Effects of Atomic Oxygen Irradiation on Transparent Conductive Oxide Thin Films

Transparent conductive oxide （TCO） thin film is a kind of functional material which has potential applications in solar cells and atomic oxygen （AO） resisting systems in spacecrafts. Of TCO, ZnO：Al （ZAO） and In2O3：Sn （ITO） thin films have been widely used and investigated. In this study, ZAO and ITO thin films were irradiated by AO with different amounts of fluence. The as-deposited samples and irradiated ones were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and Hall-effect measurement to investigate the dependence of the structure, morphology and electrical properties of ZAO or ITO on the amount of fluence of AO irradiation. It is noticed that AO has erosion effects on the surface of ZAO without evident influences upon its structure and conductive properties. Moreover, as the amount of AO fluence rises, the carrier concentration of ITO decreases causing the resistivity to increase by at most 21.7%.

Dopant-Tunable Ultrathin Transparent Conductive Oxides for Efficient Energy Conversion Devices

Ultrathin film-based transparent conductive oxides(TCOs)with a broad work function(WF)tunability are highly demanded for e cient energy conversion devices.However,reducing the film thickness below 50 nm is limited due to rapidly increasing resistance;furthermore,introducing dopants into TCOs such as indium tin oxide(ITO)to reduce the resistance decreases the transparency due to a trade-o between the two quantities.Herein,we demonstrate dopant-tunable ultrathin(≤50 nm)TCOs fabricated via electric field-driven metal implantation(m-TCOs;m=Ni,Ag,and Cu)without com-promising their innate electrical and optical properties.The m-TCOs exhibit a broad WF variation(0.97 eV),high transmittance in the UV to visible range(89–93%at 365 nm),and low sheet resistance(30–60Ωcm-2).Experimental and theoretical analyses show that interstitial metal atoms mainly a ect the change in the WF without substantial losses in optical transparency.The m-ITOs are employed as anode or cathode electrodes for organic light-emitting diodes(LEDs),inorganic UV LEDs,and organic photovoltaics for their universal use,leading to outstanding performances,even without hole injection layer for OLED through the WF-tailored Ni-ITO.These results verify the proposed m-TCOs enable e ective carrier transport and light extraction beyond the limits of traditional TCOs.

Enhanced light extraction of GaN-based light-emitting diodes with periodic textured SiO_2 on Al-doped ZnO transparent conductive layer

We report an effective enhancement in light extraction of Ga N-based light-emitting diodes（LEDs） with an Al-doped Zn O（AZO） transparent conductive layer by incorporating a top regular textured SiO2 layer. The 2 inch transparent throughpore anodic aluminum oxide（AAO） membrane was fabricated and used as the etching mask. The periodic pore with a pitch of about 410 nm was successfully transferred to the surface of the SiO2 layer without any etching damages to the AZO layer and the electrodes. The light output power was enhanced by 19% at 20 m A and 56% at 100 m A compared to that of the planar LEDs without a patterned surface. This approach offers a technique to fabricate a low-cost and large-area regular pattern on the LED chip for achieving enhanced light extraction without an obvious increase of the forward voltage.

Preparation and Characterization of Transparent Conductive Zinc Doped Tin Oxide Thin Films Prepared by Radio-frequency Magnetron Sputtering

High transparent and conductive thin films of zinc doped tin oxide （ZTO） were deposited on quartz substrates by the radio-frequency （RF） magnetron sputtering using a 12 wt% ZnO doped with 88 wt% SnO2 ceramic target.The effect of substrate temperature on the structural,electrical and optical performances of ZTO films has been studied.X-ray diffraction （XRD） results show that ZTO films possess tetragonal rutile structure with the preferred orientation of （101）.The surface morphology and roughness of the films was investigated by the atomic force microscope （AFM）.The electrical characteristic （including carrier concentration,Hall mobility and resistivity） and optical transmittance were studied by the Hall tester and UV- VIS,respectively.The highest carrier concentration of -1.144×1020 cm-3 and the Hall mobility of 7.018 cm2（V ·sec）-1 for the film with an average transmittance of about 80.0% in the visible region and the lowest resistivity of 1.116×10-2 Ω·cm were obtained when the ZTO films deposited at 250 oC.

