Optical properties of alumina membranes prepared by anodic oxidation process

The luminescence property of anodic alumina membranes (AAMs) with ordered nanopore arrays prepared by electrochemically anodizing aluminum in oxalic acid solutions have been investigated. Photoluminescence emission (PL) measurement shows that a blue PL band occurs in the wavelength ranges of 300-600 nm. The PL intensity and peak position of AAMs depend markedly on the excitation wavelength. A new peak located at 518 nm can be observed under a monitoring wavelength at 429 nm in the photoluminescence excitation (PLE) spectra. Convincing evidences have been presented that the PLE would be associated with the residual aluminum ions in the membrane. The PLE and PL of AAMs, as a function of anodizing times, have been discussed. It is found that the oxalic impurities incorporated in the AAMs would have important influences on the optical properties of AAMs in the initial stage of anodization. The PL and PLE spectra obtained show that there are three optical centers, of which the first is originated from the F⁺ centers in AAMs, the second is correlated with the oxalic impurities incorporated in the AAMs, and the third is associated with the excess aluminum ions in the membrane.     

Ca3MgSi2O8中Ce3+的光谱及其晶体学格位

本文合成了发射蓝紫色光的镁硅钙石Ｃａ３ＭｇＳｉ２Ｏ８：Ｃｅ＾３＋荧光体。测试了该荧光体的激发和发射光谱。利用这些光谱结果和Ｖａｍ Ｕｉｔｅｒｔ经验公式,结合对Ｃａ３ＭｇＳｉ２Ｏ８晶体的结构研究,确认Ｃａ３ＭｇＳｉ２Ｏ３：Ｃｅ＾３＋中存在两种性质有差异的Ｃｅ＾３＋发光中心,它们分别占据基质中的两种八配位的钙格位。     

On the origin of light emission from porous anodic alumina formed in sulfuric acid

We have investigated the photoluminescence (PL) property of porous anodic alumina membranes (PAAMs) formed on bulk Al foils in 0.3 M sulfuric acid. Different from that from the PAAMs formed in oxalic acid, the obtained PL spectra show two emission bands which have different origins. One centered at ∼465 nm (α-band) weakens its intensity in the PAAM annealed in O₂ and is thus attributed to optical transition in oxygen vacancies. The other in the blue (β-band) redshifts with increasing excitation wavelength. On the basis of spectral examinations and analyses, we ascribe the β-band to radiative recombination of carriers in the isolated hydroxyl groups at the surface of the pore wall, whereas the photogeneration of carriers takes place in oxygen vacancies in the pore wall. This work improves the understanding of the light-emitting property of the PAAMs formed in sulfuric and oxalic acid.     

多孔氧化铝薄膜的光致发光起源:三种缺陷中心

在草酸溶液中用二次阳极氧化法制备了纳米多孔氧化铝薄膜,分析了制备过程中氧化铝薄膜中缺陷的形成机理.场发射电子显微镜给出了薄膜的表面形貌和结构.X射线色散能谱和傅里叶红外透射光谱测试表明,进入薄膜中的草酸杂质加热到500℃未全部分解.对多孔氧化铝薄膜的光致发光PL光谱做了高斯拟合,结合测试结果和薄膜中的缺陷分析指出:多孔氧化铝薄膜的发光由F+,F和草酸杂质相关缺陷引起,对应发光中心分别在402,433,475 nm处,并提出F中心起主导作用.对不同草酸浓度中制备的多孔氧化铝薄膜的PL光谱讨论指出:随草酸浓度增加,三种发光中心的峰位不会发生变化,但相对强度发生改变,F+中心和F中心减少,草酸杂质相关发光中心增加,PL峰红移.最后提出通过控制草酸浓度来控制多孔氧化铝薄膜中的草酸杂质.此研究将对多孔氧化铝薄膜发光起源和机理有更深入的理解,同时也为多孔氧化铝薄膜的制备提供一种全新的思路.     

