Optical Analysis of Nanocrystalline ZnO Films Coated on Porous Silicon by Radio Frequency (RF) Magnetron Sputtering

Zinc oxide thin films have been deposited onto porous silicon (PSi) substrates at high growth rates by radio frequency (RF) sputtering using a ZnO target. The advantages of the porous Si template are economical and it provides a rigid structural material. Porous silicon is applied as an intermediate layer between silicon and ZnO films and it contributed a large area composed of an array of voids. The nanoporous silicon samples were adapted by photo electrochemical (PEC) etching technique on n-type silicon wafer with (111) and (100) orientation. Micro-Raman and photoluminescence (PL) spectroscopy are powerful and non-destructive optical tools to study vibrational and optical properties of ZnO nanostructures. Both the Raman and PL measurements were also operated at room temperature. Micro-Raman results showed that the A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at around 522 and 530 cm^–1, re- spectively. PL spectra peaks are distinctly apparent at 366 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The peak luminescence energy in nanocrystalline ZnO on porous silicon is blue-shifted with regard to that in bulk ZnO (381 nm). The Raman and PL spectra pointed to oxygen vacancies or Zn interstitials which are responsible for the green emission in the nanocrystalline ZnO.     

Influence of Sb in synthesize of ZnO nanowire using sandwich type substrate in carbothermal evaporation method

The paper deals with synthesis of Sb doped ZnO nanowire by considering Si coated with Sb and Au as substrate using carbothermal evaporation method. The horizontally oriented Sb doped ZnO nanowires with a diameter of 1 μm synthesized at 900 °C, which is quite high as compared to the Pure ZnO nanowires generated without the influence of Sb at 900 °C. The nanowire synthesized at 900 °C showed a measurable lower angle of about 0.06° from XRD and suppression of A₁T and E₁(L0) modes in Raman spectroscopic, this confirms the incorporation of Sb in ZnO lattice. The strong exciton emission and weak deep-level emission from room temperature PL and Strong emission attributed to the radiant recombination from neutral-acceptor-bound exciton (A⁰X) peak accompanied by two strong and broad emission of donor acceptor pair (DAP) from low temperature PL, this confirms the use of Sb as an acceptor for ZnO.     

Photoluminescence and resonant Raman scattering in N-doped ZnO thin films

A combination of studies on photoluminescence and resonant Raman scattering in N-doped ZnO thin films were carried out at room temperature. In the photoluminescence spectra, a transformation of radiative recombination mechanism from free-exciton to donor-acceptor-pair transition was observed. An enhancement of resonant Raman scattering processes as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed in the Raman spectra. Also, the nature of the 1LO phonon underwent a transformation from a pure A₁(LO) mode to a quasimode with mixed A₁ and E₁ symmetry. The underlying mechanisms accounting for the influences of N doping on the optical properties of ZnO were related to the incorporation of extrinsic defects in the crystal lattice.     

Cesium doped and undoped ZnO nanocrystalline thin films: a comparative study of structural and micro‐Raman investigation of optical phonons

Undoped and cesium‐doped zinc oxide (ZnO) thin films have been deposited on sapphire substrate (0001) using the sol–gel method. Films were preheated at 300 °C for 10 min and annealed at 600 and 800 °C for 1 h. The grown thin films were confirmed to be of wurtzite structure using X‐ray diffraction. Surface morphology of the films was analyzed using scanning electron microscopy. The photoluminescence (PL) spectra of ZnO showed a strong ultraviolet (UV) emission band located at 3.263 eV and a very weak visible emission associated with deep‐level defects. Cesium incorporation induced a blue shift of the optical band gap and quenching of the near‐band‐edge PL for nanocrystalline thin film at room temperatures because of the band‐filling effect of free carriers. A shift of about 10–15 cm⁻¹ is observed for the first‐order longitudinal‐optical (LO) phonon Raman peak of the nanocrystals when compared to the LO phonon peak of bulk ZnO. The UV resonant Raman excitation at RT shows multiphonon LO modes up to fifth order. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and optical properties of single crystalline GaN nanorods with a rectangular cross-section

