反应溅射氧化锌薄膜的结构特点及性质

以金属Zn(纯度为99.99%)作为靶材,采用离子束反应溅射法在玻璃衬底上溅射沉积了一系列ZnO薄膜样品。通过对薄膜样品X射线衍射(XRD)谱的分析,发现尽管溅射条件不同,但是ZnO薄膜只沿(0002)晶面取向生长。衬底温度和溅射气体的氧分压对薄膜沿c轴取向生长有影响,其中衬底温度的影响较明显。溅射过程中发现衬底温度为360℃最适合(0002)晶面的生长,在此温度下溅射获得了完全沿c轴取向生长且衍射峰最强的ZnO薄膜。室温下测量了ZnO薄膜的发射光谱,发现薄膜在紫外区(364nm附近)、蓝绿区(470nm附近)有较强的发光峰,在紫光区(398nm附近)、蓝光区(452nm附近)和红外区(722nm附近)有较弱的发光峰。ZnO薄膜在空气中退火,对薄膜的结构、发光和电学性质都有一定影响。合适的退火温度可以促进薄膜沿c轴的取向生长;退火后ZnO多晶薄膜的晶粒比未退火的略大;退火使部分发光峰的位置发生偏移并使薄膜的发光强度增强;退火使薄膜的电阻率显著增大,薄膜的电阻率随氧分压的增大而增大。     

ZnO薄膜的自组织设计及形貌控制

采用单源化学气相沉积(SSCVD)法,在Si(100)基片上通过改变前驱反应体与基片的入射角度,获得了可控柱状取向的ZnO薄膜.研究发现,入射角度的改变可使沉积薄膜中的柱状结构的生成方向倾斜.但X射线衍射(XRD)分析表明:ZnO薄膜的c轴(002)取向与入射角无关,且不沿ZnO柱状结构的生长方向取向.由于ZnO的(002)面为其表面自由能最低且原子密度高的晶面,ZnO薄膜的生长更易于在垂直于基片表面的方向c轴取向生长.     

脉冲激光沉积(PLD)法生长高质量ZnO薄膜及其发光性能

采用脉冲激光沉积(PLD)法在单晶Si(100)衬底上生长ZnO薄膜,以X射线衍射(XRD)、原子力显微镜(AFM)和透射电镜(TEM)等手段分析了所得ZnO薄膜的晶体结构和微观形貌。优化工艺(700℃,20Pa)下生长的ZnO薄膜呈c轴高度择优取向,柱状晶垂直衬底表面生长,结构致密均匀。室温光致发光(PL)谱分析结果表明,随着薄膜生长时O₂分压的增大,近带边紫外发光峰与深能级发光峰之比显著增强,表明薄膜的结晶性能和化学计量比都有了很大的改善。O₂分压为20Pa时所生长的ZnO薄膜具有较理想的化学计量比和较高的光学质量。     

退火对ZnO薄膜光学特性的影响

用射频磁控溅射法在蓝宝石衬底上制备出ZnO薄膜,通过X射线衍射(XRD)、扫描电镜(SEM)和光致发光(PL)谱等研究了退火温度对ZnO薄膜结构和光学性质的影响。测量结果显示,所制备的ZnO薄膜为六角纤锌矿结构,具有沿c轴的择优取向;随着退火温度的升高,(002)XRD峰强度和平均晶粒尺寸增大,(002)XRD峰半高宽(FWHM)减小,光致发光紫外峰强度增强。结果证明,用射频磁控溅射法通过适当控制退火温度可得到高质量ZnO薄膜。     

