Disorder driven optical processes in nanocrystalline ZnO

A systematic study on the modification of optical properties in mechanically milled ZnO powder has been reported here. The average grain size of the powder becomes ～20 nm within 4 h of milling. Fluctuations of average grain size have been noticed at the initial stage of milling (within 15 min). Changes in grain morphology with milling have also been noticed in scanning electron micrographs of the samples. Room temperature optical absorption data shows a systematic red shift of absorption band edge (～3.25 eV). The band tail parameter (extracted from the optical absorption just below the band edge) follows a simple exponential relation with the inverse of the average grain size. Significant increase of the band tail parameter has been noticed at low grain size regime. It has been analyzed that high values of band tail parameter is a representative of V_Zn–V_O type divacancy clusters. Room temperature photoluminescence spectra show decrease (except for 120 min milling) of band edge emission intensity with increase of milling time. Subsequent decrease of sub-band edge emission is, however, less prominent. The variation of PL intensity ratio (intensity at band edge peak with that at 2.3 eV) follows simple exponential decrease with the increase of band tail parameter. This indeed shows that band edge emission in ZnO is related with the overall disorder in the system, not grain size induced only.     

Structural and band tail state photoluminescence properties of amorphous SiC films with different amounts of carbon

Amorphous silicon carbide films are deposited by the plasma enhanced chemical vapour deposition technique,and optical emissions from the near-infrared to the visible are obtained.The optical band gap of the films increases from 1.91 eV to 2.92 eV by increasing the carbon content,and the photoluminescence(PL) peak shifts from 1.51 eV to 2.16 eV.The band tail state PL mechanism is confirmed by analysing the optical band gap,PL intensity,the Stocks shift of the PL,and the Urbach energy of the film.The PL decay times of the samples are in the nanosecond scale,and the dependence of the PL lifetime on the emission energy also supports that the optical emission is related to the radiative recombination in the band tail state.     

Enhanced luminescent properties and optical absorption of γ-irradiated KI: Ce, Tb crystals

This paper reports that KI doped with Ce³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by the Bridgman-Stockbarger method and characterized by optical absorption photoluminescence (PL), thermoluminescence (TL), photostimulated emission (PSL) and TL emission. The optical absorption measurement indicates that F and V₁, V₂ centers are formed in the crystals during the γ irradiation process. It was attempted to incorporate a broad band of Ce³⁺ activator into the narrow band emission of Tb³⁺ in the KI host without the reduction of emission intensity. Ce³⁺-co-doped KI and Tb crystals showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to the ⁵D₃-⁷F_j (j=3,4,5,6) transition of Tb³⁺, when they were excited at 240 nm.These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in the KI host. Co-doping Ce³⁺ ions greatly intensified the excitation peak at 260 nm for the emission at 393 nm of Tb³⁺, which means that more lattice defects, involved in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ co-doping. The integrated light intensity is an order of magnitude higher as compared to the undoped samples for similar doses of irradiation and heating rates. The defects generated by irradiation were monitored by optical absorption and TSL Trap parameters for the TL process are calculated and presented.     

Theoretical and experimental study on the photoluminescence in BaTiO3 amorphous thin films prepared by the chemical route

A polymeric precursor method was used to synthesize BaTiO₃ amorphous thin film processed at low temperature. The luminescence spectra of BaTiO₃ amorphous thin films at room temperature revealed an intense single-emission band in the visible region. The visible emission band was found to be dependent of the thermal treatment history. Photoluminescence (PL) properties for different annealing temperatures were investigated. It was concluded that the intensity of PL is strongly dependent on both the heat treatment of the films and the presence of an inorganic disordered phase. Experimental optical absorption measurements showed the presence of a tail. These results are interpreted by the nature of these exponential optical edges and tails, associated with defects promoted by the disordered structure of the amorphous material. We discuss the nature of visible PL at room temperature in amorphous barium titanate in the light of the results of recent experimental and quantum mechanical theoretical studies. Our investigation of the electronic structure involved the use of first-principle molecular calculations to simulate the variation of the electronic structure in the barium titanate crystalline phase, which is known to have a direct band gap, and we also made an in-depth examination of amorphous barium titanate.     

