Effect of substrate temperature on structural, optical and electrical properties of ZnO thin films deposited by pulsed laser deposition

ZnO thin films were grown by the pulse laser deposition (PLD) method using Si (100) substrates at various substrate temperatures. The influence of the substrate temperature on the structural, optical, and electrical properties of the ZnO thin films was investigated. All of the thin films showed c-axis growth perpendicular to the substrate surface. At a substrate temperature of 500 °C, the ZnO thin film showed the highest (002) peak with a full width at half maximum (FWHM) of 0.39°. The X-ray Photoelectron Spectroscopy (XPS) study showed that Zn was in excess irrespective of the substrate temperature and that the thin film had a nearly stoichiometrical composition at a substrate temperature of 500 °C. The photoluminescence (PL) investigation showed that the narrowest UV FWHM of 15.8 nm and the largest ratio of the UV peak to the deep-level peak of 32.9 were observed at 500 °C. Hall effect measurement systems provided information about the carrier concentration, mobility and resistivity. At a substrate temperature of 500 °C, the Hall mobility was the value of 37.4 cm²/Vs with carrier concentration of 1.36 × 10¹⁸ cm⁻³ and resistivity of 2.08 × 10⁻¹ Ω cm.     

The effect of growth conditions and N<Subscript>2</Subscript>/O<Subscript>2</Subscript> ambient on LO-phonon replicas during epitaxial growth of ZnO on c-sapphire

High quality heteroepitaxial thin films of ZnO:N were grown by pulsed laser deposition using a two-step growth method and annealed in situ at different temperatures and ambient conditions. Films were analyzed by X-ray diffraction (XRD), electrical measurements, and photoluminescence experiments at low temperatures to investigate the effect of nitrogen doping. The XRD results demonstrate epitaxial growth on the c-sapphire substrates, with average grain size of 57 nm. Photoluminescence spectra reveals a peak at 3.061 eV (405.1 nm) which is part of the longitudinal-optical-phonon replicas of excitons bound to neutral acceptors \textA₁⁰  \textX_\textA {\text{A}}_{1}^{0} \,{\text{X}}_{\text{A}} at 3.348 eV (370.4 nm), attributed in recent investigations to a newly reported donor–acceptor pair. Electrical resistivity and Hall effect measurements were performed using standard four point van der Pauw geometry at room temperature. Fresh films exhibited a resistivity of 3.1 × 10⁻³ Ω cm, a carrier density of 1.3 × 10¹⁹ cm⁻³, and a mobility of 53 cm²/V s. During approximately 2 weeks the as-deposited films presented a p-type behavior, as shown by the positive sign of the Hall constant measured. Thereafter, films reverted to n-type. From electrical measurements and photoluminescence spectra, the acceptor energy was determined to be 150 meV, in close agreement with reported values. These results are consistent with those presented in the literature for high purity crystals or homoepitaxial thin films, even though samples for the present study were processed at lower annealing temperature.     

Annealing effect on the microstructure and photoluminescence of ZnO thin films

Zinc oxide thin films have been obtained by pulsed laser ablation of a ZnO target in O₂ ambient at a pressure of 0.13 Pa using a pulsed Nd:YAG laser. ZnO thin films deposited on Si (1 1 1) substrates were treated at annealing temperatures from 400 °C up to 800 °C after deposition. The structural and optical properties of deposited thin films have been characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, photoluminescence spectra, resistivity and IR absorption spectra. The results show that the obtained thin films possess good single crystalline with hexagonal structure at annealing temperature 600 °C. Two emission peaks have been observed in photoluminescence spectra. As the post-annealing temperature increase, the UV emission peaks at 368 nm is improved and the intensity of blue emission at 462 nm decreases, which corresponds to the increasing of the optical quality of ZnO film and the decreasing of Zn interstitial defect, respectively. The best optical quality for ZnO thin films emerge at post-annealing temperature 600 °C in our experiment. The measurement of resistivity also proves the decrease of defects of ZnO films. The IR absorption spectra of sample show the typical Zn–O bond bending vibration absorption at wavenumber 418 cm⁻¹.     