氧压对飞秒激光沉积ZnO/Si(100)薄膜光学性能的影响

利用飞秒脉冲激光沉积法在n-Si（100）单晶衬底上制备了ZnO薄膜, 分析了衬底温度、激光能量、氧压及退火处理对薄膜结构和光学性能的影响. X射线衍射结果表明, 当激光能量为15?mJ、氧压为10?mPa时, 80?℃生长的薄膜取向性最好. 场扫描电子显微镜结果显示薄膜的晶粒尺寸随激光能量的增加而减小、随衬底温度的升高而增大且退火后明显变大. 紫外-可见透射光谱显示薄膜具有90%以上的可见光透过率.光致发光谱表明当氧压为10 mPa时,除了ZnO的紫外本征峰外, 还有一波长为410 nm的强紫光峰, 当氧压增至20 mPa以上, 所有缺陷峰均消失, 只有376 nm处的紫外本征峰. 与纳秒激光法所制备的薄膜特性进行了比较, 结果表明, 虽然纳秒激光沉积所制备的薄膜具有更高的c轴取向度, 但飞秒激光沉积制备的薄膜具有更好的发光性能. 关键词： 氧化锌 飞秒脉冲激光沉积 透过率 光致发光     

磁控溅射制备ZnO薄膜及其声表面波特性

通过射频磁控溅射技术在GaAs，Au/GaAs，Si和玻璃基片上成功制备了ZnO多晶薄膜，利用X射线衍射对ZnO薄膜的取向、结晶性进行了表征，结果表明ZnO薄膜呈完全c轴取向，Au缓冲层可以有效地改善ZnO薄膜的晶体质量，X射线摇摆曲线结果表明ZnO(002)衍射峰的半高宽仅为2.41°，同时发现Au缓冲层的结晶质量对ZnO薄膜的c轴取向度有很大影响，通过扫描电子显微镜对ZnO/GaAs和ZnO/Au/GaAs薄膜的表面形貌进行了观测，利用网络分析仪对IDT/ZnO/GaAs薄膜的声表面波特性进行了测量. 关键词： ZnO薄膜 X射线衍射 声表面波     

退火对ZnO薄膜质量的影响

用金属有机化学气相沉积法（MOCVD）在蓝宝石（0001）衬底上制备了c轴取向的高质量的ZnO薄膜,通过在生长温度下氧气和氮气中退火处理的比较,研究了退火对ZnO薄膜结构和发光特性的影响。通过X射线衍射测量得知,经过氮气和氧气退火都可以使其002峰增强,且在氧退火中表现得尤为明显。光致发光测量发现氮气中退火的ZnO薄膜的紫外发光峰明显增强,而深能级发光峰明显减弱;而氧气中退火的ZnO薄膜的紫外发光峰略有减弱,而深能级峰显著增强。     

溶胶-凝胶法制备MgxZn1-xO薄膜的结构及光学特性

用溶胶-凝胶法制备了一系列的Mg_xZn_1-xO(0≤x≤0.3)薄膜,并用X射线衍射(XRD)和光致发光(PL)研究了不同的退火温度和Mg的掺杂含量对Mg_xZn_1-xO薄膜的结构和光学性质的影响.研究表明:Mg_xZn_1-xO薄膜为单相六角纤锌矿结构,并且具有沿c轴的择优取向;发现了中间热处理温度为350℃的Mg_xZn_1-xO薄膜退火温度的转折点为700℃,低于这个温度时随退火温度的升高,(002)衍射峰强度增强且掺Mg的薄膜既有紫外光又有绿光发射;800℃退火时,薄膜的(002)衍射峰强度减小,出现了(100)和(101)衍射峰,且掺Mg的薄膜只有紫外发光峰.不同的掺杂浓度对于发光也有影响,低于700℃退火时,ZnO薄膜只出现紫外发光峰,掺Mg的薄膜却出现了紫外和绿光两个发光峰.     

