Lasing with guided modes in ZnO nanorods and nanowires

A vertically arranged nearly parallel array of ZnO nanorods and randomly oriented nanowires has been grown by low pressure chemical vapor deposition (CVD) on silica substrates and on stainless steel gauze woven from a wire with a diameter of 40 μm, respectively. The quality of the produced material is high enough to act as a gain medium for stimulated emission in the ultraviolet spectral region. Multiple sharp lasing peaks were realized from single hexagonal nanorods and arrays of hexagonal ZnO nanorods. The lasing peaks display successive onset and saturation with increasing excitation power density and fit well the expected resonance spectrum of guided modes in hexagonal nanorods. The behavior of lasing spectra from shot to shot of pumping in randomly oriented nanowires along with the independence of the lasing threshold on the excitation spot area suggest that the emission spectrum results from the superposition of lasing modes in individual nanowires, rather than from random lasing due to photon coherent scattering.     

Multi-photon-pumped stimulated emission from ZnO nanowires: A time-resolved study

In this work, we study temporal evolution of multi-photon-pumped stimulated emission from ZnO nanowires. In addition to second harmonic generation, ultraviolet stimulated emission is observed in ZnO nanowires under femtosecond pulse excitation at 800 nm. Sharp emission peaks appear when excitation flux reaches a threshold of 80 mJ/cm², which can be interpreted as lasing action in self-formed nanowire microcavities. Temporal evolution of the emission captured by Kerr shutter technique shows strong excitation-power dependence. The dynamic trace of stimulated emission exhibits a fast decay with a lifetime about 4.5 ps at intermediate excitation (∼100 mJ/cm²) and a lifetime about 2 ps at high excitation (>160 mJ/cm²). The difference in the lifetime can be attributed to different gain mechanisms related to excitonic interaction and electron-hole plasma, respectively.     

Stimulated emission from trapped excitons in SnO2 nanowires

The pump fluence dependent photoluminescence (PL) spectra of SnO₂ nanowires were investigated, which were synthesized with a high-temperature chemical reduction method. The integrated intensity of the narrower peak at 3.2 eV experiences a strong superlinear dependence on the pump fluence, and the narrowest width of the sharp peak is only 19 meV. Moreover, under high excitation fluence, an ultrafast decay time (less than 20 ps) appears in the time-resolved PL spectra. The emission of these SnO₂ nanowires shows strong apparent stimulated emission behaviors although the SnO₂ is a dipole forbidden direct gap semiconductor. The stimulated emission should relate to the localized islands on the surface of nanowire, which was observed through the high resolution transmission electron microscopy (HRTEM) image. The giant-oscillator-strength effect of bound exciton generated from the localized islands was considered to induce the stimulated emission of SnO₂ nanowires.     

Multiphoton route to ZnO nanowire lasers

With intense femtosecond laser excitation, multiphoton absorption-induced stimulated emission and laser emission in ZnO bulk crystal and nanowires have been demonstrated at room temperature. UV-stimulated emission peaks appeared in both bulk crystal and nanowires when the excitation exceeded certain thresholds, and a sharp lasing peak with a linewidth of ~0.5 nm was observed from ZnO nanowires. The emission properties were attributed to the band-edge emission of the recombination of carriers excited by two- and three-photon absorption processes in the wide-bandgap semiconductor.     

纳米结构ZnO晶体薄膜室温紫外激光发射

文章综述了纳米结构的氧化锌半导体薄膜在室温下自由激子的自发辐射以及由自由激子引起的受激发射的特性，阐述了在不同激发密度下室温紫外受激发射的机理．纳米结构氧化锌半导体薄膜是用激光分子束外延(L-MBE)技术生长在蓝宝石衬底上的．薄膜由密集而规则排列的纳米尺度的六角柱组成．这些纳米六角柱起着限制激子运动的作用，激子的量子尺寸效应，使激子的跃迁振子强度大幅度增强．同时六角柱之间的晶面组成了一个天然的激光谐振腔．室温下用三倍频的YAG脉冲激光激发，可从这些纳米结构的氧化锌薄膜中观测到很强的紫外激光发射．研究发现，在中等激发密度下，紫外受激发射是由于激子与激子间碰撞而引起的辐射复合．在高密度激发条件下，由于激子趋于离化，紫外受激发射主要由电子-空穴等离子体的辐射复合引起．由于纳米结构中激子的跃迁振子增强效应，在室温下测量到的光学增益高达320cm^-1，这比在同样条件下测量到的块状氧化锌晶体的光学增益要高一个量级以上．与传统的电子-空穴等离子体激光辐射相比，激子引起的受激发射可在较低的激发密度条件下实现．这在实际应用上很有价值．     

