Polycrystalline ZnO Thin Films Research Articles

Improvement of electrical and optoelectronic properties of ZnO thin films by plasma nitridation treatment

Understanding and controlling the effects of trap sites in ZnO semiconductors are crucial for optimizing device performance and enabling various technological applications. To passivate the trap sites, the N atoms are incorporated into polycrystalline ZnO thin films via a plasma nitridation (PN) process using NH3 gas. The results show that the contact resistivity, sheet resistance, and transfer length of the ZnO photodetector are improved after the PN treatment. The photo-to-dark current ratio (PDCR) and responsivity values increase from 42.52 to 103.19 and from 344.36 A/W to 5727.63 A/W, respectively, after the PN treatment. This improvement in photodetector properties is attributed to the introduced N atoms, which effectively reduce the trap sites in the ZnO thin film. This PN treatment technology has the potential to improve device performance in both electronic and optoelectronic applications.

Structural insight into nanoscale inhomogeneity of electrical properties in highly conductive polycrystalline ZnO thin films doped using methane

Recently, methane has been demonstrated as an effective n-type dopant for ZnO thin films deposited using the RF-magnetron sputtering method. It was shown that the major electrical doping effect of methane is caused by hydrogen released during methane decomposition. This work investigates the origin of the observed increase in conductivity of methane-doped ZnO films with the increase in thickness. The study is aimed at describing the nature of this thickness-dependent effect through a detailed analysis of the thickness-dependent morphology and crystalline structure. A combination of structural, electrical, and optical characterization revealed a transition from fine-grained films with a random orientation at early stages to partially (002)-textured films with columnar grains at later stages of growth. It is demonstrated that grain/sub-grain boundaries increase the electrical conductivity and that the contribution of such buried inner boundaries increases with increasing thickness. It is proposed that hydrogen diffuses along the grain and sub-grain boundaries during growth, leading to continuous doping of the buried interfaces. This hydrogen diffusion mechanism results in an apparent ‘additional doping’ of thicker films. The results provide new insights into the thickness-dependent conductivity of doped polycrystalline ZnO films mediated by hydrogen diffusion along internal interfaces.

Effects of Ar Ion Sputtering on Surface of ZnO Polycrystalline Thin Films Measured by XPS

Effects of Ar Ion Sputtering on Surface of ZnO Polycrystalline Thin Films Measured by XPS

In-plane lattice thermal conductivity predictions of thin films within columnar grains

Polycrystalline thin films are widely used for devices and energy-related applications, such as power electronics, solar cells, and thermal management of devices. In many cases, large-scale crystallization during thin-film growth is challenging, so columnar grains are often found in metal and semiconductor thin films. These rough columnar grain boundaries may also have different phonon specularities from that for typically smoother top/bottom film surfaces. A simple analytical model to separately treat these boundaries and interfaces for phonon scattering is currently unavailable, although the in-plane thermal transport is critical to heat spreading within thin-film devices. In this paper, we extend the effective medium formulation from three-dimensional polycrystalline bulk materials to columnar-grained thin films. The model predictions agree well with those given by frequency-dependent phonon Monte Carlo simulations, considering varied phonon specularity at top/bottom film surfaces and grain-boundary phonon transmissivity. The analytical model is further used to analyze the existing data on polycrystalline ZnO thin films with columnar grains.

Fabrication of transparent polycrystalline zinc oxide thin film UV sensing transistor using polymeric electrolyte gate dielectric

The fabrication of electric double layer thin film transistors (EDLTFTs) using polymeric electrolyte as gate dielectric on chemically grown polycrystalline ZnO thin film channel has the lower threshold voltage at 0.4 V and the saturation current at 3 µA in the dark. The lower threshold voltage is -1 V and the saturation current is 10 µA in the UV illumination. In the dark and under UV light, the off state ID is 1 nA and 0.3 µA respectively and under gate and UV illumination the on current shows more than 3 times enhancement. This improvement in photocurrent is due to the combined effect of gate and UV illumination. The field effect mobility of the TFT is 0.06 cm2/Vs in the dark and 0.16 cm2/Vs under UV illumination. This increase in mobility under illumination and gate bias is due to the increase in carrier concentration and reduction of charged defects in the channel length.

