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.

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.

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.

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.

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.

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.

Modified textured surface MOCVD-ZnO:B transparent conductive layers for thinfilm solar cells

Modified textured surface boron-doped ZnO （ZnO：B） transparent conductive layers for thin-film solar cells were fabricated by low-pressure metal organic chemical vapor deposition （LP-MOCVD） on glass substrates. These modified textured surface ZnO：B thin films included two layers. The first ZnO：B layer, which has a pyramid- shaped texture, was deposited under conventional growth conditions, and the second layer, which has a sphere- like structure, at a relatively lower growth temperature. Typical bi-layer ZnO：B thin films exhibit a high electron mobility of 27.6 cm^2/（V.s） due to improved grain boundary states. For bi-layer ZnO：B, the haze value increases and the total transmittance decreases with the increasing film thickness of the second modification layer. When applied in hydrogenated microcrystalline silicon （μc-Si：H） thin-film solar cells, the modified textured surface ZnO：B layers present relatively higher conversion efficiency than conventional ZnO：B films.

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.

Structural and Physical Property Analysis of ZnO-SnO_2—In_2O_3—Ga_2O_3 Quaternary Transparent Conducting Oxide System

The increasing demand in the diverse device applications of transparent conducting oxides （TCOs） requires synthesis of new TCOs of n- or p-type conductivity. This article is about materials engineering of ZnO-SnO2- In2O3-Ga2O3 to synthesize powders of the quaternary compound Zn2-xSn1-xlnxGaxO4-δ in the stoichiometry of x = 0.2, 0.3, and 0.4 by solid state reaction at 1275℃. Lattice parameters were determined by X-ray diffraction （XRD） technique and solubility of In3＋ and Ga3＋ in spinel Zn2SnO4 was found at 1275℃. The solubility limit of In3＋ and Ga3＋ in Zn2SnO4 is found at below x = 0.4. The optical transmittance approximated by the UV-Vis reflectance spectra showed excellent characteristics while optical band gap was consistent across 3.2 eV with slight decrease along increasing x value. Carrier mobility of the species was considerably higher than the older versions of zinc stannate spinel co-substitutions whereas the carrier concentrations were moderate.

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.

Synthesis and Characterization of Indium Niobium Oxide Thin Films via Sol—Gel Spin Coating Method

In the present study, niobium-doped indium oxide thin films were prepared by sol-gel spin coating technique. The effects of different Nb-doping contents on structural, morphological, optical, and electrical properties of the films were characterized by means of X-ray diffraction （XRD）, field emission scanning electron microscopy （FESEM）, atomic force microscopy （AFM）, UV-Vis spectroscopy, and four point probe methods. XRD analysis confirmed the formation of cubic bixbyite structure of In203 with a small shift in major peak position toward lower angles with addition of Nb. FESEM micrographs show that grain size decreased with increasing the Nb-doping content. Optical and electrical studies revealed that optimum opto-electronic properties, including minimum electrical resistivity of 119.4 × 10^-3 Ω cm and an average optical transmittance of 85% in the visible region with a band gap of 3.37 eV were achieved for the films doped with Nb-doping content of 3 at.%. AFM studies show that addition of Nb at optimum content leads to the formation of compact films with smooth surface and less average roughness compared with the prepared ln2O3 films.

Type Inversion and Certain Physical Properties of Spray Pyrolysed SnO_2:Al Films for Novel Transparent Electronics Applications

Aluminium doped tin oxide films have been deposited onto glass substrates by using a simplified and low cost spray pyrolysis technique. The AI doping level varies between 0 and 30 at.% in the step of 5 at.%. The resistivity （p） is the minimum （0.38 Ω cm） for 20 at.% of AI doping. The possible mechanism behind the phenomenal zig-zag variation in resistivity with respect to AI doping is discussed in detail. The nature of conductivity changes from n-type to p-type when the AI doping level is 10 at.%. The results show that 20 at.% is the optimum doping level for good quality p-type SnO2：AI films suitable for transparent electronic devices.

Figure of Merit Enhancement of Surface Plasmon Resonance Biosensor Using Ga-Doped Zinc Oxide in Near Infrared Range

This work presents a surface plasmon resonance biosensor for the figure of merit enhancement by using Ga-doped zinc oxide(GZO),i.e.,nanostructured transparent conducting oxide as plasmonic material in place of metal at the telecommunication wavelength.Two-dimentional graphene is used here as a biorecognition element(BRE)layer for stable and robust adsorption of biomolecules.This is possible due to stronger van der Waals forces between graphene’s hexagonal cells and carbon-like ring arrangement present in biomolecules.The proposed sensor shows improved biosensing due to fascinating electronic,optical,physical,and chemical properties of graphene.This work analyses the sensitivity,detection accuracy,and figure of merit for the GZO/graphene SPR sensor on using the dielectric layer in between the prism and GZO.The highest figure of merit of 366.7 RIU^(−1) is achieved for the proposed SPR biosensor on using the nanostructured GZO at the 3000 nm dielectric thickness.The proposed SPR biosensor can be used practically for sensing of larger size biomolecules with due availability of advanced techniques for the fabrication of the nanostructured GZO and graphene.

