Dependency of photoluminescence from SiO_2 thin films containing Si_(1-x)Ge_x quantum dots on Ge/Si doping ratio

SiO2 thin films containing Si1-xGex quantum dots （QDs） are prepared by ion implantation and annealing treatment. The photoluminescence （PL） and microstructural properties of thin films are investigated. The samples exhibit strong PL in the wavelength range of 400-470 nm and relatively weak PL peaks at 730 and 780 nm at room temperature. Blue shift is found for the 400-nm PL peak, and the intensity increases initially and then decreases with the increase of Ge-doping dose. We propose that the 400-470 nm PL band originates from multiple luminescence centers, and the 730- and 780-nm PL peaks are ascribed to the Si=O and GeO luminescence centers.     

SiO/SiO_2超晶格结构界面发光的研究

利用热蒸发技术在硅衬底上制备了层厚不同的SiO/SiO2超晶格样品.对其光致发光谱进行研究发现,随着SiO/SiO2超晶格中SiO层厚度的增加,发光峰在400～600 nm之间移动.研究表明,样品的发光中心来自于SiO/SiO2界面处的缺陷发光(界面态发光).即在样品沉积的过程中,在SiO/SiO2的界面处由于晶格的不连续性,会形成大量的Si-O悬挂键,这些悬挂键本身相互结合可以形成一定数量的缺陷,同时由于O原子容易脱离Si原子的束缚而产生扩散,因此,这些悬挂键可以与扩散的O原子结合,随着SiO层厚度的增加,在SiO/SiO2的界面处先后出现WOB(O3<≡Si-O-O·),NOV(O3≡Si-Si≡O3),E'中心(O≡Si·),NBOHC(O3≡Si-O·)等缺陷,这些缺陷在SiO层厚度增大的过程中对发光先后起到主导作用,从而使得发光峰产生红移.     

退火温度对富硅氮化硅薄膜发光特性和结构的影响

采用直流等离子体增强化学气相沉积(PECVD)法在(100)单晶硅片表面生长富硅氮化硅薄膜,研究了不同的退火温度对氮化硅薄膜发光性质和结构的影响。研究发现,随着退火温度的升高,氮化硅薄膜的发光强度逐渐减弱,发光是由缺陷能级引起的,在900 ℃时荧光基本消失。XPS测试表明,在N₂氛围900 ℃下退火,氮化硅薄膜中未有硅相析出,故未表现出硅量子点的发光。FTIR测试也为PL结论提供了一定的证据。     

Room temperature photoluminescence from amorphous silicon nanoparticles in SiOx thin films

Amorphous SiO_x thin films with four different oxygen contents (x=1.15, 1.4, 1.5, and 1.7) have been prepared by thermal evaporation of SiO in vacuum and then annealed at 770 or 970 K in argon for various times ?40 min. The influence of annealing conditions and the initial film composition on photoluminescence (PL) from the annealed films has been explored. Intense room temperature PL has been observed from films with x?1.5, visible with a naked eye. It has been shown that PL spectra of most samples consists of two main bands: (i) a ‘green’ band centered at about 2.3 eV, whose position does not change with annealing conditions and (ii) an ‘orange-red’ band whose maximum moves from 2.1 to 1.7 eV with increasing annealing time and temperature and decreasing initial oxygen content. These observations have been explained assuming recombination via defect states in the SiO_x matrix for the first band and emission from amorphous Si nanoparticles for the second one.     

Photoluminescence properties of powder and pulsed laser-deposited PbS nanoparticles in SiO2