Reliability of transparent conductive oxide in ambient acid and implications for silicon solar cells

Transparent conductive oxide(TCO)films,known for their role as carrier transport layers in solar cells,can be adversely affected by hydrolysis products from encapsulants.In this study,we explored the morphology,optical-electrical properties,and deterioration mechanisms of In2O3-based TCO films under acetic acid stress.A reduction in film thickness and carrier concentration due to acid-induced corrosion was observed.X-ray photoelectron spectroscopy and inductively coupled plasma emission spectrometry analyses revealed that TCOs doped with less-reactive metals exhibited enhanced corrosion resistance.The efficiency of silicon heterojunction(SHJ)solar cells with tin-doped indium oxide,titanium-doped indium oxide,and zinc-doped indium oxide films decreased by 10%,26%,and 100%,respectively,after 200h of corrosion.We also found that tungsten-doped indium oxide could effectively safeguard SHJ solar cells against acetic acid corrosion,which offers a potential option for achieving long-term stability and lower levelized cost of solar cell systems.This research provides essential insights into selecting TCO films for solar cells and highlights the implications of ethylene-vinyl acetate hydrolysis for photovoltaic modules.

Effect of Cu-Excess on the Electrical Properties of Cu_xAlO_2(1≤x≤1.06)

Cu-excess CuxAlO2 ceramics with delafossite phases were synthesized using sol-gel. In the composition range of 1≤x〈1. 04,there are no detectable non-delafossite phases. Weak diffraction peaks of CuO are observed when x ≥1.04. The room temperature conductivity of the CU1.04AlO2 sample is improved by nearly an order of magnitude over that of the CuAlO2 sample. The major defect mechanism responsible for the conductivity enhancement is proposed to be substitution defects of CuAl （Cu^2 ＋ ions substitute Al^3 ＋ ions）. The composition formula unit for Cu-excess Cux AlO2 may be expressed as Cu（All yCuy）O2.

Crystallization Behavior and Properties of B-Doped ZnO Thin Films Prepared by Sol-Gel Method with Different Pyrolysis Temperatures

Boron-doped zinc oxide transparent （BZO） films were prepared by sol-gel method. The effect of pyrolysis temperature on the crystallization behavior and properties was systematically investigated. XRD patterns revealed that the BZO films had wurtzite structure with a preferential growth orientation along the c-axis. With the increase of pyrolysis temperature, the particle size and surface roughness of the BZO films increased, suggesting that pyrolysis temperature is the critical factor for determining the crystallization behavior of the BZO films. Moreover, the carrier concentration and the carrier mobility increased with increasing the pyrolysis temperature, and the mean transmittance for every film is over 90% in the visible range.

Tunable and reconfigurable metasurfaces and metadevices

Metasurfaces, two-dimensional equivalents of metamaterials, are engineered surfaces consisting of deep subwavelength features that have full control of the electromagnetic waves. Metasurfaces are not only being applied to the current de-vices throughout the electromagnetic spectrum from microwave to optics but also inspiring many new thrilling applica-tions such as programmable on-demand optics and photonics in future. In order to overcome the limits imposed by pas-sive metasurfaces, extensive researches have been put on utilizing different materials and mechanisms to design active metasurfaces. In this paper, we review the recent progress in tunable and reconfigurable metasurfaces and metadevicesthrough the different active materials deployed together with the different control mechanisms including electrical, ther-mal, optical, mechanical, and magnetic, and provide the perspective for their future development for applications.

A comparison of transmittance properties between ZnO∶Al films for transparent conductors for solar cells deposited by sputtering of AZO and cosputtering of AZO/ZnO

Aluminum-doped zinc oxide (AZO) thin films were deposited on sapphire (002) and glass substrates by two different sputtering techniques radio frequency magnetron cosputtering of AZO and ZnO targets and sputtering of an AZO target. The dependence of the photoluminescence (PL) and transmittance properties of the AZO films deposited by cosputtering and sputtering on the AZO/ZnO target power ratio, R and the O2/Ar flow ratio, r were investigated, respectively. Only a deep level emission peak appears in the PL spectra of cosputtered AZO films whereas both UV emission and deep level emission peaks are observed in the PL spectra of sputtered AZO films. The absorption edges in the transmittance spectra of the AZO films shift to the lower wavelength region as R and r increase. Effects of crystallinity, surface roughness, PL on the transmittance of the AZO films were also explained using the X-ray diffraction (XRD), atomic force microscopy (AFM), and PL analysis results.