Transition in the preferred orientation of RF sputtered ZnO/Si thin films by thermal annealing: Structural, morphological, and optical characteristics

Polycrystalline ZnO thin films having preferential growth along the polar (002) plane are prepared on Si (111) substrate using RF sputtering technique. A gradual build-up of the semipolar (103) plane with the dominant (002) polar plane of 400–700 °C annealed films is revealed by the Glancing incidence angle X-Ray diffraction (GXRD) pattern. However, a change in preferred orientation from polar (002) to semi-polar (103) and non-polar (100) planes is observed with further annealing in the temperature range 800–1200 °C. This occurs due to an increase in the mobility of adatoms due to annealing which encourages diffusion across grain boundaries and competitive growth among planes leading to the growth of (103) plane. This structural deviation of film from (002) plane to (103) plane leads to the change in surface morphology of annealed films around 800 °C as depicted in Field Emission Scanning Electron Microscopy (FESEM) images. The observed changes in surface morphology of films are further correlated with the variation in optical band gap values and diffuse reflectance spectra. The low reflectance values of the samples represent their anti-reflection property which makes ZnO/Si thin film a conceivable applicant in optoelectronics.

Characteristics and mechanism of light-induced resistance effect in ZnO thin film/SiO2/Si heterojunction

The polycrystalline ZnO thin films have been deposited on p-Si(100) substrate with a native SiO2 layer by radio frequency magnetron sputtering. The photoinduced position sensitivity of the ZnO thin film/SiO2/Si heterojunction has been investigated. The resistance relative change ratio of ZnO/SiO2/Si was about 1041% at 1.0 bias voltage when the different positions of the heterojunction surface were illuminated by a He-Ne laser with 5 mW power and 50 μm diameter spot. A gradient distribution of light-generated electrons in the sample varied with the location of the light spot. The reason was that the distribution of carrier density is different between the illuminated and unilluminated location.

Enhancement of Nonlinear Absorption in Defect Controlled ZnO Polycrystalline Thin Films by Means of Co‐Doping

The structural, optical, and nonlinear optical absorption properties of ZnO polycrystalline thin films are investigated. Energy bandgap values are obtained with linear absorption spectrum and depending on either sole doping of Al or co‐doping, bandgap energies shift toward higher or lower energies. With Al‐only doping, bandgap of the ZnO thin film shifts toward higher energies which can be attributed to Moss–Burstein effect, and with co‐doping (Al–Cu or Al–Co) bandgap energies shift toward lower energies due to defect states residing within the bandgap. Urbach energies and grain sizes are calculated to study the effect of defect states on the nonlinear absorption, and these calculations indicate that co‐doping drastically reduces the grain size thereby increasing the contribution to the defect density by means of boundary defects. To analyze the transmission in open aperture Z‐scan data, a theoretical model incorporating one‐photon, two‐photon, and free‐carrier absorptions as well as their saturations is used. By this modeling, saturation intensity thresholds and effective nonlinear absorption coefficients are extracted from fitting of the experimental data. Highest saturation intensity threshold and effective nonlinear absorption coefficient are found for ZnO:(Al, Co) and ascribed to having the smallest bandgap energy and highest Urbach energy.

Transport mechanisms in Co-doped ZnO (ZCO) and H-irradiated ZCO polycrystalline thin films.

In the present study, the electrical resistivity (ρ) as a function of the temperature (T) has been measured in polycrystalline ZnO, Co-doped ZnO (ZCO) and H irradiated ZCO (HZCO) samples, in the 300-20 K range. The achieved results show impressive effects of Co doping and H irradiation on the ZnO transport properties. The Co dopant increases the ZnO resistivity at high T (HT), whereas it has an opposite effect at low T (LT). H balances the Co effects by neutralizing the ρ increase at HT and strengthening its decrease at LT. A careful analysis of the ρ data permits to identify two different thermally activated processes as those governing the charge transport in the three materials at HT and LT, respectively. The occurrence of such processes has been fully explained in terms of a previously proposed model based on an acceptor impurity band, induced by the formation of Co-oxygen vacancy complexes, as well as known effects produced by H on the ZnO properties. The same analysis shows that both Co and H reduce the effects of grain boundaries on the transport processes. The high conductivity of HZCO in the whole T-range and its low noise level resulting from electric noise spectroscopy make this material a very interesting one for technological applications.

Polarization Dependent Excitation and High Harmonic Generation from Intense Mid-IR Laser Pulses in ZnO.