Thin films of lead sulfide (PbS) nanoparticles embedded in an amorphous silica (SiO₂) host were grown on Si(1 0 0) substrates at different temperatures by the pulsed laser deposition (PLD) technique. Surface morphology and photoluminescence (PL) properties of samples were analyzed with scanning electron microscopy (SEM) and a 458 nm Ar⁺ laser, respectively. The PL data show a blue-shift from the normal emission at ∼3200 nm in PbS bulk to ∼560-700 nm in nanoparticulate PbS powders and thin films. Furthermore, the PL emission of the films was red-shifted from that of the powders at ∼560 to ∼660 nm. The blue-shifting of the emission wavelengths from 3200 to ∼560-700 nm is attributed to quantum confinement of charge carriers in the restricted volume of nanoparticles, while the red-shift between powders and thin-film PbS nanoparticles is speculated to be due to an increase in the defect concentration. The red-shift increased slightly with an increase in deposition temperature, which suggests that there has been a relative growth in particle sizes during the PLD of the films at higher temperatures. Generally, the PL emission of the powders was more intense than that of the films, although the intensity of some of the films was improved marginally by post-deposition annealing at 400 °C. This paper compares the PL properties of powder and pulsed laser-deposited thin films of PbS nanoparticles and the effects of deposition temperatures.     

Interrelation between microstructure and optical properties of erbium-doped nanocrystalline thin films

Nanocrystalline silicon thin films codoped with erbium, oxygen and hydrogen have been deposited by co-sputtering of Er and Si. Films with different crystallinity, crystallite size and oxygen content have been obtained in order to investigate the effect of the microstructure on the photoluminescence properties. The correlation between the optical properties and microstructural parameters of the films is investigated by spectroscopic ellipsometry. PL response of the discussed structures covers both the visible wavelength range (a crystallite size-dependent photoluminescence detected for 5–6 nm sized nanocrystals embedded in a SiO matrix) and near IR range at 1.54 μm (Er-related PL dominating in the films with 1–3 nm sized Si nanocrystals embedded in a-Si:H). It is demonstrated that the different PL properties can be also discriminated on the basis of ellipsometric spectra.     

Effects of annealing temperature on the structural and photoluminescence properties of nanocrystalline ZrO2 thin films prepared by sol-gel route

Highly transparent nanocrystalline zirconia thin films were prepared by the sol-gel dip coating technique. XRD pattern of ZrO₂ thin film annealed at 400 °C shows the formation of tetragonal phase with a particle size of 13.6 nm. FT-IR spectra reveal the formation of Zr-O-Zr and the reduction of OH and other functional groups as the temperature increases. The transmittance spectra give an average transmittance greater than 80% in the film of thickness 262 nm. Photoluminescence (PL) spectra give intense band at 391 nm and a broad band centered at 300 nm. The increase of PL intensity with elevation of annealing temperature is related to reduction of OH groups, increase in the crystallinity and reduction in the non-radiative related defects. The luminescence dependence on defects in the film makes it suitable for luminescent oxygen-sensor development. The “Red shift” of excitation peak is related to an increase in the oxygen content of films with annealing temperature. The “Blue shift” of PL spectra originates from the change of stress of the film due to lattice distortion. The defect states in the nanocrystalline zirconia thin films play an important role in the energy transfer process.     

Preparation and characterization of Mg-doped ZnO thin films by sol-gel method

Undoped and Mg-doped ZnO thin films were deposited on Si(1 0 0) and quartz substrates by the sol-gel method. The thin films were annealed at 873 K for 60 min. Microstructure, surface topography and optical properties of the thin films have been measured by X-ray diffraction (XRD), atomic force microscope (AFM), UV-vis spectrophotometer, and fluorophotometer (FL), respectively. The XRD results show that the polycrystalline with hexagonal wurtzite structure are observed for the ZnO thin film with Mg:Zn = 0.0, 0.02, and 0.04, while a secondary phase of MgO is evolved for the thin film with Mg:Zn = 0.08. The ZnO:Mg-2% thin film exhibits high c-axis preferred orientation. AFM studies reveal that rms roughness of the thin films changes from 7.89 nm to 16.9 nm with increasing Mg concentrations. PL spectra show that the UV-violet emission band around 386-402 nm and the blue emission peak about 460 nm are observed. The optical band gap calculated from absorption spectra and the resistivity of the ZnO thin films increase with increasing Mg concentration. In addition, the effects of Mg concentrations on microstructure, surface topography, PL spectra and electrical properties are discussed.     