Recent Progress of Electrode Materials for Flexible Perovskite Solar Cells

Flexible perovskite solar cells(FPSCs) have attracted enormous interest in wearable and portable electronics due to their high power-per-weight and low cost. Flexible and efficient perovskite solar cells require the development of flexible electrodes compatible with the optoelectronic properties of perovskite. In this review, the recent progress of flexible electrodes used in FPSCs is comprehensively reviewed. The major features of flexible transparent electrodes, including transparent conductive oxides, conductive polymer, carbon nanomaterials and nanostructured metallic materials are systematically compared. And the corresponding modification strategies and device performance are summarized. Moreover, flexible opaque electrodes including metal films, opaque carbon materials and metal foils are critically assessed. Finally, the development directions and difficulties of flexible electrodes are given.

Optical and electrical properties of TiO_2/Au/TiO_2 multilayer coatings in large area deposition at room temperature

TiO2/Au/TiO2 multilayer thin films were deposited at polymer substrate at room temperature using dc （direct current） magnetron sputtering method. By varying the thickness of each layer, the optical and electrical properties of the TiOz/Au/TiO2 multilayer films can be tailored to suit different applications. The thickness and optical properties of the Au layer and the quality of the Au-dielectric interfaces are critical for the electrical and optical performance of the Au-dielectric multilayer thin films. At the thickness of 8 rim, the Au layer forms a continuous structure having the lowest resistivity and it must be thin for high transmittance. The multilayer stack can be optimized to have a sheet resistance of 6 D./sq. at a transmittance over 80% at 680 nm in wavelength. The peak transmittance shifts towards the long wavelength region when the thickness of the two TiO2 （upper and lower） layers increases. When the film thickness of the two TiO2 film is 45 nm, a high transmittance value is obtained for the entire visible light wavelength region.

The properties of transparent conducting molybdenum-doped ZnO films grown by radio frequency magnetron sputtering

Transparent conducting molybdenum-doped zinc oxide films are prepared by radio frequency（RF） magnetron sputtering at ambient temperature.The MoO3 content in the target varies from 0 to 5 wt%,and each film is polycrystalline with a hexagonal structure and a preferred orientation along the c axis.The resistivity first decreases and then increases with the increase in MoO3 content.The lowest resistivity achieved is 9.2 × 10^-4.cm,with a high Hall mobility of 30 cm^2.V-1.s-1 and a carrier concentration of 2.3×10^20 cm^-3 at an MoO3 content of 2 wt%.The average transmittance in the visible range is reduced from 91% to 80% with the increase in the MoO3 content in the target.

Using HF rather than NH_4F as doping source for spray-deposited SnO_2:F thin films

Fluorine doped tin oxide SnO2：F thin films were prepared by the spray pyrolysis （SP） technique on glass substrates by using SnC12.2H2O as a precursor and NH4F and HF as doping compounds. A comparison between the properties of the films obtained by using the two doping compounds was performed by using I-V characteristics in the dark at room temperature, AC measurements, and transmittance. It is found that the films prepared by using HF have smaller resistivity, lower impedance and they are less capacitive than films prepared by using NH4F. In addition, these films have higher transmittance, higher optical bandgap energy and narrower Urbach tail width. These results are interesting for the use of SnO2：F as forecontact in CdS/CdTe solar cells.