氧分压对PLD制备ZnO薄膜结构和发光性质的影响

采用脉冲激光沉积(PLD)技术,在Si(100)衬底上制备出高度c轴取向的ZnO薄膜。通过X射线衍射(XRD)谱,扫描电镜(SEM)和室温光致发光(PL)光谱的测量,研究了生长气氛压强的改变对薄膜结构和光致发光的影响。实验结果表明,当氧压从10Pa升高到100Pa时ZnO(002)衍射峰的半峰全宽(FWHM)增大。可以认为这是由于较高的氧压下,到达衬底表面的离子动能减小。这样部分离子没有足够的能量迁移到生长较快的(002)面,c轴取向变差,导致(002)衍射峰的强度降低,半峰全宽增大。随着氧压增大,紫外发光强度增强。这可能是氧压变大,薄膜的化学配比升高,说明化学配比对UV发光的影响要大于薄膜微结构的影响。改变氧气压强对薄膜的表面形貌也有较大的影响。     

Ni掺杂ZnO薄膜的结构与光学特性研究

使用射频磁控溅射法成功制备了不同掺杂浓度（0—7at.%）的ZnO:Ni薄膜.X射线衍射的θ-2θ和摇摆曲线扫描结果表明,5at.%Ni掺杂ZnO薄膜具有沿c轴方向最佳的择优取向生长特性,（002）衍射峰向大角度方向移动揭示了Ni杂质被掺入ZnO晶格中占据Zn位.ZnO:Ni薄膜具有较好的可见光透明特性,拟合发现薄膜的光学带隙随Ni掺杂量的增加由3.272 eV线性降低到3.253 eV.未掺杂薄膜在550 nm处呈现出一个绿色发光峰,掺入Ni杂质后薄膜主要表现了以430 nm为中心的蓝色发光,分析认为它们分别源于薄膜中O空位和Zn填隙缺陷发光. 关键词： ZnO:Ni薄膜 结构特性 光学带隙 光致发光     

分子束外延生长的ZnO压电薄膜及其声表面波器件特性

用RF-MBE在蓝宝石(0001)衬底上引入MgO和低温ZnO双缓冲层生长了ZnO薄膜,并制备了声表面波器件。在ZnO薄膜中,仅观测到(0002)面的XRD,且衍射峰增强,半高宽减小,表明ZnO薄膜c轴取向性更好,晶体结构更优。室温下自由激子吸收峰更尖锐和吸收边更陡峭以及仅观测到自由激子发光,且发光线宽变窄、发光强度变大,表明ZnO薄膜缺陷密度减小,薄膜质量提高。测得该ZnO压电薄膜的电阻率高达4×10⁷ Ω·cm,其声表面波的速度高达5 010 m/s。     

籽晶层对喷雾热分解法生长ZnO薄膜结晶质量和光电性能的影响

通过脉冲激光沉积(PLD)方法在Si(100)衬底上沉积一层高质量的ZnO籽晶层,在籽晶层上进一步采用超声喷雾热分解(USP)法生长ZnO薄膜,研究了籽晶层对ZnO薄膜结晶质量和ZnO/Si异质结光电特性的影响。研究结果表明,在籽晶层的诱导作用下,USP法生长ZnO薄膜由多取向结构变为(002)单一取向,结晶性能得到了显著改善;籽晶层上生长的薄膜呈现出垂直于衬底生长的柱状晶结构,微观结构更加致密。通过研究紫外光照前后ZnO/Si异质结的整流特性,发现引入籽晶层后,反向偏压下异质结的光电响应显著增加,并且在开路状态下出现明显的光伏效应。     

Induced growth of high quality ZnO thin filmsby crystallized amorphous ZnO

This paper reports the induced growth of high quality ZnO thin film by crystallized amorphous ZnO. Firstly amorphous ZnO was prepared by solid-state pyrolytic reaction, then by taking crystallized amorphous ZnO as seeds (buffer layer), ZnO thin films have been grown in diethyene glycol solution of zinc acetate at 80℃. X-ray Diffraction curve indicates that the films were preferentially oriented [001] out-of-plane direction of the ZnO. Atomic force microscopy and scanning electron microscopy were used to evaluate the surface morphology of the ZnO thin film. Photoluminescence spectrum exhibits a strong ultraviolet emission while the visible emission is very weak. The results indicate that high quality ZnO thin film was obtained.     