Effect of Doped Boron on the Properties of ZnO Thin Films Prepared by Sol-gel Spin Coating

Transparent conductive boron-doped ZnO thin films were prepared by sol-gel spin coating method. The effect of doped boron concentration on the properties of the films was systematically discussed. The films were characterized by X-ray diffraction, atomic force microscopy, spectrophotometry, and Hall effect measurement system. All the doped and undoped ZnO films were of a single hexagonal structure, and showed a preferred orientation of （002）. The particle size and surface roughness of the films decreased with increased doped boron concentration. All the films exhibited an average transmittance of approximate 90% in visible-light region and an energy gap of about 3.3 cV. The maximum carrier concentration, the highest carrier mobility and the lowest resistivity were observed at a doped boron concentration of 0.5%（molar fraction）. Based on these results, we suggested that the saturation concentration of doped boron in ZnO film is 0.5%（molar fraction）.

Structural and optical properties of Zn-doped β-Ga_2O_3 films

Intrinsic fi-Ga203 and Zn-doped β-Ga203 films were prepared using RF magnetron sputtering. The effects of the Zn doping and thermal annealing on the structural and optical properties are investigated. In compar- ison with the intrinsic β-Ga203 films, the microstructure, optical transmittance, optical absorption, optical energy gap, and photoluminescence ofZn-doped β-Ga203 films change significantly. The post-annealed β-Ga203 films are polycrystalline. After Zn doping, the crystallization deteriorates, the optical band gap shrinks, the transmittance decreases and the UV, blue, and green emission bands are enhanced.

Structural, optical and electrical properties of ZnO： B thin films with different thickness for bifacial a-Si：H/c-Si heterojunction solar cells

Textured surface boron-doped zinc oxide （BZO） thin films were fabricated by metal organic chemical vapor deposition as transparent conductive oxide （TCO） for solar cells. The surface microstructure was characterized by X-ray diffraction spectrum and scan- ning electron microscope. The optical transmittance was shown by optical transmittance microscope and the electrical properties were tested by Hall measurements. The thickness of the BZO film has crucial impact on the surface morphology, optical transmittance, and resistivity. The electrical and optical properties as well as surface microstructure varied inconsistently with the increase of the film thickness. The grain size and the surface roughness increased with the increase of the film thickness. The conductivity increased from 0.96x 103 tO 6.94x 103 S/cm while the optical transmittance decreased from above 85% to nearly 80% with the increase of film thickness from 195 to 1021 nm. The BZO films deposited as both front and back transparent electrodes were applied to the bifacial p- type a-Si：H/i-type a-Si：H/n-type c-Si/i-type a-Si：H/n＋-type a-Si：H heterojunction solar cells to obtain the optimized parameter of thickness. The highest efficiency of all the samples was 17.8% obtained with the BZO film thickness of 829 nm. Meanwhile, the fill factor was 0.676, the open- circuit voltage was 0.63 Vand the short-circuit density was 41.79 mA/cm2. The properties of the solar cells changing with the thickness were also investigated.

Effects of reductive annealing on insulating polycrystalline thin films of Nb-doped anatase TiO2:recovery of high conductivity

We studied the effects of reductive annealing on insulating polycrystalline thin films of anatase Nb- doped TiO2 （TNO）. The insulating TNO films were intentionally fabricated by annealing conductive TNO films in oxygen ambient at 400 ℃. Reduced free carrier absorption in the insulating TNO films indicated carrier com- pensation due to excess oxygen. With H2-annealing, both carrier density and Hall mobility recovered to the level of conducting TNO, demonstrating that the excess oxygen can be efficiently removed by the annealing process without introducing additional scattering centers.

Ultra-broadband spatial light modulation with dual-resonance coupled epsilon-near-zero materials

It has been found that the dielectric constants of transparent conductive oxides(TCOs)can be adjusted in an extremely large range by tuning the carrier density.Due to the remarkable light confinement property of the epsilon-near-zero(ENZ)effect of TCOs,it has attracted extensive interests of light modulation.However,the operation wavelength bandwidth is usually limited by optical resonance that is applied to enhance the light-TCOs interaction.In this work,a dual-resonance light coupling scheme is proposed to expand the modulation depth-bandwidth product with almost one order-of-magnitude improvement.In a metallic subwavelength grating structure with deep trenches backed by a ground plane,the ENZ mode can be coupled to both magnetic resonance and Fabry-Perot resonance respectively by tuning the bias.Decent light modulation can be obtained in a large operation wavelength band covering two resonances by optimizing the dual-resonance configuration.Such a reconfigurable efficient broadband modulation is important for robust communication link and possesses remarkable capacity for wavelength division multiplexing.

Structure and properties of indium-doped ZnO films prepared by RF magnetron sputtering under different pressures

High conductive and transparent In-doped ZnO thin films were deposited on glass substrates by radio-frequency(RF)magnetron sputtering at 250℃.Argon gas was used as the sputtering gas,and its pressure varies from 0.1 to 4.0 Pa.The influences of deposition pressure on the structural,electrical and optical properties of the films were investigated by means of X-ray diffraction(XRD),scanning electron microscope(SEM)and Hall and transmittance measurements.The optical constant of the films was estimated from transmittance data using a nonlinear programming method.It is found that the deposition pressure affects the properties of the films significantly.The film deposited at 2.0 Pa shows the optimal crystal quality with a high transmittance of 85%in the visible range and a low resistivity of 2.4×10^(−3)Ω·cm and can thus be used as a transparent electrode.