Annealing time dependent structural, morphological, optical and electrical properties of RF sputtered p-type transparent conducting SnO_2/Al/SnO_2 thin films

Transparent p-type conducting SnO2/Al/SnO2 multilayer films were fabricated on quartz substrates by radio frequency(RF) sputtering using SnO2 and Al targets. The deposited films were annealed at a fix temperature of 500 °C for different time durations(1-8 h). The effect of annealing time on the structural, morphological, optical and electrical performances of SnO2/Al/SnO2 multilayer films was studied. X-ray diffraction(XRD) results show that all the p-type conducting films possess polycrystalline SnO2 with tetragonal rutile structure. Hall-effect results indicate that 500 °C for 1 h is the optimum annealing condition for p-type SnO2/Al/SnO2 multilayer films, resulting in a hole concentration of 1.14×1018 cm-3 and a low resistivity of 1.38 ?·cm, respectively. The optical transmittance of the p-type SnO2/Al/SnO2 multilayer films is above 80% within annealing time range of 1-8 h, showing maximum for the films annealed for 1 h.

Preparation of ZAO film by low-temperature hydrothermal approach and its electrical property

Al-doped ZnO (ZAO) films were successfully deposited on the surface of common glasses by using low-temperature hydrothermal approach. In the reaction solution, the molar ratio of Al3+ to Zn2+ was 1∶100, the annealing temperature and time were 200 ℃ and 2-6 h, respectively. The structure of the thin films was identified by X-ray diffraction (XRD), the surface morphology and thickness of the thin films were observed by scanning electron microscopy (SEM), and the electrical performance of the thin films was measured by four-point probes. It was shown that the films with an average particle size of 27.53 nm had a preferential orientation along (002), Al3+ had replaced the position of Zn2+ in the lattice without forming the Al2O3 phase and its thickness was 20-25 μm. With the increased annealing time, the intensity of diffraction peaks was decreased, the film exhibited irregular surface morphology gradually, and the resistivity of ZAO films was increased. The lowest resistivity obtained in this study was 3.45×10-5Ω·cm.

Characteristics of SnO_(2):F Thin Films Deposited by Ultrasonic Spray Pyrolysis:Effect of Water Content in Solution and Substrate Temperature

Fluorine doped tin oxide, SnO2:F, thin films were deposited by ultrasonic chemical spray starting from tin chloride and hydrofluoric acid. The physical characteristics of the films as a function of both water content in the starting solution and substrate temperature were studied. The film structure was polycrystalline in all cases, showing that the intensity of (200) peak increased with the water content in the starting solution. The electrical resistivity decreased with the water content, reaching a minimum value, in the order of 8 × 10-4 Ωcm, for films deposited at 450℃ from a starting solution with a water content of 10 ml per 100 ml of solution;further increase in water content increased the corresponding resistivity. Optical transmittances of SnO2:F films were high, in the order of 75%, and the band gap values oscillated around 3.9 eV. SEM analysis showed uniform surface morphologies with different geometries depending on the deposition conditions. Composition analysis showed a stoichiometric compound with a [Sn/O] ratio around 1:2 in all samples. The presence of F into the SnO2 lattice was detected, within 2 at % respect to Sn.

THE BAND STRUCTURE AND WORK FUNCTION OF TRANSPARENT CONDUCTING ALUMINUM AND MANGANESE CO-DOPED ZINC OXIDE FILMS

Al and Mn co-doped-ZnO films have been prepared at room temperature by DC reacti ve magnetron sputtering technique. The optical absorption coefficient, apparent and fundamental band gap, and work function of the films have been investigated using optical spectroscopy, band structure analyses and ultraviolet photoelectro n spectroscopy (UPS). ZnO films have direct allowed transition band structure, w hich has been confirmed by the character of the optical absorption coefficient. The apparent band gap has been found directly proportional to N2/3, showing that the effect of Burstein-Moss shift on the band gap variations dominates over the many-body effect. With only standard cleaning protocols, the work function of ZnO: (Al, Mn) and ZnO: Al films have been measured to be 4.26 and 4.21eV, respec tively. The incorporation of Mn element into the matrix of ZnO, as a relatively deep donor, can remove some electrons from the conduction band and deplete the d ensity of occupied states at the Fermi energy, which causes a loss in measured p hotoemission intensity and an increase in the surface work function. Based on th e band gap and work function results, the energy band diagram of the ZnO: (Al, M n) film near its surface is also given.