ZnO薄膜的掺杂特性

通过MOCVD方法生长的ZnO薄膜一般为富锌生长,呈n型电导,要想得到高阻或低阻p-ZnO薄膜需要对其进行掺杂施主或受主杂质.主要研究在生长过程中通过NH₃对ZnO薄膜进行氮掺杂的情况,利用优化生长条件,即生长温度为610℃,Ar气(携带DEZn)流量为4sccm,O₂流量为120sccm,N₂流量为600sccm,得到在NH₃流量为80sccm时生长样品的结晶质量最高,在掺杂薄膜中NH₃流量高于或低于80sccm时,样品的表面形貌都将变差,只有在80sccm时表面粗糙度最低晶粒最小,表明该流量下获得的样品表面较光滑致密.所以80sccmNH₃流量为在R面蓝宝石上生长<110>取向ZnO薄膜的最佳掺杂流量.Hall测量结果表明,NH₃流量为50sccm的样品电导呈弱p型,电阻率为102Ω·cm,空穴载流子浓度为+1.69×10¹⁶cm^-3,迁移率为3.6cm²·V^-1·s^-1;当NH₃流量增加时样品的电导呈n型,电阻率最高达10⁸Ω·cm,我们认为与进入ZnO薄膜的H的量有关,并对其变化机理进行了详细的分析.     

Low-temperature MOVPE growth of ZnO thin films by using a buffer layer

ZnO thin films have been grown on a-plane (1,1,−2,0) sapphire substrates by metalorganic vapor phase epitaxy (MOVPE) at low substrate temperature of 350 °C. It is showed that the crystal and electrical quality of the thin films was improved by using a ZnO buffer layer. The photoluminescence (PL) measurements indicate that the ZnO thin films grown at such a low substrate temperature have a strong UV emission.     

p-type ZnO thin films grown by RF plasma beam assisted Pulsed Laser Deposition

The high exciton binding energy and band gap energy of ZnO thin films open the prospect of fabricating semiconductor lasers in the ultraviolet spectral range. A prerequisite for laser diode fabrication is highly p-doped ZnO which was not reproducibly obtained up to now. Without intentional doping ZnO exhibits n-type conduction. ZnO thin films have been obtained by radio-frequency assisted pulsed laser deposition. A metallic Zn target was used for ablation in an oxygen and nitrogen RF discharge. The electrical and morphological properties of the films grown on Si were studied by Atomic Force Microscopy (AFM), X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), optical absorption and Hall Effect measurements for different ratios between the nitrogen and oxygen content. The AFM images of the as-grown ZnO films reveal high quality surfaces with low values for the surface roughness and a sharp distribution of grains sizes as an effect of the RF discharge. The XRD patterns for all samples exhibit only (002) and (004) peaks indicating that the c-axis is always oriented normal to the substrate surface. The films present p-type conductivity with different carrier concentration and mobility depending on the nitrogen/oxygen ratio.     

Self-limiting growth of ZnO films on (0 0 0 1) sapphire substrates by atomic layer deposition at low temperatures using diethyl-zinc and nitrous oxide

Atomic layer deposition (ALD) of zinc oxide (ZnO) films on (0 0 0 1) sapphire substrates was conducted at low temperatures by using diethyl-zinc (DEZn) and nitrous oxide (N₂O) as precursors. It was found that a monolayer-by-monolayer growth regime occurred at 300 °C in a range of DEZn flow rates from 5.7 to 8.7 μmol/min. Furthermore, the temperature self-limiting process window for the ALD-grown ZnO films was also observed ranging from 290 to 310 °C. A deposition mechanism is proposed to explain how saturated growth of ZnO is achieved by using DEZn and N₂O. Transmission spectroscopic studies of the ZnO films prepared in the self-limiting regime show that the transmittances of ZnO films are as high as 80% in visible and near infrared spectra. Experimental results indicate that ZnO films with high optical quality can be achieved by ALD at low temperatures using DEZn and N₂O precursors.     

