycles. These results suggest that IZTO films have excellent mechanical durability and flexibility in comparison to ITO films.     

Optical and electrical properties of BaSnO3 and In2O3 mixed transparent conductive films deposited by filtered cathodic vacuum arc technique at room temperature

For the crystalline temperature of BaSnO$_{3}$ (BTO) was above 650 ℃, the transparent conductive BTO-based films were always deposited above this temperature on epitaxy substrates by pulsed laser deposition or molecular beam epitaxy till now which limited there application in low temperature device process. In the article, the microstructure, optical and electrical of BTO and In$_{2}$O$_{3}$ mixed transparent conductive BaInSnO$_x$ (BITO) film deposited by filtered cathodic vacuum arc technique (FCVA) on glass substrate at room temperature were firstly reported. The BITO film with thickness of 300 nm had mainly In$_{2}$O$_{3}$ polycrystalline phase, and minor polycrystalline BTO phase with (001), (011), (111), (002), (222) crystal faces which were first deposited at room temperature on amorphous glass. The transmittance was 70%-80% in the visible light region with linear refractive index of 1.94 and extinction coefficient of 0.004 at 550-nm wavelength. The basic optical properties included the real and imaginary parts, high frequency dielectric constants, the absorption coefficient, the Urbach energy, the indirect and direct band gaps, the oscillator and dispersion energies, the static refractive index and dielectric constant, the average oscillator wavelength, oscillator length strength, the linear and the third-order nonlinear optical susceptibilities, and the nonlinear refractive index were all calculated. The film was the n-type conductor with sheet resistance of 704.7 $\Omega /\Box $, resistivity of 0.02 $\Omega \cdot$cm, mobility of 18.9 cm$^{2}$/V$\cdot$s, and carrier electron concentration of $1.6\times 10^{19}$ cm$^{-3}$ at room temperature. The results suggested that the BITO film deposited by FCVA had potential application in transparent conductive films-based low temperature device process.     

Search for new oxide-ion conducting materials in the ceria family of oxides

We have adopted a modified combustion route, namely, a mixed fuel process (MFP) to prepare a novel series of nano-crystalline single- and multiple-doped ceria compositions with controlled powder characteristics, large surface area, finer particle size, high sinterability, and high oxide ion conductivity at intermediate temperatures (500–700 °C). Using the mixed fuel process, we have prepared nano-particles of single- and multiple-doped ceria powders with dopants such as Ca, Gd, and Sm and a suitable combination of the same. In the pursuit for identifying new oxide-ion-conducting materials in this family of oxides, we have pursued the idea of co-doping effect on the single doped compositions with proper introduction of a second dopant. Effect of these dopants on the thermal decomposition and physico–chemical characteristics of the precursor and the powders prepared thereby were studied in detail. Finally, the effects of multiple co-doping on the microstructural and electrical properties were compared to understand the origin of the effect of dopant characteristics on the oxide ion conductivity of Ce_1−x M _x O₂ solid solutions. Our experimental results established unequivocally that co-doping is very effective in identifying new materials with remarkably high ionic conductivity with substantial reduction in the cost for technological applications. Among the studied compositions, the maximum conductivity with minimum activation energy was observed for the triply co-doped CCGS composition (; E _a = 0.56 eV), which is much higher compared to the conductivity exhibited by most of the reported co-doped ceria compositions. In conclusion, an effective way to improve the oxide ion conductivity of ceria-based oxides by proper choice of dopants and co-doping is achieved.