Activation of phosphorous doping in high quality ZnO thin film grown on Yttria-stabilized zirconia (1 1 1) by thermal treatment

Phosphorous doped (P-doped) ZnO thin films are grown on c-sapphire and Yttria-stabilized zirconia (YSZ) (111) substrates by pulsed laser deposition. Post growth annealing is carried out to activate phosphorous to act as acceptor. The rocking curve of annealed P-doped ZnO films grown on YSZ (111) has full width at half maximum of 0.08°, more than two times narrower than that of the as-grown one. Neutral acceptor bound exciton (A⁰X) is observed from low temperature photoluminescence with estimated activation energy of 11.3 meV. Low carrier concentration of as-grown P-doped ZnO films indicated phosphorous doping creates acceptor states and/or reduced the oxygen vacancies. The carrier concentration of annealed samples is reduced by five order magnitudes from 3.21 × 10¹⁸ cm^− 3 to 1.21-8.19 × 10¹³ cm^− 3. At annealing temperature of 850 °C, the sample has the lowest carrier concentration and highest resistivity. This is an indication that the phosphorous in P-doped ZnO has been activated.     

Nitrogen-doped p-type ZnO thin films and ZnO/ZnSe p-n heterojunctions grown on ZnSe substrate by radical beam gettering epitaxy

We investigate the p-type doping in ZnO prepared by the method of radical beam gettering epitaxy using NO gas as the oxygen source and nitrogen dopant. Secondary ion mass spectroscopy measurements demonstrate that N is incorporated into ZnO film in concentration of about 8 × 10¹⁸ cm^− 3. The hole concentration of the N-doped p-type ZnO films was between 1.4 × 10¹⁷ and 7.2 × 10¹⁷ cm^− 3, and the hole mobility was 0.9-1.2 cm²/Vs as demonstrated by Hall effect measurements. The emission peak of 3.312 eV is observed in the photoluminescence spectra at 4.2  of N-doped p-type ZnO films, probably neutral acceptor bound. The activation energy of the nitrogen acceptor was obtained by temperature-dependent Hall-effect measurement and equals about 145 meV. The p-n heterojunctions ZnO/ZnSe were grown on n-type ZnSe substrate and have a turn-on voltage of about 3.5 V.     

Rapid Thermal Annealing of ZnO Nanocrystalline Films for Dye-Sensitized Solar Cells

Nanocrystalline ZnO thin films were prepared by the sol–gel method and annealed at 600 °C by conventional (CTA) and rapid thermal annealing (RTA) processes on fluorine-doped tin oxide (FTO)-coated glass substrates for application as the work electrode for a dye-sensitized solar cell (DSSC). ZnO films were crystallized using a conventional furnace and the proposed RTA process at annealing rates of 5 °C/min and 600 °C/min, respectively. The ZnO thin films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM) analyses. Based on the results, the ZnO thin films crystallized by the RTA process presented better crystallization than films crystallized in a conventional furnace. The ZnO films crystallized by RTA showed higher porosity and surface area than those prepared by CTA. The results show that the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) values increased from 4.38 mA/cm² and 0.55 V for the DSSC with the CTA-derived ZnO films to 5.88 mA/cm² and 0.61 V, respectively, for the DSSC containing the RTA-derived ZnO films.     

Electrical properties of boron- and phosphorous-doped microcrystalline silicon thin films prepared by magnetron sputtering of heavily doped silicon targets

The boron(B)- and phosphorous(P)-doped microcrystalline silicon (Si) thin films were prepared by magnetron sputtering of heavily B- and P-doped Si targets followed by rapid thermal annealing (RTA), their electrical properties were characterized by temperature-dependent Hall and resistivity measurements. It was observed that the dark conductivity and carrier concentration of the 260 nm B-doped Si films annealed at 1,100 °C in Ar were 3.4 S cm^?1 and 1.6 × 10¹⁹ cm^?3, respectively, which were about one order of magnitude higher than that of P-doped Si films. The activation energy of the B- and P-doped Si films were determined to be 0.23 eV and 0.79 eV, respectively. The dark conductivity of B- and P-doped Si films increased with the increase of film thickness, RTA temperature, and the incorporation of H₂ in Ar during RTA. The present work provides an easy and non-toxic method for the preparation of doped microcrystalline Si thin films.     