不同退火条件对纳米多孔氧化铝薄膜光致发光的影响

以草酸为电解液,采用二次阳极氧化法制备出了纳米多孔氧化铝薄膜,经不同退火温度和退火气氛处理氧化铝薄膜后,通过分析其光致发光光谱得出：相同的退火气氛中, 退火温度T≤600 ℃ 时,T=500 ℃具有最大的光致发光强度;退火温度T≥700 ℃时,随着退火温度的升高,样品的发光强度增大。在不同的退火气氛中,多孔氧化铝薄膜随着退火温度的升高,发光峰位改变不同,即在空气中退火处理后,随着退火温度的升高,发光峰位蓝移,而在真空中退火处理后,发光峰位并不随退火温度的升高而变化;通过对1 100 ℃高温退火处理后的氧化铝薄膜的光致发光曲线的高斯拟合,可以看出,经退火处理后的多孔氧化铝,主要存在三个发光中心,发光曲线在350～600 nm范围内对应三个发射峰, 发射波长分别为387,410,439 nm。相同的退火温度下,空气中退火得到的氧化铝薄膜的光致发光强度大于真空中退火处理后的氧化铝薄膜。基于实验结果,结合X射线色散能谱(EDS)、红外反射光谱等表征手段,探讨了多孔氧化铝薄膜的发光机制,并对经过不同退火条件得到的多孔氧化铝薄膜的光致发光特性的改变做出了合理的解释。     

Effect of heat treatment on the structure of incorporated oxalate species and photoluminescent properties of porous alumina films formed in oxalic acid

The present work focuses on the use of IR spectroscopy and photoluminescence spectral measurements for studying the treatment temperature effect on the compositional and luminescent properties of oxalic acid alumina films. In line with the recent researches we have also found that heat treatment of porous alumina films formed in oxalic acid leads to considerable changes in their photoluminescence properties: upon annealing the intensity of photoluminescence (PL) increases reaching a maximum at the temperature of around 500 °C and then decreases. IR spectra of as-grown and heat-treated films have proved that PL emission in the anodic alumina films is related with the state of ‘structural’ oxalate species incorporated in the oxide lattice. These results allowed us to conclude that PL behavior of oxalic acid alumina films can be explained through the concept of variations in the bonding molecular orbitals of incorporated oxalate species including σ- and π-bonds.     

硫酸根离子对草酸-硫酸混合酸中制备的多孔阳极氧化铝光致发光特性的影响

采用电化学阳极氧化法,分别在草酸、硫酸及两者不同浓度比的混合酸中制备了AAO薄膜样品,并分别观察了在250,296 nm光激发下的光致发光(PL)特性。结果表明:草酸和混合酸中制备的AAO薄膜,在250~550 nm范围内的光致发光与不同存在或分布形式的草酸杂质形成的发光中心相关。硫酸根离子对混合酸中制备的AAO薄膜的PL特性有很大影响,随硫酸根离子浓度的增加发光峰位逐渐蓝移。分析了出现上述实验现象的原因。     

Dependence of blue-emitting property on nanopore geometrical structure in Al-based porous anodic alumina membranes

Porous anodic alumina (PAA) membranes were fabricated using anodization of Al foils. Based on morphology observations and photoluminescence (PL) measurements, it is revealed that the peak position of the observed blue PL band has an evident dependence on nanopore geometrical structure. The blue PL band is asymmetrical and can be Gaussian divided into two subbands, which originate in two kinds of oxygen-deficient centers, F⁺ and F centers. On raising the anodic voltage, the two subbands red shift and the intensity of the subband from the F⁺ centers relative to that from the F centers increases. This suggests that the increases of nanopore size and porosity make partial F⁺ centers convert into F centers. The mechanism of this conversion is further discussed on the basis of the PL behavior of the PAA membrane under ultraviolet irradiation. This work will be beneficial to the better understanding of the PL property of the PAA membrane. PACS 78.55.-m; 82.45.Cc; 76.30.Mi     