Deuterium in In-based quantum wells

The photoluminescence (PL) of high quality InGaAs/GaAs typically shows one strong intrinsic band, due to the heavy-bole free-exciton (HHFE) recombination. After sample irradiation with deuterium, two bands appear at energies below that of HHFE: a deeper band, D, due to radiative recombination at a deuterium-related site, and a shallower band, (D,X), attributed to an exciton bound to the same state. A maximum of the binding energy has been observed as a function of the well width for both states. As the indium molar fraction x increases, the strength of the D band decreases, together with its binding energy, until the band becomes no more detectable at x=0.37. The (D,X) band cannot be resolved for x ≥ 0.19. Deuterium diffusion has no beneficial effect on the PL intensity of InGaAs/GaAs quantum wells. Different is the case of InAs/GaAs quantum wells having well width below 2 monolayers. Although no strain relaxation occurs in the samples, the PL of the virgin samples is typical of structures with a high number of defects. After deuterium diffusion, the PL intensity increases by one to three orders of magnitude, depending whether non-radiative centers or thermal escape of carriers from the well rule the PL efficiency.     

Indium-incorporation-induced transformation of optical, photoluminescence and lasing properties of InGaN epilayers

A comparative combined study of photoluminescence (PL), PL kinetics, stimulated emission (SE) and photoreflectance (PR) properties in In_xGa_1−xN epilayers is carried out in the composition range 0≤x≤0.19. In-incorporation up to 4% leads to the sufficient longer radiative recombination decay time due to the decrease in non-radiative recombination channels, which are peculiar to GaN, and band-to-band optical transitions predominate the spontaneous PL spectrum. Further In-incorporation (x>4%) leads to the localization of carriers and/or excitons at band-tails in the In-rich areas. Correlation between the position of dominant low-energy PR oscillation due to the main band gap and SE peak position shows that band-to-band transitions are responsible for lasing and dominate the PL spectrum in all highly pumped In_xGa_1−xN samples.     

Optical and theoretical investigations of V ions in CdZnTe crystal

High-resistivity CdZnTe:V crystals are investigated by photoluminescence (PL) and by time-resolved PL in the infrared spectral range. A double peaked emission band is detected around 0.8 eV and it is related to vanadium doping. No-phonon lines of the internal transitions were detected. This emission is interpreted as a balance between the ⁴T₁(⁴P)→⁴T₁(⁴F) internal transition and an electronic transition from the conduction band to the ⁴T₁(⁴F) ground state of V²⁺. The corresponding decay time after laser excitation gives evidence to the contribution of two different recombination processes. These two emission bands are separated by time-resolved luminescence. Crystal-field calculations of the detected transition energies based on Tanabe-Sugano scheme are presented and the Racah parameter B and crystal-field intensity D_q were determined.In addition, a model is developed in terms of one-electron orbital, to explain the characteristics of the PL excitation processes of V²⁺. Excitations with above and below band edge energy confirm the proposed schemes.     

InN分凝的InGaN薄膜的光致发光与吸收谱

我们用低压MOCVD在蓝宝石衬底生长了InGaN/GaN外延层.用X射线衍射(XRD),光致发光谱(PL),光吸收谱等测量手段,研究了InGaN的辐射发光机制.In组分利用Vegard定理和XRD测量得到.我们发现随着In组分的增加,在光吸收谱上发现吸收边的红移和较宽的Urbach带尾;PL谱中低能端的发射渐渐成为主导,并且在PL激发谱中InGaN峰也变宽.我们认为压电效应改变了InGaN的能带结构,从而影响了光学吸收特性.而在InN量子点中的辐射复合则是InGaN层发光的起源.     

Photoluminescence and optical properties of He ion bombarded ultra-high molecular weight polyethylene

Ion bombardment is a suitable tool to improve the physical and chemical properties of polymer surface. In this study UHMWPE samples were bombarded with 130 keV He ions to the fluences ranging from 1 × 10¹² to 1 × 10¹⁶ cm⁻². The untreated and ion beam modified samples were investigated by photoluminescence, and ultraviolet-visible (UV-vis) spectroscopy. Remarkable decrease in integrated luminescence intensity with increasing ion fluences was observed. The reduction in PL intensity with increase of ion fluence might be attributed to degradation of polymer surface and formation of defects. The effect of ion fluence on the optical properties of the bombarded surfaces was characterized. The values of the optical band gap E_g, and activation energy E_a were determined from the optical absorption. The width of the tail of the localized states in the band gap (E_a) was evaluated using the Urbach edge method. With increasing ion fluences a decrease in both the energy gap and the activation energy were observed. Increase in the numbers of carbon atoms (N) in a formed cluster with increasing the He ion fluence was observed.     