The generation of high order harmonics from femtosecond mid-IR laser pulses in ZnO has shown great potential to reveal new insight into the ultrafast electron dynamics on a few femtosecond timescale. In this work we report on the experimental investigation of photoluminescence and high-order harmonic generation (HHG) in a ZnO single crystal and polycrystalline thin film irradiated with intense femtosecond mid-IR laser pulses. The ellipticity dependence of the HHG process is experimentally studied up to the 17th harmonic order for various driving laser wavelengths in the spectral range 3–4 µm. Interband Zener tunneling is found to exhibit a significant excitation efficiency drop for circularly polarized strong-field pump pulses. For higher harmonics with energies larger than the bandgap, the measured ellipticity dependence can be quantitatively described by numerical simulations based on the density matrix equations. The ellipticity dependence of the below and above ZnO band gap harmonics as a function of the laser wavelength provides an efficient method for distinguishing the dominant HHG mechanism for different harmonic orders.

Comparison of TiO2 and ZnO electron selective layers on the inverted-type polymer solar cells

In this study, P3HT:PCBM polymer-based solar cell devices with TiO2 and ZnO electron selective layers were separately investigated to compare effects of metal oxide layer in the inverted-type polymer solar cell structures. R.f. magnetron sputtering technique was used to fabricate highly oriented polycrystalline TiO2 and ZnO thin film layers onto FTO-coated glass substrates. The surface morphology, structural and optical properties of TiO2 and ZnO electron selective layers were studied by performing X-ray diffraction (XRD), confocal Raman spectroscopy, transmittance spectra and Atomic Force Microscope (AFM). Photovoltaic performance of inverted-type polymer solar cell based on Poly (3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-Phenyl C61 butyric acid methyl ester (PCBM) with different electron selective layers was executed to analyze the effects of TiO2 and ZnO thin film layers on the power conversion efficiency (PCE) value of inverted polymer solar cell (IPSC) devices. Produced devices with TiO2 and ZnO thin film indicated the best device performance with maximum PCE values of 2.88 and 3.49%, respectively.

Controlling electrical and optical properties of zinc oxide thin films grown by thermal atomic layer deposition with oxygen gas

The preparation of ZnO thin films with controlled electrical resistivity and optical properties is often challenged by the presence of defects, such as oxygen vacancies or interstitial zinc. Here, we investigate the material properties of ZnO polycrystalline thin films prepared by thermal Atomic Layer Deposition (ALD) with the presence of molecular oxygen pulsing during the growth. By means of structural, electrical and optical characterizations, we identify key growth parameters of this unusual ALD process. Unexpectedly, the influence of oxygen molecules on the crystallography, microstructure and morphology of ZnO films is significant from hundred-nanometers to micrometer thick film. The electrical resistivity of the films grown with oxygen gas shows a dramatic increase from 3 to 4 orders of magnitude. Additionally, photoluminescence measurements reveal that deep-level emissions caused by defects located deep in the band gap can be reduced by applying an adequate pulsing of oxygen gas during the process. Finally, we conclude with a discussion about the degree of consistency between the chemical composition, the inner strain and the optical and electrical properties of the films obtained with the different thermodynamic parameters of growth. Several hypotheses are discussed in order to understand the dominance of (002) orientation in the presence of oxygen during the ALD growth process.

Characterization of ZnO/AlO x /benzene thin-film heterostructures grown through atomic layer deposition/molecular layer deposition

Multilayer thin-film structures are promising for many future high-tech applications. We investigate the structure of polycrystalline ZnO thin films with sub-nanometer amorphous inorganic (AlO x ) and organic (benzene) layers grown by atomic/molecular layer deposition. Small quantities of aluminium are typically introduced in ZnO films for doping, while one of the intended functions of the organic layers is to block thermal conductivity. We apply the AlO x and benzene layers both simultaneously and separately, and investigate the resultant superlattice films with transmission electron microscopy, x-ray reflectivity and x-ray diffraction measurements. The study reveals that both AlO x and benzene form distinct layers in the ZnO matrix even down to one atomic/molecular layer. Furthermore, we demonstrate that despite the clear layering, the ZnO grains can penetrate through thin (below ca. 2 nm) benzene and AlO x layers.