GaN nanorods were synthesized from the reaction of a Ga/Ga₂O₃ mixture with NH₃ on Si substrates by chemical vapor deposition. The synthesized products were characterized by scanning and transmission electron microscopy, X-ray diffraction, photoluminescence and Raman spectroscopy. The nanorods are highly single crystalline and possess uniform smooth surfaces. PL revealed only a strong emission at 3.268 eV, ascribed to free exciton (FX) transitions, at room temperature; while the well-known yellow luminescence band centered at 2.2-2.3 eV was not detected. Four first-order phonon modes, corresponding to the A₁(TO), E₁(TO), E₂(high), and A₁(LO) at ∼531, 554, 564, and 721 cm⁻¹, respectively, were observed by Raman backscattering. The red-shift of the FX emission peak and the down-shifts of the Raman modes by a few wave numbers are attributed to the presence of tensile strain inside GaN nanorods.     

The optical properties of high quality ZnO/ZnMgO quantum wells on Si(111) substrates

The ZnO/Zn_0.85Mg_0.15O multiple quantum wells (MQWs) were fabricated on Si(111) substrates by plasma-assisted molecular beam epitaxy (P-MBE) using ZnMgO as buffer layers. The RHEED images indicated that the MQWs were of high quality. The free exciton (FE) emission line originated from the well region and its phonon replicas (FE-1LO, FE-2LO and FE-3LO) were observed in the 86 K photoluminescence (PL) spectrum. Blueshift of the FE line in the MQW sample as compared to that in the ZnO bulk was found at temperatures as high as room temperature. Time-resolved PL study on the FE line showed a fast lifetime of 140 ps. The high quality of the MQW structure was revealed by the observation of the quantum-confinement-induced blueshift and shortened lifetime of the FE emission.     

Multiphonon resonant Raman scattering in N‐doped ZnO

Multiphonon resonant Raman scattering in N‐doped ZnO films was studied, and an enhancement of the resonant Raman scattering process as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed at room temperature. The resonant Raman scattering intensity of the 1LO phonon in N‐doped ZnO appears three times as strong as that of undoped ZnO, which mainly arises from the defect‐induced Raman scattering caused by N‐doping. The nature of the 1LO phonon at 578 cm⁻¹ is interpreted as a quasimode with mixed A₁ and E₁ symmetry because of the defects formed in the ZnO lattice. In addition, the previously neglected impurity‐induced two‐LO‐phonon scattering process was clearly observed in N‐doped ZnO. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of substrate temperature on the growth of pulsed-laser deposited ZnO nanostructures

We report on the growth of highly c-axis-oriented ZnO nanostructures by pulsed laser deposition technique without using any catalyst. The full-width-at-half-maximum of (002) peak decreased with an increase in substrate temperature. However, a dip at 150 °C is attributed to the contribution from both the small- and large-size particles. FE-SEM images show that the increase in substrate temperature results in the formation of larger particles. Photoluminescence emission is observed both from near band edge as well as defect-related states for all the nanostructures. The presence of E ₂(low) and E ₂(high) Raman mode intensity and respective increase in the intensity with substrate temperature indicates better crystallinity. Both PL and Raman spectra indicate that A ₁(LO) mode may arise due to the defect related to interstitial zinc.     