Time-resolved photoluminescence on the stimulated emission in polycrystalline ZnO nanoparticles

The detailed room temperature stimulated emission including its optical characteristics from ZnO nanoparticles, which were prepared by a homogenous precipitation method, has been investigated by the time-resolved spectroscopy. The light emission originates from a free exciton recombination at a lower excitation level; the amplified spontaneous emission appears at a moderate excitation level, in which the threshold excitation intensity is 0.65 GW cm⁻². The resonant stimulated emission was observed in ZnO nanoparticles at a higher excitation intensity. Also, the emission lifetime is drastically reduced. Compared to the fluorescence decay curves, the time-resolved spectrum of the stimulated emission suggests the Gaussian-like decay time with only a few of picoseconds. The dynamic processes of lasing behavior and the characteristics of lasing emission in ZnO nanoparticles could provide the information on the crystal quality, the exciton and the lasing action in the particles.     

Guided mode lasing in ZnO nanorod structures

Quasi-two-dimensional arrays of nearly parallel hexagonal ZnO nanorods and a three-dimensional cylindrical microstructure consisting of ZnO nanorods have been grown by low pressure chemical vapor deposition (CVD) and carbothermal evaporation technologies, respectively. The technology ensures high optical quality of the produced nanostructures so as to act as a gain medium for stimulated emission in the ultraviolet spectral region in combination with high quality factor laser resonators. Multiple sharp lasing peaks were realized from the produced structures under nanosecond pulse optical excitation. The lasing peaks display successive onset and saturation with increasing excitation power density in accordance with the lasing behavior of guided modes in ZnO nanorods. The produced structures are expected to find applications in integrated nanoscale optoelectronics, photonics, and sensor technologies.     

Abnormal blueshift of UV emission in single-crystalline ZnO nanowires

Single-crystalline ZnO nanowires (NWs) were synthesized by a facile vapor transport method. The good orientation and high crystal quality were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and high-resolution transmission electron microscope (HRTEM) measurements. Excitation-power-dependence photoluminescence spectra of ZnO NWs show that the UV emission displayed an evident blueshift with increasing excitation power and the corresponding energy shift might be as large as 10 meV. This anomalous phenomenon correlates to the band bending level caused by the surface built-in electric field due to the existence of substantial oxygen vacancies. By increasing the excitation power, the enhanced neutralization effect near the surface will reduce the built-in electric field and lead to a reduction of band bending which triggers the blueshift of the UV emission.     

利用金作为反射镜的氧化锌纳米棒光泵激光

通过水热法在溅射了一层金的Si片上生长了ZnO纳米棒。实验观察到ZnO纳米棒的室温光致发光谱中出现了强的紫外发射峰,同时还伴随有弱的缺陷相关的发射,这表明通过该种方法生长的ZnO纳米棒晶体质量较好。同时,通过光泵浦也观察到了ZnO纳米棒中的激光发射。当激发光功率密度超过阈值,且进一步增加时则出现多个发射峰,其积分强度随着激发功率密度的增大呈非线性增长,进一步表明存在受激发射。利用金属层作为反射镜可以进一步降低损耗,从而达到降低阈值的目的。     

Photoluminescence and time-resolved photoluminescence of star-shaped ZnO nanostructures

Optical properties of star-shaped ZnO nanostructures were studied. The temperature-dependent photoluminescence (PL) was examined up to fourth-order longitudinal optical (LO) phonon assisted emissions of free excitons and confirmed that the nature of the room temperature PL in ZnO is 1-LO phonon assisted emission of free excitons. Low threshold ultraviolet stimulated emissions (SE) were obtained for our powder samples at room temperature. Picosecond time-resolved PL measurements detected a bi-exponential decay behavior which is strongly dependent on the excitation intensity: the slow decay term decreased faster than the fast decay term as the excitation intensity increased and the emission decays were dominated by the fast one. We also found that the emission decays decreased super-linearly before the appearance of the SE. This behavior may be used to deduce the threshold of SE or lasing.     