Influence of the temperature on the photoluminescence of silicon clusters embedded in a silicon oxide matrix

Amorphous silicon oxide thin films were prepared by co-evaporation of Si and SiO in ultra-high vacuum. Different compositions were obtained by changing the evaporation rate of silicon. After thermal annealing treatments, the dissociation of the silicon oxide in pure silicon and silicon dioxide leads to the formation of silicon clusters embedded in a silicon oxide matrix. Thus the samples were annealed to different temperatures up to 950°C. Depending on the annealing temperature and on the composition, different cluster sizes were obtained. The photoluminescence (PL) energy depends on the cluster size and a large range of wavelengths is obtained from 500 to 750 nm. The PL, attributed to a confinement effect of the electron–hole pairs in the silicon particles, is studied as a function of the temperature. It is demonstrated that the continuous decrease of PL intensity with the temperature from 77 to 500 K depends on the structure of the samples. For samples with well-separated clusters, the PL decreases rapidly with the temperature. For samples containing clusters separated by a small distance, the PL weakly depends on the temperature. No shift of the energy is observed. The results are discussed by taking into account the competition between the radiative recombination in the silicon clusters and the non-radiative escape of the carriers via a hopping mechanism.     

Band structure of silicon and germanium thin films based on first principles

In nanomaterials, optical anisotropies reveal a fundamental relationship between structural and optical properties, in which directional optical properties can be exploited to enhance the performance of optoelectronic devices. First principles calculation based on density functional theory(DFT) with the generalized gradient approximation(GGA) are carried out to investigate the energy band gap structure on silicon(Si) and germanium(Ge) nanofilms. Simulation results show that the band gaps in Si(100) and Ge(111) nanofilms become the direct-gap structure in the thickness range less than 7.64 nm and7.25 nm respectively, but the band gaps of Si(111) and Ge(110) nanofilms still keep in an indirect-gap structure and are independent on film thickness, and the band gaps of Si(110) and Ge(100) nanofilms could be transferred into the direct-gap structure in nanofilms with smaller thickness. It is amazing that the band gaps of Si~((1-x)/2)Ge~xSi~((1-x)/2)sandwich structure become the direct-gap structure in a certain area whether(111) or(100) surface. The band structure change of Si and Ge thin films in three orientations is not the same and the physical mechanism is very interesting, where the changes of the band gaps on the Si and Ge nanofilms follow the quantum confinement effects.     

Synthesis of Light-emitting Silicon Nanoparticles by Intense Pulsed ion-beam Esvaporation

Synthesis of photoluminescent Si nanoparticles has been successfully prepared using an intense pulsed ion-beam evaporation (IBE) technique in vacuum. Si nanoparticles are produced by the IBE method without any post-annealings. Photoluminescence (PL) mainly in blue range with a peak of 455 nm and a shoulder near 510 nm is observed in as-deposited Si nanoparticles at room temperature. The blue light emission is relatively stable with no noticeable change, as the samples have already stored in air more than 4 months. The observed PL does not fit the quantum confinement model, since a majority of particle size is around ~20 nm, estimated by SEM and XRD measurements. Moreover, hydrofluoric acid (HF) corrosion tests on the Si nanoparticles also indicate a correlation between the presence of the surface oxide layers and the PL. Oxide-related luminescence is likely the source of this blue light emission.     

Excitonic photoluminescence characteristics of amorphous silicon nanoparticles embedded in silicon nitride film

We have investigated the photoluminescence (PL) properties of amorphous silicon nanoparticles (a-Si NPs) embedded in silicon nitride film (Si-in-SiN_x) grown by helicon wave plasma-enhanced chemical vapor deposition (HWP-CVD) technique. The PL spectrum of the film exhibits a broad band constituted of two Gaussian components. From photoluminescence excitation (PLE) measurements, it is elucidated that the two PL bands are associated with the a-Si NPs and the silicon nitride matrix surrounding a-Si NPs, respectively. The existence of Stokes shift between PL and absorption edge indicates that radiative recombination of carriers occurs in the states at the surface of the Si NPs, whereas their generation takes place in the a-Si NPs cores and the silicon nitride matrix, respectively. The visible PL of the film originates from the radiative recombination of excitons trapped in the surface states. At decreasing excitation energy (E_ex), the PL peak energy was found to be redshifted, accompanied by a narrowing of the bandwidth. These results are explained by surface exciton recombination model taking into account there existing a size distribution of a-Si NPs in the silicon nitride matrix.     

