ZnO/Cu2O Superlattice Thin Films : Growth by Sputtering Deposition and Characterizations of Physical Properties PDF Download
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Author: 鄭彥平
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Languages : en
Pages : 0
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Author: 鄭彥平
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Languages : en
Pages : 0
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Author: 鄧鈞元
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Languages : en
Pages : 0
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Author: 龔柏誠
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Languages : en
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Author: 洪于萱
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Languages : en
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Author: Chennupati Jagadish
Publisher: Elsevier
ISBN: 0080464033
Category : Science
Languages : en
Pages : 600
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With an in-depth exploration of the following topics, this book covers the broad uses of zinc oxide within the fields of materials science and engineering: - Recent advances in bulk , thin film and nanowire growth of ZnO (including MBE, MOCVD and PLD), - The characterization of the resulting material (including the related ternary systems ZgMgO and ZnCdO), - Improvements in device processing modules (including ion implantation for doping and isolation ,Ohmic and Schottky contacts , wet and dry etching), - The role of impurities and defects on materials properties - Applications of ZnO in UV light emitters/detectors, gas, biological and chemical-sensing, transparent electronics, spintronics and thin film
Author: Van Duren, Stephan
Publisher: Universitätsverlag der TU Berlin
ISBN: 3798330646
Category : Technology & Engineering
Languages : en
Pages : 188
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In recent years, kesterite Cu2ZnSnS4 (CZTS) has become an interesting alternative to copper indium gallium (di)selenide (CIGS) due to its non-toxic and earth abundant constituents. A variety of methods is being used to fabricate kesterite thin films, such as coevaporation, sputtering, electrodeposition, spray pyrolysis and others. Most of them include an annealing step to stimulate elemental mixing and interdiffusion. Although conversion efficiencies of kesterite solar cells have increased among different research groups, the record value of 12.6% set by IBM in 2014 has not been broken yet. Therefore, experimental and theoretical studies are needed to predict the effect of the secondary phases and detrimental defects on the electronical properties of the CZTS based solar devices. The work presented here studies non-destructive techniques for in situ process control and monitoring. With the aim to detect phases and phase transitions to optimize crucial processing steps such as pre-annealing of metal precursors, high temperature annealing and vacuum deposition of Cu-Sn-Zn-S based thin films. The research consists of three parts in which Raman spectroscopy, X-ray diffraction (XRD) and reflectometry are used to explore this objective. In the first part Raman spectroscopy is investigated as an in situ monitoring technique during high temperature annealing of thin films. It investigates whether the occurrence of CZTS can be monitored when it is created from annealing a Mo/CTS/ZnS layered thin film. CuS, SnS, ZnS and CTS (Cu-Sn-S) films are prepared by physical vapor deposition. The Raman scattering intensity was compared to investigate whether their specific vibrational modes can be distinguished from each other at room temperature. Then, the CTS film is annealed between 50 and 550 °C in order to investigate whether CTS vibrational modes can be identified at elevated temperatures and to see which transitions take place within the thin film. Also, a CZTS reference film is annealed between 50 and 550 °C for reference purposes. The temperature dependence of the main CZTS modes