Temperature-dependent luminescence dynamics for ZnO thin films

The paper presents the photoluminescence investigation of zinc oxide thin films. A high quality ZnO films fabricated by dip-coating (sol–gel) method were grown on quartz wafers. The films with different thickness (number of layers) were annealed at different temperatures after the preparation process. It was found that high quality, transparent ZnO thin films could be produced on quartz substrates at relatively low annealing temperature (450–550  $^{\circ }\mathrm{C}$ ). The dependence of the ZnO thin film quality was studied by X-ray diffraction and atomic force microscopy techniques. Optical properties were investigated by classic and time-resolved photoluminescence (TRPL) measurements. Photoluminescence spectra allowed us to estimate energy of the free excitons, bond excitons and their longitudinal optical (LO) phonon replicas as a function of the annealing temperature. An innovative TRPL technique let us precisely measure the decay time of the free- and bond excitons’ in the real time. TRPL measurements as a function of temperature reveal a biexponential decay behavior with typical free/bound exciton decay constants of 970/5310 ps for the as-grown sample and 1380/5980 ps after annealing process. Presented spectra confirm high structural and optical quality of investigated films. We proved that the thermal treatment improve both optical and structural quality and extend the photoluminescence’s lifetimes. The obtained experimental results are important for identification of exciton’s peaks and their LO phonon replicas for the investigated ZnO films.     

Zinc Oxide Thin Films for Memristive Devices: A Review

Zinc Oxide (ZnO) thin films have been addressed as promising candidates for the fabrication of Resistive Random Access Memory devices, which are alternative to conventional charge-based flash memories. According to the filamentary conducting model and charge trapping/detrapping theory developed in the last decade, the memristive behavior of ZnO thin films is explained in terms of conducting filaments formed by metallic ions and/or oxygen vacancies, and their breaking through electrochemical redox reactions and/or recombination of oxygen vacancies/ions. A comparative review of the memristive properties of ZnO thin films grown by sputtering, atomic layer deposition (ALD), pulsed laser deposition (PLD), and sol-gel methods is here proposed. Sputtered ZnO thin films show promising resistive switching behaviors, showing high on/off ratios (10–10⁴), good endurance, and low operating voltages. ALD is also indicated to be useful for growing conformal ZnO layers with atomic thickness control, resulting in important resistive switching characteristics, such as relatively high on/off ratios and low operating voltages. High insulating epitaxial ZnO thin films can be obtained by PLD, showing reliable switching properties at low voltages and with good retention. On the contrary, the sol-gel approach generally results in ZnO thin films with poor resistive switching behaviors. Nevertheless, thin films derived from ZnO NPs show improved switching performances, with higher on/off ratios and lower operating voltages. Independently of the synthetic approach, doped ZnO thin films exhibit better resistive switching behaviors than pristine ones, coupling a strong increase of the on/off ratio with a more stable switching response.     

射频辅助N掺杂ZnO薄膜的生长及其光电特性

在MOCVD设备中采用改进的射频辅助生长装置,通过裂解N2及N-Al共掺杂的方法进行ZnO的p型掺杂研究。通过二次离子质谱(SIMS)、X射线衍射(XRD)、原子力显微镜(AFM)、光致发光(PL)谱等方法分析了薄膜中N杂质的浓度,以及射频功率与晶体质量、表面形貌以及光学特性之间的关系,并与Al掺杂和N掺杂的ZnO薄膜进行对比。实验结果表明,N掺杂的浓度高达1020cm-3;N-Al共掺杂极大地增加了ZnO的成核速率,其主要原因是N离化所起的作用;N-Al共掺的ZnO薄膜显示出p型性质,而N掺杂的ZnO薄膜由于N原子处于非激活状态而呈现高阻,这说明N-Al共掺杂对ZnO中N原子的活化起到一定作用。