Near infrared to UV dielectric functions of Al doped ZnO films deposited on c-plane sapphire substrate using pulsed laser deposition

Transparent conducting polycrystalline Al-doped ZnO (AZO) films were deposited on sapphire substrates at substrate temperatures ranging from 200 to 300 °C by pulsed laser deposition (PLD). X-ray diffraction measurement shows that the crystalline quality of AZO films was improved with increased substrate temperature. The electrical and optical properties of the AZO films have been systematically studied via various experimental tools. The room-temperature micro-photoluminescence (µ-PL) spectra show a strong ultraviolet (UV) excitonic emission and weak deep-level emission, which indicate low structural defects in the films. A Raman shift of about 11 cm⁻¹ is observed for the first-order longitudinal-optical (LO) phonon peak for AZO films when compared to the LO phonon peak of bulk ZnO. The Raman spectra obtained with UV resonant excitation at room temperature show multi-phonon LO modes up to third order. Optical response due to free electrons of the AZO films was characterized in the photon energy range from 0.6 to 6.5 eV by spectroscopic ellipsometry (SE). The free electron response was expressed by a simple Drude model combined with the Cauchy model are reported.     

Photoluminescence properties of nitrogen-doped ZnO films deposited on ZnO single crystal substrates by the plasma-assisted reactive evaporation method

Photoluminescence (PL) spectra of nitrogen-doped ZnO films (ZnO:N films) grown epitaxially on n-type ZnO single crystal substrates by using the plasma-assisted reactive evaporation method were measured at 5 K. In PL spectra, free exciton emission at about 3.375 eV was very strong and emissions at 3.334 and 3.31 eV were observed. These two emissions are discussed in this paper. The nitrogen concentration in ZnO:N films measured by secondary ion mass spectroscopy was 10^19-20 cm⁻³. Current-voltage characteristics of the junction consisting of an n-type ZnO single crystal substrate and ZnO:N film showed good rectification. Also, ultraviolet radiation and visible light were emitted from this junction under a forward bias at room temperature. It is therefore thought that ZnO:N films have good crystallinity and that doped nitrogen atoms play a role as acceptors in ZnO:N films to form a good pn junction. From these phenomena and the excitation intensity dependency of PL spectra, emissions at 3.334 and 3.31 eV were assigned to neutral acceptor-bound exciton (A⁰X) emission and a donor-acceptor pair (DAP) emission due to doped nitrogen, respectively.     

高质量ZnO及BeZnO薄膜的发光性质

用分子束外延设备插入缓冲层在c面蓝宝石上生长得到高质量ZnO和BeZnO薄膜。XRD测试显示薄膜具有六方结构和c轴取向,并具有良好的晶体质量,其中ZnO薄膜的半高宽仅为108 arcsec,Be_xZn_1-xO薄膜的半高宽小于600 arcsec。对ZnO和BeZnO薄膜的拉曼光谱进行对比研究发现,随着Be元素的掺入,A₁(LO)、A₁(2LO)声子模频率往大波数方向移动,并且首次发现了与Be元素掺杂有关的局域振动模。利用变温光致发光光谱研究了薄膜的发光性质,结果显示ZnO薄膜室温光致发光只出现一个紫外发发光峰(378 nm),而低温光谱(80 K)则出现了很强的自由激子发光峰。随着温度的升高,束缚激子发光逐渐湮灭向自由激子发光转变,并且峰值位置红移。相对于ZnO薄膜,BeZnO薄膜的紫外发光主峰位置蓝移,并且由于Be元素的掺入导致薄膜晶体质量下降,在低温(80 K)光致发光光谱中没有出现强的自由激子发光峰。另外,在低温光致发光及拉曼光谱中,主峰位置在100~200 K之间有局部最大值,推测为由于合金晶格热膨胀系数失配而引起的应力效应。     

磁控溅射制备ZnO薄膜的受激发射特性的研究

用射频磁控反应溅射法在二氧化硅衬底上制备ZnO薄膜。得到了在不同温度下ZnO薄膜的吸收与光致发光。观测到了纵光学波 (LO)声子吸收峰与自由激子吸收峰 ;室温 (30 0K)下 ,PL谱中仅有自由激子发光峰。这些结果证实了ZnO薄膜具有较高的质量。探讨了变温ZnO薄膜的发光特性。研究了ZnO薄膜的受激发射特性。     