is examined to investigate whether it can be used for in situ temperature control. Finally, a ZnS layer is deposited on the unannealed CTS film to obtain a Mo/CTS/ZnS layered film. This film is used to study the conversion of CTS/ZnS into CZTS at elevated temperatures. It was found that Raman spectroscopy can successfully be used to monitor formation of CZTS by identifying its main vibrational mode during the annealing process. The intensity of the CTS modes reduces at elevated temperatures. At 450 °C, the main CZTS mode at 338 cm-1 can be clearly identified. The second part also focuses on high temperature annealing. However, in this part the focus lies on annealing of the metal precursor films. It is explored whether specific alloys benefit or hinder the formation of secondary phases during formation of the CZTS absorber films. Also, to what extent this influences solar cell performance. In situ XRD was investigated for in situ monitoring of the pre-annealing process. Cu-poor metal precursor films are prepared by sputtering deposition. The precursors are annealed at 150 °C, 200 °C, 300 °C and 450 °C in a three zone tube furnace. The effect on the structural properties is analysed by XRD to study the formation mechanism of alloys. The precursor films are then sulfurized in a three zone tube furnace. The structural properties of the absorber are analysed and correlated with structures in the precursor. It is found that formation of SnS2 in the absorber is proportional to the remaining Sn in the pre-annealed precursor. Also, electron micrographs showed that pre-annealing temperature influences grain growth and surface precipitation of Sn-S and Zn-S. Pre-annealed absorbers at 450 °C did not exhibit these phases on the surface. Solar devices are fabricated from the absorber films and best performing devices were obtained from pre-annealed absorbers at 450 °C. They showed absence of Sn and SnS2 in, respectively, the precursor and absorber. It could be concluded that SnS2 phases are detrimental to device efficiency and that SnS2 XRD peak intensity follows an inverse proportionality with device efficiency. The third part explores reflectometry as a method to monitor a growing film during thermal evaporation in a physical vapor deposition (PVD) system. A set of six CZTS absorbers is examined by ex situ Raman spectroscopy and reflectometry to study the influence of secondary phases CuS and ZnS on reflection spectra. Composition strongly influences reflection spectra and CuS leaves a characteristic dip in the reflection spectrum at about 600 nm. An integration method was used to analyze this phenomenon quantitatively. Subsequently, a reflectometry setup is designed, developed and integrated in the PVD system. Four different CZTS co-evaporated and multi-layered films are deposited. Structural, morphological and vibrational properties are investigated. The reflection spectra are monitored during deposition and time-dependent reflection spectra are analyzed for characteristic aspects related to properties such as thickness, band gap and phase formation. CuS could not be detected in the films by the integration method due to the superposition of the CuS dip with developing interference fringes during film growth. However, in multilayered CTS/ZnS film it is found that the onset of ZnS deposition can be detected by increased reflection intensity due to reduced surface roughness. Additionally, the shifting onset of the interference fringes to lower photon energies can be used as a characteristic fingerprint during the deposition process. In conclusion, this work showed that Raman spectroscopy, XRD and reflectometry could be successfully implemented for in situ process control and monitoring of high temperature annealing and vacuum deposition of Cu-Sn-Zn-S based precursors and absorbers. The application of these in situ techniques can lead to the optimization of thin film material properties and solar cells. As such, this study has paved the way for further improvement of Cu-Sn-Zn-S based precursors