Cathodoluminescence properties of silicon nanocrystallites embedded in silicon oxide thin films

Cathodoluminescence (CL) spectra for the Si nanocrystallites embedded in a matrix of silicon oxide films are measured at room temperature. The CL spectra consist of two principal bands whose peak energies are in a near-infrared (NIR) region (<1.6 eV) and in a blue region (2.6 eV), respectively. The spectral feature of the NIR CL band is similar to the corresponding PL spectra. The strong correlation between the presence of Si nanocrystallites and the formation of the NIR CL band are found as well as the PL spectrum. The peak energy of the blue CL band is slightly lower than that of the luminescence band originating from oxygen vacancies (≡Si–Si≡) in SiO₂. Therefore, the blue CL band is considered to come from Si_n clusters with n3 in the oxide matrix. Under irradiation of electron beams, degradation of the intensity is observed for both the CL bands but the decay characteristics are different.     

镱铒共掺Al2O3薄膜光致发光特性优化

用中频磁控溅射方法在SiO2/Si基底上制备了五组固定掺铒浓度不同镱铒浓度比率的镱铒共掺Al2O3薄膜样品.室温下测量了薄膜在1.430 μm~1.630 μm波段范围内光致发光光谱.研究发现,镱的掺入有效地提高了三价铒离子的光致发光强度,最优的镱铒掺杂为：掺铒0.33 mol%,Yb3+∶Er3+=10∶1,比相同掺铒浓度单掺铒样品光致发光峰值强度增强40倍;确定的掺铒浓度,有着固定的最佳镱铒浓度比率,主要是镱铒离子间的正向和反向能量传递相互作用的结果,但最佳镱铒浓度比率随着掺铒浓度的增加呈现下降趋势;单掺铒薄膜的光致发光峰值强度随掺铒浓度呈现近Gauss形状变化,而最佳镱铒共掺样品的光致发光峰值强度随掺铒浓度呈现了倒Gauss形状变化.     

Room temperature photoluminescence mechanism of SiOx film after annealing at different temperatures

SiO_x films were deposited on Si(1 0 0) substrates by evaporation of SiO powder. The samples were annealed from room-temperature (RT) to 1100 °C. After the samples were cooled down to RT, photoluminescence (PL) spectra from these samples were measured. It was found that when the annealing temperature Ta is not higher than 1000 °C, there is a PL centered at 620 nm, and with Ta increasing the intensity increases at first and then decreases when Ta is higher than 500 °C. When Ta is no less than 1000 °C another PL peak located at 720 nm appears. Combined with Raman and XRD spectra, we confirm that the latter PL is from Si nanocrystals that start to form when Ta is higher than 1000 °C. PL spectra for Ta<900 °C were discussed in detail and was attributed to defects in the matrix rather than from Si clusters.     

Visible photoluminescence of co-sputtered Ge–Si duplex nanocrystals

The photoluminescence (PL) characteristics of co-sputtered Ge–Si duplex nanocrystal films were examined under excitation by a 325-nm HeCd laser, combined with Raman and Fourier-transform infrared reflection spectra analysis. A broad visible PL spectrum from the as-deposited Ge–Si nanocrystal films was observed in the wavelength range 350–700 nm. Basically, the PL spectrum can be considered to consist of two distinct parts originating from different emission mechanisms: (i) the spectrum in the range 350–520 nm, consisting of characteristic double peaks at 410 and 440 nm with PL intensities decreasing after vacuum annealing, probably due to vacancy defects in Si nanocrystals; and (ii) the spectrum in the range 520–700 nm, consisting of a characteristic peak at 550 nm with a PL intensity not affected by vacuum annealing, probably due to Ge-related interfacial defects. No size dependence of PL peak energy expected from quantum confinement effects was observed in the wavelength range investigated. However, with an increase of crystal size, the PL peak intensity in the blue zone decreased. The PL intensity is found to be strongly affected by silicon concentration. A film heated in air has a different PL mechanism from the as-deposited and vacuum-annealed films. PACS 78.67.Bf; 81.05.Cy; 81.15.Cd     

Effect of temperature on pulsed laser deposition of ZnO films

ZnO thin films have been deposited on Si(1 1 1) substrates at different substrate temperature by pulsed laser deposition (PLD) of ZnO target in oxygen atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the deposition temperature on the thickness, crystallinity, surface morphology and optical properties of ZnO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), photoluminescence (PL) spectrum and infrared spectrum. The results show that in our experimental conditions, the ZnO thin films deposited at 400 °C have the best surface morphology and crystalline quality. And the PL spectrum with the strongest ultraviolet (UV) peak and blue peak is observed in this condition.     