Room-temperature laser emission of ZnO nanowires explained by many-body theory

Are excitons involved in lasing in ZnO nanowires or not? Our recently developed and experimentally tested quantum many-body theory sheds new light on this question. We measured the laser thresholds and Fabry-Pérot laser modes for three radically different excitation schemes. The thresholds, photon energies, and mode spacings can all be explained by our theory, without invoking enhanced light-matter interaction, as is needed in an earlier excitonic model. Our conclusion is that lasing in ZnO nanowires at room temperature is not of excitonic nature, as is often thought, but instead is electron-hole plasma lasing.     

垂直氧化锌纳米线中的激射现象

通过水热的方法以退火0.5 h的ZnO薄膜作为籽晶,得到垂直的ZnO纳米线.在X射线衍射谱中,除了Si的(400)衍射峰以外,只观察到了ZnO的(002)衍射峰.室温光致发光谱中出现了强的紫外发射峰,同时也伴随着弱的缺陷相关的发射.这些数据表明垂直的ZnO纳米线序列有着较好的晶体质量.同时,通过光泵浦也观察到了ZnO纳...     

高分子软模板法自组装生长ZnO纳米线及其光学性能

采用自组装技术,利用均聚极性高分子(聚丙烯酰胺、聚乙烯醇等)长分子链作为自组装模板在半导体硅衬底上自组装生长出ZnO纳米线。采用扫描电镜(FE-SEM)和透射电镜(HRTEM)对样品的表面形貌和结构分析表征的结果表明,ZnO纳米线直径约50~80nm、长度大于4μm,具有六方纤锌矿单晶结构,且沿c轴方向择优取向生长。采用室温下光致发光(PL)谱和紫外吸收(UV)光谱对制得的ZnO纳米线的光学性能研究表明,其PL光谱上有较强的紫外发射和较弱的蓝光发射,UV吸收光谱表明样品在紫外区有强的宽带吸收,且随着纳米线粒径的减小,吸收峰出现了蓝移现象。研究探讨了高分子诱导ZnO纳米线自组装定向生长机制、发光机理及其与工艺条件的内在联系。     

ZnO粉末中无序激射现象时间分辨的研究

采用抽运-探测时间分辨方法实验研究了半导体材料ZnO纳米颗粒粉末中的无序激射现象.在2 67nm激光的抽运下，通过精确控制抽运光的能量和样品表面的抽运面积，获得了宽度小于1n m的单模无序激射光谱和多峰的多模无序激射光谱.时间分辨的抽运-探测结果显示，此时样 品的上能级寿命仅为几个皮秒，证明了ZnO粉末的单模无序光谱是受激辐射的结果. 关键词： 高散射介质 多重散射 抽运-探测 无序激射     

Aligned growth of ZnO nanowires by NAPLD and their optical characterizations

Not only vertically aligned ZnO nanowires but also horizontally aligned ZnO nanowires have been successfully grown on the annealed (0 0 0 1) c-cut and (1 1 2 0) a-cut sapphire substrates, respectively using catalyst-free nanoparticle-assisted pulsed-laser ablation deposition (NAPLD). The as-synthesized ZnO nanowires exhibit an ultraviolet emission at around 390 nm and the absent green emission under room temperature. The single ZnO nanowire was collected in the electrode gap by dielectrophoresis (DEP). Under the optical pumping, the single ZnO nanowire exhibited UV emission at around 390 nm with several sharp peaks whose energy spacings are almost constant, which greatly differs from the broad UV emission of the film with many nanowires, suggesting ZnO nanowires as candidates for laser media. The single ZnO nanowire showed polarized photoluminescence (PL). The as-synthesized ZnO nanowires could find many interesting applications in short-wavelength light-emitting diode (LED), laser diode and gas sensor.     