and thin film absorbers. Innerhalb der letzten Jahre hat sich Kesterit Cu2ZnSnS4 (CZTS) aufgrund seiner ungiftigen Bestandteile und deren hoher Verfügbarkeit zu einer interessanten Alternative zu Kupfer Indium Gallium (di-)Selenid (CIGS) entwickelt. Zur Herstellung von Kesterit Dünnschichten wird eine Vielzahl von Methoden verwendet wie Ko-Verdampfung, Sputtern, Elektrodeposition, Spray Pyrolyse und andere. Die meisten davon beinhalten einen Temper-Schritt um die Durchmischung und Interdiffusion der Elemente zu stimulieren. Obwohl der Wirkungsgrad der Kersterit Solarzellen von verschiedenen Forschungsgruppen erhöht wurde, ist der Rekordwert von IBM von 12,6 % noch nicht gebrochen worden. Daher werden experimentelle und theoretische Studien benötigt, die den Einfluss von Fremdphasen und schädlichen Defekten auf die elektronischen Eigenschaften der CZTS Solarzellen vorhersagen. Die vorliegende Arbeit untersucht zerstörungsfreie Methoden für die in situ Prozesskontrolle und -überwachung. Dabei ist das Ziel, entscheidende Prozessschritte wie das Vortempern der Metall-Vorläufer sowie das Hochtemperatur-Tempern und die Vakuum-Abscheidung von Cu-Sn-Zn-S basierten Schichten zu optimieren. Die Untersuchung besteht aus drei Teilen, in denen Raman-Spektroskopie, Röntgendiffraktion (XRD) und Reflektometrie benutzt werden um dieses Ziel zu erreichen. Im ersten Teil wird die Ramanspektroskopie als in situ Methode zur Überwachung des Hochtemperatur-Temperns von Dünnschichten betrachtet. Es wird untersucht, ob das Entstehen von CZTS beim Tempern von gestapelten Mo/CTS/ZnS Dünnschichten beobachtet werden kann. CuS, SnS, ZnS und CTS (Cu-Sn-S) Schichten werden durch physikalische Gasabscheidung hergestellt. Die Intensität der Raman Streuung wurde vergleichen um zu untersuchen, ob die spezifischen Vibrations-Moden bei Raumtemperatur voneinander unterschieden werden können. Dann werden die CTS Schichten zwischen 50 °C und 550 °C getempert um zu untersuchen, ob die CTS Vibrations-Moden bei höheren Temperaturen identifiziert werden können und um festzustellen, welche Übergänge innerhalb der Schicht auftreten. Außerdem wurde eine CZTS Referenzschicht zwischen 50 °C und 550 °C für Referenzzwecke getempert worden. Die Temperaturabhängigkeit der CZTS Haupt-Moden werden betrachtet, um zu untersuche, ob sie für die in situ Temperaturüberwachung verwendet werden können. Abschließend wurde eine ZnS Schicht auf einem nicht getemperten CTS Film abgeschieden, um eine gestapelte Mo/CTS/ZnS Schicht zu erhalten. Diese Schicht wird verwendet, um die Umwandlung von CTS/ZnS zu CZTS bei erhöhten Temperaturen zu untersuchen. Es wurde festgestellt, dass Raman Spektroskopie erfolgreich verwendet werden kann, um die Bildung von CZTS zu überwachen, indem die Haupt-Vibrations-Moden während des Temperns identifiziert werden. Die Intensität der CTS Moden verringert sich bei höheren Temperaturen. Bei 450 °C kann die CZTS Hauptmode bei 338 cm-1 klar identifiziert werden. Der zweite Teil konzentriert sich ebenfalls auf das Hochtemperatur-Tempern. In diesem Teil liegt der Fokus allerdings auf dem Tempern der Metal-Vorläufer-Schichten. Es wird erforscht, ob bestimmte Legierungen die Entstehung von Fremdphasen während der Entstehung der CZTS Absorberschichten begünstigen oder hemmen und welchen Einfluss dies auf die Leistung der Solarzelle hat. In situ XRD wird verwendet, um die Prozesse des Vortemperns zu überwachen. Kupfer arme Metall-Vorläufer-Schichten werden durch Sputtern aufgetragen. Die Vorläufer werden bei 150 °C, 200 °C, 300 °C und 450 °C in einem Drei-Zonen-Röhren-Ofen getempert. Die Auswirkungen auf die strukturellen Eigenschaften werden mit XRD analysiert, um den Entstehungsmechanismus der Legierungen zu untersuchen. Die Vorläuferschichten werden dann in einem Drei-Zonen-Röhren-Ofen sulfurisiert. Die strukturellen Eigenschaften des Absorbers werden analysiert und mit der Struktur der Vorläufer korreliert. Es wurde festgestellt, dass die Entstehung von SnS2 im Absorber proportional zum verbleibenden Sn im vorgetemperten Vorläufer