P-type conductivity in doped and codoped ZnO thin films synthesized by RF magnetron sputtering

N-doped and Al–N codoped ZnO thin films with different volume ratios of N₂ reactive gas were deposited on plane glass substrates using the radio frequency magnetron sputtering method. The phase transition temperature and absorption edge of the ZnO powder were studied by differential scanning calorimetry at different heating rates and with Fourier transform infrared spectroscopy, respectively. The target used for the sputtering was synthesized using a palletize machine. It was sintered at 450 °C for 5 h. The X-ray diffraction results confirm that the thin films have wurtzite hexagonal structures with a very small distortion. The results indicate that the ZnO thin films have obviously enhanced transmittance of up to 80% on an average in the visible region. The Al–N codoped ZnO thin films exhibited the best p-type conductivity with a resistivity of 0.825 Ω-cm, a hole concentration of 6.55 × 10¹⁹ cm^?3, and a Hall mobility of 1.25 cm²/Vs. The p-type conductivity was observed after doping and codoping of the ZnO thin film.     

Deposition of AgGaS<Subscript>2</Subscript> thin films by double source thermal evaporation technique

In this study, polycrystalline AgGaS₂ thin films were deposited by the sequential evaporation of AgGaS₂ and Ag sources with thermal evaporation technique. Thermal treatment in nitrogen atmosphere for 5 min up to 700 °C was applied to the deposited thin films and that resulted in the mono phase AgGaS₂ thin films without the participation of any other minor phase. Structural and compositional analyses showed the structure of the films completely changes with annealing process. The measurements of transmittance and reflectance allowed us to calculate the band gap of films lying in 2.65 and 2.79 eV depending on annealing temperature. The changes in the structure with annealing process also modify the electrical properties of the films. The resistivity of the samples varied in between 2 × 10³ and 9 × 10⁶ (Ω-cm). The room temperature mobility depending on the increasing annealing temperature was in the range of 6.7–37 (cm² V⁻¹ s⁻¹) with the changes in carrier concentrations lying in 5.7 × 10¹³–2.5 × 10¹⁰ cm⁻³. Mobility-temperature dependence was also analyzed to determine the scattering mechanisms in the studied temperature range with annealing. The variations in the electrical parameters of the films were discussed in terms of their structural changes.     

Investigation into the thermal annealing effects on CuIn(S,Se)2 thin films prepared by solution processes

CuIn(S,Se)₂ polycrystalline films were grown on soda-lime glass substrates by a solution process. Different annealing temperatures led to the variations of structural and electrical properties of the thin films. The pre-annealing temperatures changed from room temperature (RT) to 250°C, and all the post-annealing temperatures were set at 550°C. High quality film was obtained after post-annealing when the pre-annealing temperature increased to 250°C. The (112) X-ray diffraction peak’s position shifted at different pre-annealing temperatures after post-annealing, and the intensity of the (112) orientation increased with the pre-annealing temperature rising. Raman spectra exhibited A₁ mode was stable and the mixed B₂-E modes disappeared gradually with pre-annealing temperature increasing. The band gap energy of the film pre-annealed at 250°C is about 1.29 eV. The resistivity of the films without pre-annealing was 1230 Ω·cm, and 1.5 Ω·cm was achieved when the pre-annealing temperature was 250°C.     

Sol–gel derived Co<Subscript>3</Subscript>O<Subscript>4</Subscript> thin films: effect of annealing on structural,morphological and optoelectronic properties

Nanocrystalline Co₃O₄ thin films were prepared on glass substrates by using sol–gel spin coating technique. The effect of annealing temperature (400–700 °C) on structural, morphological, electrical and optical properties of Co₃O₄ thin films were studied by X-ray diffraction (XRD), Scanning Electron Microscopy, Electrical conductivity and UV–visible Spectroscopy. XRD measurements show that all the films are nanocrystallized in the cubic spinel structure and present a random orientation. The crystallite size increases with increasing annealing temperature (53–69 nm). These modifications influence the optical properties. The morphology of the sol–gel derived Co₃O₄ shows nanocrystalline grains with some overgrown clusters and it varies with annealing temperature. The optical band gap has been determined from the absorption coefficient. We found that the optical band gap energy decreases from 2.58 to 2.07 eV with increasing annealing temperature between 400 and 700 °C. These mean that the optical quality of Co₃O₄ films is improved by annealing. The dc electrical conductivity of Co₃O₄ thin films were increased from 10⁻⁴ to 10⁻² (Ω cm)⁻¹ with increase in annealing temperature. The electron carrier concentration (n) and mobility (μ) of Co₃O₄ films annealed at 400–700 °C were estimated to be of the order of 2.4–4.5 × 10¹⁹ cm⁻³ and 5.2–7.0 × 10⁻⁵ cm² V⁻¹ s⁻¹ respectively. It is observed that Co₃O₄ thin film annealing at 700 °C after deposition provide a smooth and flat texture suited for optoelectronic applications.     