Eu掺杂SiC_xO_y薄膜的Eu~(3+)发光机制

利用磁控溅射技术在低温250℃下制备Eu掺杂SiC_xO_y薄膜,研究薄膜的Eu~(3+) 发光激发机制。实验结果表明,薄膜的发光谱由来自基体材料的蓝光和来自Eu~(3+) 的红光组成;随着薄膜中Eu含量由0.19%增加到2.27%,其红光强度增加3倍左右,而蓝光逐渐减弱。Raman光谱及荧光瞬态谱分析表明,其蓝光由中立氧空位缺陷发光中心引起。结合薄膜的Eu~(3+) 激发光谱分析,SiC_xO_y∶Eu薄膜的红光增强源于薄膜中Eu~(3+) 离子浓度的增加和/或基体材料的中立氧空位缺陷发光中心与Eu~(3+) 离子的能量转移。     

退火对ZnS/PS复合体系光致发光特性的影响

用脉冲激光沉积(PLD)技术以多孔硅(PS)为衬底生长了ZnS薄膜,分别测量了ZnS、PS以及ZnS/PS复合体系在室温下的光致发光(PL)光谱。结果发现,ZnS/PS复合体系的PL光谱中PS的发光峰位相对于新制备的PS有所蓝移。把该ZnS/PS样品分成三块,在真空400℃分别退火10,20,30 min,研究不同退火时间对ZnS/PS复合体系光致发光特性的影响。发现退火后样品的PL光谱中都出现了一个新的绿色发光带,归结为ZnS的缺陷中心发光。随着退火时间的延长,PS的发光强度逐渐降低且峰位红移。把ZnS的蓝、绿光与PS的红光相叠加,整个ZnS/PS复合体系在可见光区450~700 nm形成一个较宽的光致发光谱带,呈现较强的白光发射。     

The effect of annealing on the photoluminescent and optical properties of porous anodic alumina films formed in sulfamic acid

Photoluminescent and optical properties of porous oxide films formed by two-step aluminum anodization at a constant potential of 30 V in sulfamic acid have been investigated after their annealing, ranging from room temperature up to 600 °C. X-ray diffraction reveals the amorphous nature of porous oxide films. Infrared and energy dispersive spectroscopy indicates the presence of sulfuric species incorporated in oxide films during the anodization. Photoluminescence (PL) measurements show PL bands in the range from 320 to 600 nm. There are two peaks in emission and excitation spectra. One emission peak is at constant wavelength centered at 460 nm and the other shifts from 390 to 475 nm, depending on excitation wavelength. For excitation spectra, one spectral peak is at constant wavelength at 270 nm and the other also shifts to longer wavelengths while increasing emission wavelength. Upon annealing of the as-prepared oxide films PL increases reaching maximum value at about 300 °C and then decreases. The results indicate the existence of two PL centers, one placed at surface of the pore wall, while the other positioned inside the oxide films.     

多孔氧化铝薄膜的制备和光学特性研究

采用阳极氧化法制备了二维有序纳米孔氧化铝膜.研究了工艺参数对多孔薄膜有序性、孔径、膜厚度等的影响，测量了多孔氧化铝有序膜的光透过、光吸收和光发射等光学特性.结果表明，在波长360 nm附近多孔氧化铝有序膜的光透过谱线和光吸收谱线发生突变，波长大于360 nm时，光透过增强；波长小于360 nm时，光吸收增强.多孔氧化铝有序膜的光致发光强度和峰位与激发光波长有关，光致发光谱范围在340~600 nm.     

Variation of double-peak structure in photoluminescence spectra from porous silicon with excitation wavelength

We have systematically observed at room temperature the variations of photoluminescence(PL) from porous silicon(PS) with excitation wavelength in a range from 260 to 460nm at 20nm intervals. In the range from 260 to 320nm, the PL spectra for one of the two studied samples show clear double-peak structure. Each spectrum can be fitted by two Gaussian functions with their peaks centered at about 610nm and 710nm, respectively. The peak position and the full width at half maximum of the two Gaussian functions change little with excitation wavelength. The above phenomena seem hard to interpret using the quantum confinement model, but can be understood in the quantum confinement/luminescence centers model (G.G.Qin and Y.Q.Jia, Solid State Commun. 86, 559(1993)), if we suppose that there are two kinds of luminescence centers adsorbed on the surfaces of nane-scale silicon (NS) units or situated in the SiO_x layers covering the NS units in PS.     