ist. Außerdem zeigen Bilder des Rasterelektronenmikroskops, dass die Temperatur des Vortemperns das Kornwachstum und das Abschieden von Sn-S und Zn-S an der Oberfläche beeinflusst. Bei 450 °C vorgetemperte Absorber weisen keine dieser Phasen an der Oberfläche auf. Solarzellen werden aus diesen Absorber-Schichten hergestellt und die besten Zellen entstanden aus den bei 450 °C vorgetemperten Absorbern. Bei diesen traten Sn und SnS2 weder im Vorläufer noch im Absorber auf. Es konnte geschlussfolgert werden, dass SnS2 Phasen schädlich für den Wirkungsgrad der Zellen sind und dass die Intensität der SnS2 XRD Peaks invers proportional zum Wirkungsgrad der Zellen ist. Der dritte Teil erforscht die Reflektometrie als Methode zur Überwachung des Schichtwachstums während des thermischen Verdampfens in einer Anlage zur physikalischen Gasabscheidung (PVD). Ein Satz aus sechs CZTS Absorbern wird mittels ex situ Raman-Spektroskopie und Reflektometrie vermessen, um den Einfluss der Fremdphasen CuS und ZnS auf die Reflexionsspektren zu untersuchen. Die Zusammensetzung beeinflusst die Reflexionsspektren stark und CuS hinterlässt eine charakteristische Senkung bei 600 nm im Reflexionsspektrum. Eine Integrationsmethode wurde verwendet um dieses Phänomen quantitativ zu analysieren. Anschließend wurde ein Reflektometrieaufbau entworfen, entwickelt und in die PVD-Anlage integriert. Vier verschiedene CZTS koverdampfte und Mehrschicht-Filme wurden abgeschieden. Strukturelle, morphologische und Vibrationseigenschaften werden untersucht. Die Reflexionsspektren werden während des Abscheidens aufgenommen und zeitabhängige Reflexionsspektren werden auf charakteristische Aspekte im Zusammenhang mit Eigenschaften wie Dicke, Bandlücke und Entstehung von Phasen untersucht. CuS konnte in den Schichten mit der Integrations-Methode wegen der Überlagerung der CuS Senkung mit dem entstehenden Interferenzmuster nicht detektiert werden. Allerdings wurde in gestapelten CTS/ZnS Schichten beobachtet werden, dass der Beginn der ZnS Abscheidung durch eine ansteigende Intensität der Reflektion aufgrund der verringerten Oberflächenrauigkeit detektiert werden kann. Zusätzlich kann die Verschiebung des Startpunkts der Interferenzen zu niedrigeren Photonenenergien als charakteristischer Fingerabdruck während des Abscheidungsprozesses verwendet werden. Zusammenfassend zeigt diese Arbeit, dass Raman-Spektroskopie, XRD und Reflektrometrie erfolgreich als in situ Prozesskontrolle und –überwachung bei Hochtemperatur-Tempern und Vakuum-Abscheidung von Cu-Sn-Zn-S basierten Vorläufern und Absorbern realisiert werden konnten. Die Anwendung dieser in situ Techniken kann zu einer Optimierung der Eigenschaften von Dünnschicht-Materialien und von Solarzellen führen. Als solche hat diese Untersuchung den Weg für weitere Verbesserung von Cu-Sn-Zn-S basierte Vorläufer und Dünnschicht-Absorber geebnet.
Author: Paolo Mele
Publisher:
ISBN: 9781536160864
Category : Zinc oxide thin films
Languages : en
Pages : 0
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Zinc oxide (ZnO) is an n-type semiconductor with versatile applications such as optical devices in ultraviolet region, piezoelectric transducers, transparent electrode for solar cells and gas sensors. This book "ZnO Thin Films: Properties, Performance and Applications" gives a deep insight in the intriguing science of zinc oxide thin films. It is devoted to cover the most recent advances and reviews the state of the art of ZnO thin films applications involving energy harvesting, microelectronics, magnetic devices, photocatalysis, photovoltaics, optics, thermoelectricity, piezoelectricity, electrochemistry, temperature sensing. It serves as a fundamental information source on the techniques and methodologies involved in zinc oxide thin films growth, characterization, post-deposition plasma treatments and device processing. This book will be invaluable to the experts to consolidate their knowledge and provide insight and inspiration to beginners wishing to learn about zinc oxide thin films.