Doping-induced transition from polycrystals to single crystals in ZnO thin films

The growth of high quality ZnO thin films is a hot research topic in the field of optoelectronic materials. In this study, high quality ZnO thin films with a double-layer structure were obtained by sol-gel method. Al-doping induced transition from polycrystals to single crystals in the ZnO thin films was found. The results show that Al-doping improves the c-axis orientation of ZnO thin films. When the Al-doping concentration is higher than 4at%, the frustum of hexagonal pyramid (FHP) shaped ZnO nanostructures are formed on the polycrystalline ZnO thin films surface. As the Al-doping concentration further rises, the areal density of the FHP-shaped nanostructures also gradually increases and the size becomes more uniform. Both SAED patterns and high-resolution TEM images indicate that the FHP-shaped ZnO nanostructures are single crystals. It is of great scientific significance to transform polycrystalline ZnO into single crystal ZnO by Al-doping combined with a simple heat-treatment process. Compared with pure ZnO thin films, the FHP-shaped nanostructures on the surface show better UV emission performance, suggesting these materials are ideal ones for the preparation of ZnO-based UV emitters. The authors propose that the growth mechanism of FHP-shaped ZnO nanostructure is a multi-step solid-solid reaction dominated by surface diffusion of zinc atoms.

Quantifying competitive grain overgrowth in polycrystalline ZnO thin films

The grain size evolution of polycrystalline thin films, which form by competitive grain overgrowth as commonly interpreted using the van der Drift model, is understood to follow a power-law scaling of the average grain size d with film thickness h, i.e. d ∝ hα. While simulations have identified a growth exponent α = 0.4 for three-dimensional growth, previous experimental studies did not confirm this value, instead finding α values in the range of ∼0.5–0.7. Here we study competitive grain overgrowth using a system of ZnO thin films grown by low-pressure metal–organic chemical vapor deposition. We present quantitative data on the evolution of grain size and orientation across the thickness of thin films, obtained by automated crystal orientation mapping of “double-wedge” transmission electron microscopy samples. The data from a-textured ZnO films, grown under three different conditions, are compared against van der Drift model predictions of self-similarity of the grain size distribution and the power-law scaling. The results are further interpreted by comparing to simulations of faceted polycrystalline film growth, which we adapt to the ZnO system by including idiomorphic growth shapes with a six-fold symmetry and random or biased nuclei orientations. As well as showing the predicted self-similarity of grain size distributions during growth, for the first time our experimental data confirm a power-law growth exponent of α = 0.4, as also predicted by the simulations using randomly oriented nuclei. Nevertheless, interpretation of this result is contingent on the absence of factors such as textured nucleation and renucleation during film growth. Indeed, only one film, grown at a higher ratio of H2O/DEZ precursor gases, displaying random initial nucleation, and minimal grain renucleation during growth, shows a proper conformance to the model nature and predictions.

Quantifying Competitive Grain Overgrowth in Polycrystalline ZnO Thin Films

The grain size evolution of polycrystalline thin films, which form by competitive grain overgrowth as commonly interpreted using the van der Drift model, is understood to follow a power-law scaling of the average grain size d with film thickness h, i.e. d ∝ hα. While simulations have identified a growth exponent α = 0.4 for three-dimensional growth, previous experimental studies did not confirm this value, instead finding α values in the range of ~0.5-0.7. Here we study competitive grain overgrowth using a system of ZnO thin films grown by low-pressure metal-organic chemical vapor deposition. We present quantitative grain data on the evolution of grain size and orientation across the thickness of thin films, obtained by automated crystal orientation mapping of double-wedge transmission electron microscopy samples. The data from a-textured ZnO films, grown under three different conditions, are compared against van der Drift model predictions of self-similarity of the grain size distribution and the power-law scaling. The results are further interpreted by comparing to simulations of facetted polycrystalline film growth, which we adapt to the ZnO system by including idiomorphic growth shapes with a six-fold symmetry and random or biased nuclei orientations. As well as showing the predicted self-similarity of grain size distributions during growth, for the first time our experimental data confirm a power-law growth exponent of α = 0.4, as also predicted by the simulations using randomly oriented nuclei. Nevertheless, interpretation of this result is contingent on the absence of factors such as textured nucleation and renucleation during film growth. Indeed, only one film, grown at a higher ratio of H2O/DEZ precursor gases, displaying random initial nucleation, and minimal grain renucleation during growth, shows a proper conformance to the model nature and predictions.