Temperature dependence of excitonic luminescence from nanocrystalline ZnO films

The properties of the excitonic luminescence for nanocrystalline ZnO thin films are investigated by using the dependence of excitonic photoluminescence (PL) spectra on temperature. The ZnO thin films are prepared by thermal oxidation of ZnS films prepared by low-pressure metalorganic chemical vapor deposition (LP-MOCVD) technique. The X-ray diffraction (XRD) indicates that ZnO thin films have a polycrystalline hexagonal wurtzite structure with a preferred (0 0 2) orientation. A strong ultraviolet (UV) emission peak at 3.26 eV is observed, while the deep-level emission band is barely observable at room temperature. The strength of the exciton-longitudinal-optical (LO) phonon coupling is deduced from the temperature dependence of the full-width at half-maximum (FWHM) of the fundamental excitonic peak, decrease in exciton-longitudinal-optical (LO) phonon coupling strength is due to the quantum confinement effect.     

Annealing-induced changes of the 3.31 eV emission in ZnO nanorods

The effect of annealing on the 3.31 eV (A line) emission in ZnO nanorods is studied in detail by temperature-dependent photoluminescence (PL). Annealing results in obvious changes in peak energy and lineshape of the A line, indicating different luminescence origin in the as-grown and annealed ZnO nanorods. In the as-grown nanorods, the A line is a result of competition between free-to-neutral acceptor (FA) transition and the first longitude optical phonon replica of free exciton (FX-1LO) recombination. While for the annealed nanorods, FA transition disappears and the A line is attributed to FX-1LO only. In combination with trace impurity analysis, the results allow us to conclude that the acceptor involved in the FA transition is stacking faults rather than unintentional acceptor impurities.     

Photoluminescence study of ZnO nano-islands

ZnO nano-islands, with much more uniform size, have been grown through two-step method by metal organic chemical vapor deposition (MOCVD). The room temperature band-edge UV emission intensity of nano-islands was usually undetectable or much smaller than that of thin film. Photoluminescence (PL) emission of those nano-islands shows the high intensity nearly as that of ZnO thin film, which is great different from previous reports. By meaningfully analyzing both PL and growth condition of those three samples (bulk ZnO wafer, nano-islands and film), neutral-donor-bound-exciton (D⁰X) emission observed on ZnO nano-islands sample is eventually attributed to hydrogen and aluminum, respectively. The abnormal phenomenon of nano-islands PL intensity has been explained by the point of zinc vacancies (V_Zn) complex defects. It is considered to govern the nonradiative combination and lead enhanced intensity of UV emission in ZnO nano-islands.     

Studies of luminescence properties of ZnO and ZnO:Zn nanorods prepared by solution growth technique

Pyramidal ZnO nanorods with hexagonal structure having c-axis preferred orientation are grown over large area silica substrates by a simple aqueous solution growth technique. The as-grown nanorods were studied using XRD, SEM and UV-vis photoluminescence (PL) spectroscopy for their structural, morphological and optical properties, respectively. Further, the samples have also been annealed under different atmospheric conditions (air, O₂, N₂ and Zn) to study the defect formation in nanorods. The PL spectra of the as-grown nanorods show narrow-band excitonic emission at 3.03 eV and a broad-band deep-level emission (DLE) related to the defect centers at 2.24 eV. After some mild air annealing at 200 °C, fine structures with peaks having energy separation of ∼100 meV were observed in the DLE band and the same have been attributed to the longitudinal optical (LO) phonon-assisted transitions. However, the annealing of the samples under mild reducing atmospheres of N₂ or zinc at 550 °C resulted in significant modifications in the DLE band wherein high intensity green emission with two closely spaced peaks with maxima at 2.5 and 2.7 eV were observed which have been attributed to the V_O and Zn_i defect centers, respectively. The V-I characteristic of the ZnO:Zn nanorods shows enhancement in n-type conductivity compared to other samples. The studies thus suggest that the green emitting ZnO:Zn nanorods can be used as low voltage field emission display (FED) phosphors with nanometer scale resolution.     