Density functional theory analysis of electronic structure and optical properties of La-doped Cd_2SnO_4 transparent conducting oxide

The electronic structural, effective masses of carriers, and optical properties of pure and La-doped Cd2SnO4 are calculated by using the first-principles method based on the density functional theory. Using the GGA＋U method, we show that Cd2SnO4 is a direct band-gap semiconductor with a band gap of 2.216 eV, the band gap decreases to 2.02 eV and the Fermi energy level moves to the conduction band after La doping. The density of states of Cd2SnO4 shows that the bottom of the conduction band is composed of Cd 5s, Sn 5s, and Sn 5p orbits, the top of the valence band is composed of Cd 4d and O 2p, and the La 5d orbital is hybridized with the O 2p orbital, which plays a key role at the conduction band bottom after La doping. The effective masses at the conduction band bottom of pure and La-doped Cd2SnO4 are 0.18m0 and 0.092m0, respectively, which indicates that the electrical conductivity of Cd2SnO4 after La doping is improved. The calculated optical properties show that the optical transmittance of La-doped Cd2SnO4 is 92%, the optical absorption edge is slightly blue shifted, and the optical band gap is increased to 3.263 eV. All the results indicate that the conductivity and optical transmittance of Cd2SnO4 can be improved by doping La.

Barium-doped Pr_(2)Ni_(0.6)Cu_(0.4)O_(4+δ) with triple conducting characteristics as cathode for intermediate temperature proton conducting solid oxide fuel cell

Proton conducting solid oxide fuel cell(H-SOFC)is an emerging energy conversion device,with lower activation energy and higher energy utilization efficiency.However,the deficiency of highly active cathode materials still remains a major challenge for the development of H-SOFC.Therefore,in this work,K_(2)NiF_(4)-type cathode materials Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ)(x=0,0.1,0.2,0.3),single-phase tripleconducting(e-/O^(2-)/H^(+))oxides,are prepared for intermediate temperature H-SOFCs and exhibit good oxygen reduction reaction activity.The investigation demonstrates that doping Ba into Pr_(2-x)BaxNi_(0.6)Cu_(0.4)O_(4+δ) can increase its electrochemical performance through enhancing electrical conductivity,oxygen vacancy concentration and proton conductivity.EIS tests are carried at 750℃ and the minimum polarization impedances are obtained when x=0.2,which are 0.068 Ω·cm^(2) in air and 1.336 Ω·cm^(2) in wet argon,respectively.The peak power density of the cell with Pr_(1.8)Ba_(0.2)Ni_(0.6)Cu_(0.4)O_(4+δ) cathode is 298 mW·cm^(-2) at 750℃ in air with humidified hydrogen as fuel.Based on the above results,Ba-doped Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ) can be a good candidate material for SOFC cathode applications.

Transparent conductive SnO_(2)thin films via resonant Ta doping

Transparent conductive oxide(TCO)thin films are highly desired as electrodes for modern flat-panel displays and solar cells.Alternative indium-free TCO materials are highly needed,because of the scarcity and the high price of indium.Based on the mechanism of resonant doping,Ta has been identified as an effective dopant for SnO_(2)to achieve highly conductive and transparent TCO.In this work,we fabricated a series of Ta-doped SnO_(2)thin films(Sn_(1-x)Ta_(x)O_(2),x=0.001,0.01,0.02,0.03)with high conductivity and high optical transparency via a low-cost sol-gel spin coating method.The Sn_(0.98)Ta_(0.02)O_(2)film achieves the highest electrical conductivity of 855 S cm-1with a carrier concentration of2.3×10^(20)cm^(-3)and high mobility of 23 cm^(2)V^(-1)s^(-1).The films exhibit a very high optical transparency of 89.5%in the visible light region.High-resolution X-ray photoemission spectroscopy and optical spectroscopy were combined to gain insights into the electronic structure of the Sn_(1-x)Ta_(x)O_(2)films.The optical bandgaps of the films are increased from 3.96 eV for the undoped SnO_(2)to 4.24 eV for the Sn_(0.98)Ta_(0.02)O_(2)film due to the occupation of the bottom of conduction band by free electrons,i.e.,the Burstein-Moss effect.Interestingly,a bandgap shrinkage is also directly observed due to the bandgap renormalization arising from many-body interactions.The double guarantee of transparency and conductivity in Sn_(1-x)Ta_(x)O_(2)films and the low-cost growth method provide a new platform for optoelectronic and solar cell applications.