Author: Vladimir Petukhov
Publisher: Cuvillier Verlag
ISBN: 373694084X
Category : Science
Languages : en
Pages : 112
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For the electronic and optoelectronic device realization a precise control of the electrical properties in the utilized material is a very important issue. Doping profiles in realized p-njunctions influence the functionality of the devices. The morphological and crystal properties of a device material directly influence the electrical ones. Dislocations present in a region of p-n-junctions can short circuit them leading to malfunctions. Too rough surfaces during epitaxial growth could lead to inhomogeneities in a single or multiple quantum wells and superlattices. The main goal of the present work was to provide the basis for a reliable p-type doping of ZnO grown by molecular beam epitaxy. Firstly, the well established heteroepitaxial growth on c-sapphire substrates has been employed. Based on the theoretical and experimental works, suggesting nitrogen to be the impurity that builds the most shallow acceptor level in ZnO comparing to other group-V elements, it has been implied as a dopant. To generate reactive nitrogen atoms an rf-plasma source has been utilized in the MBE process. The resulting samples have been characterized by such methods as AFM, XRD, TEM, PL spectroscopy, temperature domain Hall measurements (TDHM) and ECV-profiling. First results of TDHM have shown that even in undoped samples the temperature dependencies of the electron mobility and carrier concentration have regions which are difficult to interpret. It is necessary to fit them with theoretical curves in order to extract the correct values. This task has proven to be very difficult. The complicated character of the dependencies has been explained in terms of the multilayer conduction model dividing a layer in thin interfacial region with mobility and carrier concentration μ1 and n1 respectivly and bulk region with a higher mobility μ2 and lower carrier concentration n2. The electrical transport in the bulk region has been modeled in terms of the general scattering theory in polar semiconductors. Such scattering mechanisms as scattering on polar-optical phonons, piezoelectric phonons, acoustic deformation potential, strain induced fields, dislocations, ionized and neutral impurities have been taken into account. Two cases have been considered to model transport in the interfacial region: 1) transport takes place in the conduction band of a highly doped degenerate semiconductor; 2) transport takes place in the impurity band formed by intermediate concentration of impurities and in conduction band in parallel. In the second case transport at the interface in conduction band has been neglected in the region of the low temperatures due to the impurities freeze-out and carrier concentration has been taken temperature independent like in the first case. To investigate experimentally the transport character in these two regions independently a mobility-spectrum analysis has been conducted. Theoretical results utilizing the two models have been compared with experimentally extracted mobility and carrier concentration in the interfacial region. It has been concluded that the concentration of donors in the layers is not high enough for the impurity band to merge with the conduction band and the second model is more consistent. The theoretically acquired donor concentration profiles have been compared with ECV-profiles. The agreement is very good. Simulations have revealed a shallow donor state with the ionization energy of approximately 45 meV . In the literature, this donor state in ZnO is attributed to hydrogen. However, due to the high diffusion mobility of hydrogen in ZnO, an annealing process would obviously decrease the carrier concentration in the samples which has not been the case. It has been suggested that the main donor centers are the electrically active crystal point defects generated by dislocations. Layers doped with nitrogen have been grown at very low temperatures (≈ 200°C) and at temperatures ranging from 400°C to 500°C, which are optimal for the epitaxial growth of ZnO. The samples grown at low temperatures are single crystalline with mosaic structure. In both cases, the introduction of the dopant increased the carrier concentration. This has been accounted for a bad crystal quality resulting in the inhomogeneous incorporation of nitrogen and for high background donor concentration due to the high dislocations densities. Additionally, the incorporation of acceptor centers shifts the Fermi-level increasing the formation probability of the compensating point defects. The analysis of TDHM showed an inconsistency of the one donor level model in the case of nitrogen doped samples. This fact and the decrease in the carrier concentration after annealing at 800°C for 30 minutes in ambient air can be explained by nitrogen forming donor-like defect complexes. In an attempt to improve the crystal quality of the heteroepitaxial layers, 15 periods of a ZnO/Zn0.6Mg0.4O superlattice structure have been inserted between the conventional double HT-MgO/LT-ZnO buffer and a main HT-ZnO layer. TDHM has revealed a very high mobility