m面蓝宝石上ZnO/ZnMgO多量子阱的制备及发光特性研究

利用等离子体辅助分子束外延设备(P-MBE)在m面的蓝宝石(m-Al₂O₃)衬底上制备了ZnO/Zn_0.85Mg_0.15O多量子阱.反射式高能电子衍射谱(RHEED)图样的原位观察表明,多量子阱结构是以二维模式生长的.从光致发光谱中可以看到ZnO/Zn_0.85Mg_0.15O多量子阱在室温仍具有明显的量子限域效应.在290 K时阱宽为3 nm的ZnO/Zn_{0.85关键词： 等离子体辅助分子束外延 ZnO多量子阱 光致发光}     

Effect of the annealing environment on the optical properties of ZnO/GaAs grown by MOCVD

The optical properties of ZnO grown on (1 0 0) GaAs substrate using metalorganic chemical vapor deposition are investigated by photoluminescence (PL) spectroscopy. Postgrowth annealing in nitrogen and oxygen was performed for different times and temperatures in order to incorporate As from the substrate into the ZnO thin films. The PL spectra of the samples annealed in different ambients reveal that the effect of As diffusion into the ZnO thin films is more pronounced when the annealing is performed in oxygen at 550 °C. The 11 K PL spectra show the appearance of a transition at ∼3.35 eV after annealing in oxygen at 550 °C for 1 h. A further increase in the annealing temperature leads to the disappearance of this line, while for annealing times longer than 2 h at 550 °C, it is no longer prominent. The increase in intensity of this new transition is also accompanied by the enhancement of radiative centers related to structural defects, such as the stacking fault-related transition at 3.31 eV and the Y-line. Temperature dependent PL illustrates the excitonic nature of the new transition at ∼3.35 eV, which is therefore assigned to (A⁰, X) transition, where the acceptor is possibly the 2V_Zn-As_Zn complex, with an activation energy E_A in the range of 160-240 meV. Furthermore, the enhancement of the radiative centers related to structural defects is regarded as evidence that As atoms tend to segregate in the vicinity of structural defects to relieve local strain.     

Strong ultraviolet emission from zinc oxide thin films prepared by electrophoretic deposition

In this paper, we report a simple and efficient method to prepare high-quality nanocrystalline ZnO films by electrophoretic deposition. Absorption spectrum and transmission electron microscope image indicated that the average size of ZnO nanoparticles is about 9.5 nm. A strong ultraviolet emission peak at 384 nm is observed and the deep-level emission band is barely observed at room temperature. X-ray diffraction pattern revealed that the ZnO film has a polycrystalline hexagonal wurtzite structure. The Raman spectrum showed a typical resonant multi-phonon process within the ZnO film. The frequency shift of 1 LO phonon was about 583 cm⁻¹.     

Photoluminescence and Raman spectra of the ordered vacancy compound CuGa5Se8

We studied the photoluminescence (PL) and Raman properties of the ordered defect compound CuGa₅Se₈. Twelve peaks were detected from the room-temperature Raman spectra with the A₁ mode around 160 cm⁻¹. Due to the stress in the polycrystalline thin film the corresponding frequencies of the Raman modes of a CuGa₅Se₈ single crystal were slightly shifted. One broad asymmetric PL band at 1.788 and 1.765 eV was observed at 10 K in the PL spectra of CuGa₅Se₈ single crystal and polycrystalline layer, respectively. The temperature and laser power dependencies of the PL spectra were also studied. The shape and properties of the PL band assure the presence of potential fluctuations and the analyses of the PL data suggest that the emission is due to band-to-tail (BT) or band-to-impurity (BI) recombination.