利用离子激发发光研究低温条件下ZnO发光行为EI北大核心CSCD

离子激发发光(Ions beam induced luminescence,IBIL)可以实时原位分析不同温度、不同离子辐照条件下材料内部点缺陷的演变行为。本文利用2 MeV H^(+)研究了300,200,100 K温度下ZnO单晶内部点缺陷发光及其随注量的演变行为。实验中发现ZnO深能级发射和近带边发射,结合Voigt分峰与XPS实验结果,确定红光(1.75 eV)与V_(Zn)相关,橙红光(1.95 eV)来自Zn_(i)到O_(i)跃迁;对于与V_(O)相关的绿光(2.10 eV),其红移可能由于温度降低导致更多电子由导带释放到Zn_(i)。峰中心位于3.10 eV和3.20 eV近带边发射分别来自于Zn_(i)到价带的跃迁和激子复合,红移原因分别为Zn_(i)附近局域化能级和带隙收缩。利用单指数公式对发光强度进行拟合,获得的衰减速率常数(f)可以表征缺陷的辐射硬度,对比发现深能级发射峰在200 K时辐射硬度最大,而近带边发射峰在300 K时辐射硬度最大。     

Multi-photon excitation in ZnO materials

A brief introduction on the advance in the fabrication technology of ZnO materials was given. Related research on the multi-photon excitation processes in several kinds of ZnO materials under intense pump conditions by fs pulses were reviewed. Stimulated emission properties in ZnO microtubes and nanowires have also been dealt with. Possible nonlinear effects that emerged under the extremely intense field were discussed.      

Effect of excitation intensity on fluorescence spectra in ZnO nanostructures and its origin

ZnO nanostructures with three kinds of morphologies, namely, tetrapod-, rod-, and sheet-like shape, are synthesized by chemical vapor deposition, conventional solution-phase, and hydrothermal methods, respectively. The fluorescence measurements display that the spectra of these nanostructures exhibit similar unexpected change laws with the altering excitation intensity. It is observed that when the excitation intensity increases, for the green emission band, the peak position shows a small blue-shift, the width turns broader, and the intensity grows first stronger and then weaker; for the UV emission band, the peak position exhibits a significant red-shift, and the width and intensity have the similar behaviors with those of the green band. Additionally, the relative intensity of green emission to UV emission decreases gradually. It is clarified that the origin of this abnormal phenomenon is ascribed to the local laser heating effect and the high sensitivity of nanostructures to this heating effect. Supported by the National Basic Research Program of China (Grant No. 2005CB623603)     

Effect of growth temperature on the ZnO nanowires prepared by thermal heating of Zn powders

ZnO nanowires have been synthesized by heating Zn powders under nitrogen (N₂) gas atmosphere. The influence of the growth temperature on the morphology, structure, and photoluminescence (PL) properties of ZnO nanowires has been investigated. At the higher-temperature growth process, thinner nanowires have been obtained. Interestingly, it is observed that the variation of growth temperature has significantly affected the photoluminescence spectra of the ZnO nanowires, showing an enhancement in the relative intensity of the green to UV emission bands with the increase of the growth temperature. In addition, the oxygen sensing properties of the as-synthesized ZnO nanowires were tested.     

Strong violet luminescence from ZnO nanocrystals grown by the low-temperature chemical solution deposition

The luminescence properties of zinc oxide (ZnO) nanocrystals grown from solution are reported. The ZnO nanocrystals were characterized by scanning electron microscopy, X-ray diffraction, cathodo- and photoluminescence (PL) spectroscopy. The ZnO nanocrystals have the same regular cone form with the average sizes of 100-500 nm. Apart from the near-band-edge emission around 381 nm and a weak yellow-orange band around 560-580 nm at 300 K, the PL spectra of the as-prepared ZnO nanocrystals under high-power laser excitation also showed a strong defect-induced violet emission peak in the range of 400 nm. The violet band intensity exhibits superlinear excitation power dependence while the UV emission intensity is saturated at high excitation laser power. With temperature raising the violet peak redshifts and its intensity increases displaying unconventional negative thermal quenching behavior, whereas intensity of the UV and yellow-orange bands decreases. The origin of the observed emission bands is discussed.