Enhancement in optoelectrical properties of polycrystalline ZnO thin films by Ar plasma

In this study, the effects of Ar plasma treatment on the electrical, optical, morphological, and crystalline structural properties of polycrystalline ZnO thin films have been investigated. The simultaneous enhancements in conductivity and near band edge emissions (NBEs), accompanied by a suppression of deep level emissions (DLEs), suggest a passivation effect of the Ar plasma. The dependences on plasma treatment time showed correlations between the DLE and Hall mobility as well as between carrier concentration and the NBE. The results suggested that not only radiative defects but also nonradiative defects could be passivated. The plasma treatment also led to a distortion and deterioration of crystalline structure, as well as damage on the surface, which may account for the decrease in Hall mobility for long treatment time. The incorporation of hydrogen into the ZnO film after Ar plasma treatment has been confirmed using a secondary ions mass spectroscopy. The hydrogen incorporation could be the most probable factor accounting for the significant improvement in optoelectrical properties of ZnO thin film. In addition to the role of passivant, hydrogen atoms can also act as shallow donors, contributing to the eventual increase in carrier concentration.

Influence of ZnO thin film crystallinity on in vitro biocompatibility.

This study evaluated the cytocompatibility of single- and poly-crystalline ZnO thin films using extract and direct contact methods. Exposure to poly-crystalline ZnO extract resulted in reduced cell viability, on average 82%/70% as measured by MTS/LDH assays, respectively. Direct exposure to both single- and poly-crystalline ZnO thin films resulted in reduced cell viability, which was attributed to anoikis due to inhibition of cell adhesion to the substrate by zinc. Intracellular zinc imaging suggests that single crystalline ZnO thin films do not result in a significant change in intracellular zinc concentrations. Overall, the results suggest that single-crystalline ZnO thin films have better short-term (24 h) cytocompatibility and support their potential to serve as a biocompatible sensor material.

Influence of crystallographic polarity on the opto-electrical properties of polycrystalline ZnO thin films deposited by magnetron sputtering

Herein, the influence of crystallographic polarity on the properties of ZnO polycrystalline thin films deposited by magnetron sputtering, has been studied. The electrical and optical properties of undoped ZnO and heavily Ga-doped ZnO thin films showed significant differences between Zn polarity and O polarity. The Hall mobility and carrier concentration of the undoped ZnO thin films with Zn polarity were higher than those with O polarity. The ZnO film with Zn polarity showed a dominant near-band-edge emission, while that with O polarity showed relatively intense deep-level emission in the visible wavelength region. It was suggested that acceptor-type defects tend to be formed in the ZnO films with O polarity. The Ga-doped ZnO films deposited on the Zn-polar ZnO layer showed a higher carrier concentration and Hall mobility as compared to deposition on O-polar ZnO. Crystallographic polarity is thus a very important factor for controlling the properties of polycrystalline ZnO-based thin films deposited on glass substrates.

Effect of Substrate Temperature on the Microstructural, Morphological, and Optical Properties of Electrosprayed ZnO Thin Films

Polycrystalline ZnO thin films were prepared on silicon substrates using electrospray method with vertical setup. Water and ethanol were used as solvents for zinc acetate dehydrate and no postdeposition annealing was required for formation of ZnO. The influence of substrate temperature in the range of 150–250°C on surface morphology and roughness was studied by Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), and optical profilometry. An improvement of surface quality and smoothing of the films with temperature were obtained. X-ray diffraction measurements revealed that, at all investigated substrate temperatures, the films were polycrystalline with crystallites’ sizes decreasing with temperature. Besides, the preferred crystal orientation varies with the substrate temperature. The analysis of surface chemical composition and oxidation state was performed with X-ray photoelectron spectroscopy (XPS). It was shown that, at substrate temperature of 200°C, the deposited ZnO films were closest to the stoichiometric ones. In general, the films at 150°C were oxygen-deficient, while at other studied temperatures, the films had excess of oxygen more pronouncedly at 200°C. Spectral ellipsometric measurements confirmed that the structural disorder is the highest at 150°C and improves with temperature. Refractive indexes for films at 200°C and 250°C are almost the same, 1.97 and 1.93, respectively, at wavelength of 600 nm, while for the sample deposited at 150°C, the refractive index is substantially lower, 1.67. The optical band gap is slightly influenced by the substrate temperature: 3.27 eV at 150°C and 3.32 eV at 200°C.