非晶氧化硅薄膜带尾发光特性

采用等离子体增强化学气相沉积技术,通过改变CO2流量制备了不同氧含量的非晶氧化硅薄膜。利用紫外可见吸收谱、傅里叶红外吸收谱和稳态/瞬态光致发光谱等技术研究了薄膜的微观结构和光学特性。实验结果表明,随着氧含量的增加,薄膜的带隙增大,光致发光强度增加、峰值朝高能方向移动、光谱半峰全宽展宽。时间分辨光谱显示薄膜发光峰值处的衰减时间随氧含量的增加从6.2ns单调增加到21ns,而同一样品的发光寿命随发射波长能量增加而减小。综合分析光学吸收、发射及发光衰减特性表明,薄膜的发光机制主要归结为非晶材料带尾态之间的辐射复合。     

Study of photophysical properties of capped CdS nanocrystals

Here, we have examined the role of capping agent on the optical properties of CdS nanoparticles by steady-state and time-resolved photoluminescence (PL) spectroscopy. The estimated particles sizes are 3.45, 2.5 and 2.39 nm for uncapped, capped with silica (SiO₂) and thiosalicylic acid (TSA), respectively. The absorption and emission spectra show a clear blue shift to shorter wavelengths in presence of TSA- and SiO₂-capped nanoparticles. It is found that the average decay time 〈τ〉 are 6.24, 4.54 and 2.84 ns for uncapped, capped with SiO₂ and TSA nanoparticles, respectively. Our analysis suggests that the hole or the electron is trapped on thiol molecule of TSA or hydroxyl group of SiO₂, then radiative recombination of the electron and hole is delayed, resulting in strong quenching of PL efficiency.     

Visible photoluminescence in porous GaAs capped by GaAs

A typical porous structure with pores diameters ranging from 10 to 50 nm has been obtained by electrochemical etching of (1 0 0) heavily doped p-type GaAs substrate in HF solution. Room temperature photoluminescence (PL) investigations of the porous GaAs (π-GaAs) reveal the presence of two PL bands, I₁ and I₂, located at 1.403 and 1.877 eV, respectively. After GaAs capping, the I₁ and I₂ PL bands exhibit opposite shift trends. However, the emission efficiency of these two bands is not strongly modified. Low temperature PL of capped porous GaAs versus injection levels shows that the I₁ PL band exhibits a red shift while the I₂ PL band exhibits a blue shift with increasing injection levels. The I₂ PL band intensity temperature dependence shows an anomalous behaviour and its energy location shows a blue shift as temperature increases. The observed PL bands act independently and are attributed to electron – hole recombination in porous GaAs and to the well-known quantum confinement effects in GaAs nanocrystallites. The I₂ PL band excitation power and temperature dependencies were explained by the filling effect of GaAs nanocrystallites energy states.     

Photoluminescence and photoconductive characteristics of hydrothermally synthesized ZnO nanoparticles

In the present paper, ZnO nanoparticles (NPs) with particle size of 20–50 nm have been synthesized by hydrothermal method. UV-visible absorption spectra of ZnO nanoparticles show absorption edge at 372 nm, which is blue-shifted as compared to bulk ZnO. Photoluminescence (PL) and photoconductive device characteristics, including field response, light intensity response, rise and decay time response, and spectral response have been studied systematically. The photoluminescence spectra of these ZnO nanoparticles exhibited different emission peaks at 396 nm, 416 nm, 445 nm, 481 nm, and 524 nm. The photoconductivity spectra of ZnO nanoparticles are studied in the UV-visible spectral region (366–691 nm). In spectral response curve of ZnO NPs, the wavelength dependence of the photocurrent is very close to the absorption and photoluminescence spectra. The photo generated current, I_pc = (I_total - I_dark) and dark current I_dc varies according to the power law with the applied field I_pcαV^r and with the intensity of illumination I_pcαI_L ^r, due to the defect related mechanism including both recombination centers and traps. The ZnO NPs is found to have deep trap of 0.96 eV, very close to green band emission. The photo and dark conductivities of ZnO NPs have been measured using thick film of powder without any binder.     

SnO<Subscript>2</Subscript> nanocrystals synthesized by microwave-assisted hydrothermal method: towards a relationship between structural and optical properties

The exploration of novel synthetic methodologies that control both size and shape of functional nanostructure opens new avenues for the functional application of nanomaterials. Here, we report a new and versatile approach to synthesize SnO₂ nanocrystals (rutile-type structure) using microwave-assisted hydrothermal method. Broad peaks in the X-ray diffraction spectra indicate the nanosized nature of the samples which were indexed as a pure cassiterite tetragonal phase. Chemically and physically adsorbed water was estimated by TGA data and FT-Raman spectra to account for a new broad peak around 560 cm⁻¹ which is related to defective surface modes. In addition, the spherical-like morphology and low dispersed distribution size around 3–5 nm were investigated by HR-TEM and FE-SEM microscopies. Room temperature PL emission presents two broad bands at 438 and 764 nm, indicating the existence of different recombination centers. When the size of the nanospheres decreases, the relative intensity of 513 nm emission increases and the 393 nm one decreases. UV–Visible spectra show substantial changes in the optical absorbance of crystalline SnO₂ nanoparticles while the existence of a small tail points out the presence of localized levels inside the forbidden band gap and supplies the necessary condition for the PL emission.     