close to the values measured in a bulk ZnO for the temperature range of 20 - 300 K. However, TEM investigations of the samples have not indicated any decrease in the dislocation density comparing with the similar samples without a superlattice. Such a high mobility has been attributed to an electron transport in the superlattice structure. Heteroepitaxial growth of high quality ZnO-layers has proven to be challenging leaving the homoepitaxial growth as the only possibility to obtain the epitaxial layers with the best structural and electrical properties. The hydrothermally grown bulk ZnO substrates from two supplying companies, CrysTec and TokyoDenpa, have been employed for homoepitaxy. The substrates from CrysTec have not been epi-ready. Although AFM images reveal very flat surface, this has been damaged by the process of the chemomechanical polishing. This damaged layer must be removed. This has been achieved by the thermal annealing for 3 hours at 1050°C in ambient air. The thermally treated surfaces resulted in atomically flat terraces. XRD measurements have indicated an improvement of the crystal quality after annealing. The resistivity of the bulk substrates decreased after the thermal treatment due to out-diffusion of the compensating Li atoms letting Al, Ga and In atoms to contribute to conduction. After the longer annealing processes the etch-pits have been discovered on O-polar faces. The same features could be achieved by the chemical etching in a nitric acid on Zn-polar faces. The density of the threading dislocations on both polar faces for both types of substrates calculated by the etch-pit density investigation is about 105 1/cm2. Further the thermally treated substrates with atomically flat terraces have been utilized for homoepitaxy. The differences in growth kinetics during the molecular beam epitaxy on such substrates with the improved surface quality depending on their polarity have been investigated by RHEED measurements. The growth on a Zn-polar face has a 3D-character independently on a supplier. Morphologies of the resulting O- and Zn-polar layers have shown to be different. This has been explained by the presence of dangling bonds on Opolar face and thus, shorter diffusion time of the impinging Zn atoms on the surface. XRD and TEM measurements have shown a perfect crystal quality of the overgrown layers. The PL spectra of homoepitaxial layers are governed by the donor impurities diffused from the substrates. Considering the SIMS measurements of homoepitaxial layers found in the literature it has been concluded that the diffusion of donors in the layers grown on Zn-polar faces takes less effect then for the O-polar films. This conclusion has enforced the utilization of Zn-polar substrates supplied by CrysTec for the experiments with nitrogen doping of ZnO because of their affordable price. The electrical properties measured by ECV-profiling in series of homoepitaxial layers with varied growth parameters have shown an increase of the carrier concentration with the nitrogen incorporation. In addition, it has also been shown that the resulting electrical properties near the interface are governed mostly by the initial properties of the substrates. With increasing thickness of the layers carrier concentration saturated to the values of around 1016 1/cm3. The recent successful realization of the p-type MgZnO layers on TokyoDenpa substrates by researchers from Japan suggests switching to the p-type doped alloys because the above discussed results indicate that p-type doping with nitrogen of a pure ZnO is very difficult or even impossible. This is due to a rather fundamental reason: the formation of the compensating donor centers with the incorporation of acceptor atoms. As the first step in the future works, it is obvious to try to reproduce the results of the ZnMgO p-type doping with nitrogen employing growth on ZnO substrates.
Author: Jorj Ian Owen
Publisher: Forschungszentrum Jülich
ISBN: 3893367497
Category :
Languages : en
Pages : 231
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Author: Kyeong-Won Kim
Publisher:
ISBN:
Category :
Languages : en
Pages : 121
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The superlattices showed the strain induced enhancement of magnetization and the Curie temperature of superlattices were lowered substantially with increasing strain. Phosphorus doped ZnOthin films were deposited on ZnO buffer grown under different growth conditions and the properties of thin films were examined, focusing on the role of buffer layers. Phosphorus doped ZnO thin films on buffer layer grown at low temperature were less conductive as grown state and showed a drastic change in the transport properties upon the rapid thermal annealing. This suggests that poor crystalline quality of the buffer layer grown at low temperature lead to the more incorporation of phosphorus dopants in following films. A high resolution X-ray diffraction study confirmed the poor crystalline quality of phosphorus doped thin films on low temperature deposited buffer layer by broader peaks of omega rocking curves. Also it was observed that the microstructures of the phosphorus doped ZnO thin film significantly depended on the buffer layer.