CuIn(S,Se)2 thin films prepared by selenization and sulfurization of sputtered Cu–In precursors

CuIn(S,Se)₂(CISSe) thin films have been prepared onto soda-lime-glass (SLG) substrates by selenization and sulfurization of magnetron sputtered Cu–In precursors. The results indicate that the properties of the CISSe films are strongly dependent on the post-annealing treatment. After annealing at 400 °C for 20 min, the CISSe films have formed tetragonal (chalcopyrite) crystal structure and the diffraction peaks of the films shift systematically to the left with the temperature varying from 400 °C to 500 °C. EDAX study reveals that the compositions of CISSe films are Cu_0.83In_1.17S_1.67Se_0.3, Cu_0.86In_1.13S_1.61Se_0.4 and Cu_0.82In_1.15S_1.54Se_0.49 after annealing at 400 °C, 450 °C and 500 °C, respectively. The direct optical band gaps of the films slightly decrease from 1.44 ev to 1.32 ev with the increase of the temperature from 400 °C to 500 °C, and the optical absorption coefficient is over 10⁵ cm⁻¹. The films annealed at 400 °C–500 °C are all found to be p-type and the resistivity is almost 10⁻²–10⁻³ Ω cm. The carrier mobility of the film at 500 °C is almost as high as 1.701 cm²/V S.     

Growth of p-type ZnO thin films by using an atomic layer epitaxy technique and NH3 as a doping source

Nitrogen-doped, p-type ZnO thin films have been grown successfully on sapphire (0001) substrates by atomic layer epitaxy (ALE) using Zn(C₂H₅)₂ [Diethylzinc, DEZn], H₂O and NH₃ as a zinc precursor, an oxidant and a doping source gas, respectively. The lowest electrical resistivity of the p-type ZnO films grown by ALE was 210 Ω cm with a hole concentration of 3.41 × 10¹⁶ cm^− 3. Low temperature-photoluminescence analysis results support that the nitrogen ZnO after annealing is a p-type semiconductor. Also a model for change from n-type ZnO to p-type ZnO by annealing is proposed.     

Large-sized-mismatched group-V element doped ZnO films fabricated on silicon substrates by pulsed laser deposition

Pulsed laser deposition has been utilized to synthesize impurity-doped ZnO thin films on silicon substrate. Large-sized-mismatched group-V elements (A^V) including P, As, Sb and Bi were used as dopants. Hall effect measurements show that hole concentration in the order of 10¹⁶-10¹⁸ cm⁻³, resistivity in the range of 10-100 Ω cm, Hall mobility in the range of 10-100 cm²/Vs were obtained only for ZnO:As and ZnO:Bi thin films. X-ray diffraction measurements reveal that the films possess polycrystallinity or nanocrystallinity with ZnO (002) preferred orientation. Guided by X-ray photoemission spectroscopy analyses and theoretical calculations for large-sized-mismatched group-V dopant in ZnO, the A_Zn^V-2V_Zn complexes are believed to be the most possible acceptors in the p-type A^V-doped ZnO thin films.     

Characteristics of laser-annealed ZnO thin film transistors

We investigated the effects of laser annealing on ZnO thin film transistors (TFTs). ZnO layers were deposited on a bottom-gate patterned Si substrate by radio-frequency sputtering at room temperature. Laser annealing of the ZnO films reduced the full width at half maximum of the ZnO (002) diffraction peak from 0.49° to 0.1°. It reveals that the crystalline quality is improved by annealing effect. A SiO₂ formed in low temperature was used as the gate dielectric. Unannealed ZnO-TFTs were operated in enhancement mode with a threshold voltage of 21.6 V. They had a field-effect mobility of 0.004 cm²/Vs and an on/off current ratio of 134. Laser annealing of the ZnO-TFTs by 200 laser pulses reduced their threshold voltage to 0.6 V and increased their field-effect mobility to 5.08 cm²/Vs. The increase of mobility is originated from the crystallization enhancement of ZnO films after laser annealing.     