Effect of annealing on structural, optical and electrical properties of nanostructured Ge thin films

Ge thin films with a thickness of about 110 nm have been deposited by electron beam evaporation of 99.999% pure Ge powder and annealed in air at 100-500 °C for 2 h. Their optical, electrical and structural properties were studied as a function of annealing temperature. The films are amorphous below an annealing temperature of 400 °C as confirmed by XRD, FESEM and AFM. The films annealed at 400 and 450 °C exhibit X-ray diffraction pattern of Ge with cubic-F structure. The Raman spectrum of the as-deposited film exhibits peak at 298 cm⁻¹, which is left-shifted as compared to that for bulk Ge (i.e. 302 cm⁻¹), indicating nanostructure and quantum confinement in the as-deposited film. The Raman peak shifts further towards lower wavenumbers with annealing temperature. Optical band gap energy of amorphous Ge films changes from 1.1 eV with a substantial increase to ∼1.35 eV on crystallization at 400 and 450 °C and with an abrupt rise to 4.14 eV due to oxidation. The oxidation of Ge has been confirmed by FTIR analysis. The quantum confinement effects cause tailoring of optical band gap energy of Ge thin films making them better absorber of photons for their applications in photo-detectors and solar cells. XRD, FESEM and AFM suggest that the deposited Ge films are composed of nanoparticles in the range of 8-20 nm. The initial surface RMS roughness measured with AFM is 9.56 nm which rises to 12.25 nm with the increase of annealing temperature in the amorphous phase, but reduces to 6.57 nm due to orderedness of the atoms at the surface when crystallization takes place. Electrical resistivity measured as a function of annealing temperature is found to reduce from 460 to 240 Ω-cm in the amorphous phase but drops suddenly to 250 Ω-cm with crystallization at 450 °C. The film shows a steep rise in resistivity to about 22.7 KΩ-cm at 500 °C due to oxidation. RMS roughness and resistivity show almost opposite trends with annealing in the amorphous phase.     

Large Third-Order Optical Nonlinearity of Cadmium Sulphide Nanoparticles Embedded in Polymer Thin Films

A simple method for synthesis of well dispersed cadmium sulphide nanoparticles embedded in a polyethylene glycol matrix （PEG 400） in thin film form is presented. The large blue shift of the band gap energy of the CdS nanoparticles compared to the bulk semiconductors is observed via UV-vis absorption spectra. Photoluminescence spectra of CdS nanocomposite films show that the emission peaks shift towards the longer wavelength with the increase of annealing temperature. Transmission electron microscopic images as well as Raman scattering studies confirm the CdS nanometer size particle formation within the polymer matrix. The particle size is about 8 nm. Selected area electron diffraction （SAED） shows the cubic zinc blende polycrystalline rings. Third-order optical nonlinearity of the CdS nanopartieles embedded in polymer thin films is studied with the Z-scan technique under 1064 nm excitation. The results show that the CdS nanocomposite film exhibits negative nonlinear refraction index and positive absorption coefficient. The film shows large optical nonlinearity, and the magnitude of the third-order nonlinear susceptibility of the film is calculated to be 1.73 × 10^-9 esu. The corresponding mechanism is discussed.     

多孔硅锗的制备及其近红外发光增强

用激光照射辅助电化学刻蚀硅锗合金样品能够形成多种低维纳米结构。在硅锗合金上形成的多孔状结构在波长为725 nm处有很强的光致发光(PL)峰,PL的增强效应不能单独用量子受限模型来解释。我们提出新的模型来解释这种低维纳米结构的PL增强效应。