Decay processes of photoluminescence in a nanocrystalline SiC thin film

Nanocrystalline (nc)-SiC film has been deposited by helicon wave plasma enhanced chemical vapor deposition technique and intense blue-white light emission is obtained. Microstructure analyses show that the 3C–SiC particles are embed in amorphous SiC matrix, and the average size of the nc-SiC is 3.96 nm. The photon energy of the main photoluminescence (PL) band is higher than the band gap of bulk SiC, which indicates that the optical emission mainly occurs in quantum states of 3C–SiC nanocrystals. In addition, the band tail states of amorphous SiC also contribute to the optical emission. Three decay processes are obtained from time-resolved PL spectra by deconvolution treatment, and the decay components correspond to the quantum confinement effect (QCE), surface states of nc-SiC particles, and band tail of amorphous SiC, respectively. The fractional integrated PL intensity of QCE related decay process decreases dramatically in the lower PL photon energy, indicating that the QCE mainly contributes to the short wavelength optical emission.     

Effect of annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films on sapphire (0 0 0 1) substrates by magnetron sputtering

ZnO thin films were epitaxially grown on sapphire (0 0 0 1) substrates by radio frequency magnetron sputtering. ZnO thin films were then annealed at different temperatures in air and in various atmospheres at 800 °C, respectively. The effect of the annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films are investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL). A strong (0 0 2) diffraction peak of all ZnO thin films shows a polycrystalline hexagonal wurtzite structure and high preferential c-axis orientation. XRD and AFM results reveal that the better structural quality, relatively smaller tensile stress, smooth, uniform of ZnO thin films were obtained when annealed at 800 °C in N₂. Room temperature PL spectrum can be divided into the UV emission and the Visible broad band emission. The UV emission can be attributed to the near band edge emission (NBE) and the Visible broad band emission can be ascribed to the deep level emissions (DLE). By analyzing our experimental results, we recommend that the deep-level emission correspond to oxygen vacancy (V_O) and interstitial oxygen (O_i). The biggest ratio of the PL intensity of UV emission to that of visible emission (I_NBE/I_DLE) is observed from ZnO thin films annealed at 800 °C in N₂. Therefore, we suggest that annealing temperature of 800 °C and annealing atmosphere of N₂ are the most suitable annealing conditions for obtaining high quality ZnO thin films with good luminescence performance.     

Optical properties of p-type ZnO doped by lithium and nitrogen

A lithium and nitrogen doped p-type ZnO (denoted as ZnO: (Li, N)) film was prepared by RF-magnetron sputtering and post annealing techniques with c-Al₂O₃ as substrate. Its transmittance was measured to be above 95%. Three dominant emission bands were observed at 3.311, 3.219 and 3.346 eV, respectively, in the 80 K photoluminescence (PL) spectrum of the p-type ZnO:(Li, N), and are attributed to radiative electron transition from conduction band to a Li_Zn-N complex acceptor level (eFA), radiative recombination of a donor-acceptor pair and recombination of the Li_Zn-N complex acceptor bound exciton, respectively, based on temperature-dependent and excitation intensity-dependent PL measurement results. The Li_Zn-N complex acceptor level was estimated to be about 126 meV above the valence band by fitting the eFA data obtained in the temperature-dependent PL spectra.     

Photoluminescence of bis(8-hydroxyquinoline) zinc (Znq2) and magnesium (Mgq2)

Absorption and photoluminescence (PL) spectra, PL quantum efficiency, and PL lifetime have been investigated on bis(8-hydroxyquinoline) zinc (Znq₂) and magnesium (Mgq₂) in solutions and powder. Znq₂ and Mgq₂ have the lowest-energy absorption band at 376 and 396 nm in acetonitrile solution, respectively, and emission band with peak at 555 and 480 nm. The PL quantum efficiency is 0.03 and 0.45 for Znq₂ and Mgq₂ in the solution, respectively, while 0.45 and 0.36 in powder. Unlike the case of powders, two PL lifetimes are obtained in solutions. The longer lifetime is attributed to molecule having interaction with its neighboring molecule, while the shorter one to the isolated single molecule.     

Recombination centers in phosphorous doped hydrogenated amorphous silicon

Optical absorption below the mobility gap of a-SiH_x:P films is derived from photoconductivity measurements and interpreted in terms of optical transitions from occupied localized states in the exponential valence band tail and dangling bond states 0.8 eV above the valence band edge to unoccupied free electron conduction band states. Collection efficiency measurements of Schottky barrier structures indicate that P doping introduces centers with large capture cross-section for holes.     

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.