Microstructure and properties of Al-doped ZnO thin films by nonreactive DC magnetron sputtering at room temperature following rapid thermal annealing

A series of Al-doped ZnO (AZO) thin films deposited by nonreactive DC magnetron sputtering at room temperature following rapid thermal annealing was studied to examine the influence of these Al doping concentration, sputtering power and annealing temperature on their microstructure, electrical and optical transport properties. AZO thin films with Al dopant of 3 wt% were oriented more preferentially along the (002) direction, bigger grain size and lower electrical resistivity The resistivity of AZO films decreases with the increase of Al content from 1 to 3 wt%, sputtering power from 60 to 100 W and the annealing temperature from 50 to 250 °C. Sputtering power and annealing had some effect on the average transmittance of AZO thin films. For AZO thin films with Al doping level of 3 wt%, the lowest electrical resistivity of 5.3 × 10⁻⁴ Ω cm and the highest optical transmittance of 88.7% could gain when the sputtering power was 100 W and the annealing temperature was 200 °C or above.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

Power and gas pressure effects on properties of amorphous In–Ga–ZnO films by magnetron sputtering

Amorphous In–Ga–ZnO thin films were deposited on quartz glass substrate at room temperature utilizing radio frequency magnetron sputtering technique. Sputtering power and oxygen flow rate effects on the physical properties of the In–Ga–ZnO films were systematically investigated. It is shown the film deposition rate and the conductivity of the In–Ga–ZnO films increased with the sputtering power. The as-grown In–Ga–ZnO films deposited at 500 W exhibited the Hall mobility of 17.7 cm²/Vs. Average optical transmittance of the In–Ga–ZnO films is greater than 80% in the visible wavelength. The extracted optical band gap of the In–Ga–ZnO films increased from 3.06 to 3.46 eV with increasing the sputtering power. The electrical properties of the In–Ga–ZnO films are greatly dependent on the O₂/Ar gas flow ratio and post-growth annealing process. Increasing oxygen flow rate converted the In–Ga–ZnO films from semiconducting to semi-insulating, but the resistivity of the films was significantly reduced after being annealed in vacuum. Both the as-grown and annealed In–Ga–ZnO films show n-type electrical conductivity.     

Formation of F-doped ZnO transparent conductive films by sputtering of ZnF2

Fluorine-doped ZnO transparent conductive thin films were successfully deposited on glass substrate by radio frequency magnetron sputtering of ZnF₂. The effects of rapid thermal annealing in vacuum on the optical and electrical properties of fluorine-doped ZnO thin films have been investigated. X-ray diffraction spectra indicate that no fluorine compounds, such as ZnF₂, except ZnO were observed. The specimen annealed at 500 °C has the lowest resistivity of 6.65 × 10^? 4 Ω cm, the highest carrier concentration of 1.95 × 10²¹ cm^? 3, and the highest energy band gap of 3.46 eV. The average transmittance in the visible region of the F-doped ZnO thin films as-deposited and annealed is over 90%.     

Influence of annealing temperature on structural,electrical and optical properties of undoped zinc oxide thin films

The undoped zinc oxide thin films were grown on quartz substrate at a substrate temperature of 750 °C by radio frequency magnetron sputtering and post annealed at different temperatures (600–800 °C) for a period of 30 min. The influence of annealing temperature on the structure, electrical and optical properties of undoped ZnO thin films was investigated by X-ray diffraction, Hall-effect, photoluminescence and optical transmission measurements. Results indicated that the electrical properties of the thin films were extremely sensitive to the annealing temperature and the conduction type could be changed dramatically from n-type to p-type, and finally changed to weak p-type when the temperature increased from 600 to 800 °C. Electrical and photoluminescence results indicate that native defects, such as oxygen and zinc vacancies, could play an important role in determining the conductivity of these nominally undoped ZnO thin films. The conversion of the conduction type was attributed to the competition between Zn vacancy acceptor and oxygen vacancy and interstitial Zn donors. At an intermediate annealing temperature of 750 °C, the film behaves the best p-type characteristic, which has the lowest resistivity of 12 Ωcm, hall mobility of 2.0 cm²/V s and carrier concentration of 1.5 × 10¹⁷ cm^?3. The photoluminescence results indicated that the Zn vacancy might be responsible for the intrinsic better p-type characteristic in ZnO thin films.