Hydrothermal synthesis and optical properties of full-color-emission ZnS:Cu, Al nanocrystals

ZnS:Cu, Al nanocrystals were synthesized by a hydrothermal method at 200 degrees C and their optical properties were studied. The analysis of XRD and TEM show that the spherical-like nanocrystals had a grain size of approximately 15 nm and were well dispersed, with a zinc blende structure. The energy dispersive X-ray spectroscopy (EDX) and atomic absorption spectrometry were applied to the analysis of S, Zn and Cu content in the sample. The results proved that a large number of zinc vacancies exist and Cu is incorporated into the sample lattice. The photoluminescence (PL) spectra were investigated. The PL mechanism is discussed. The excitation spectrum is broad. Under 337 nm excitation the sample emits bright green light. Under 370-410 nm excitation the sample emits white light. The broad emission spectra are almost coincident with any excitation wavelength of between 370 and 410 nm making them attractive as conversion phosphors for LED applications and full-color fluorescence display devices. The emitted white light under 375 nm excitation was found to be the result of blue, green, and orange emission bands. For Cu/Zn, Cu/Al and S/Zn molar ratios of 3 x 10(-4), 2 and 3, respectively, the near blue white light can be observed with the naked eye in daylight.     

BaClxBr2-x∶Eu2+材料光激励光谱及色心研究

采用高温固相法制备了BaClxBr2-x∶Eu2+光激励发光材料,利用XRD、激发、发射以及激励光谱研究了所制备材料的结构和光学性能。XRD图像表明所制备的材料为单一纯相,随X值增大,衍射角向大角度偏移。发射光谱中位于405nm的窄带谱峰,由Eu2+的4f65d→4f7能级跃迁所引起,监测405nm发射峰,所得激发光谱是位于250～380nm之间的宽带,谱峰位于303nm;光激励波段位于480～800nm,激励峰位于575nm。通过光谱曲线拟合,发现激励光谱由550,610和685nm左右的光谱叠加而成,分别对应F(Cl-),F(Cl-Br),F(Br-)色心,激励峰随Cl/Br比值增加而蓝移。     

Photoluminescence and magneto-optical properties of multilayered type-II ZnTe/ZnSe quantum dots

Multilayered Zn–Se–Te structures grown by migration enhanced epitaxy are studied by temperature- and excitation-dependent photoluminescence (PL) as well as magneto-PL. The PL consists of two bands: a blue band, overlaid with band edge sharp lines, dominant at low temperatures and high excitation, and a green band, which appears at elevated temperature and low excitation. Upon varying excitation intensity by four orders of magnitude, the green band peak energy shifts by ∼60 meV, indicating recombination of excitons in type-II quantum dots (QDs); no significant shift is observed for the blue band. Therefore, the green emission is attributed to ZnTe/ZnSe type-II QDs, which co-exist with isoelectronic centers, responsible for the blue and band edge emissions. The existence of type-II ZnTe/ZnSe QDs is further confirmed by magneto-PL, for which the observed oscillations in the PL intensity as a function of magnetic field is explained in terms of the optical Aharonov–Bohm effect.     

Luminescence properties of oxide coatings on aluminum alloys

This is a study of the luminescence properties of coatings formed on aluminum alloys by anodizing in electrolytic solutions based on oxalic, sulfuric, and tartaric-sulfonic acids. At least two emission centers, with band maxima in the ranges of 390–410 and 470–510 nm, can be reliably identified in the photoluminescence spectra. The first type of center is characterized by single-band photoluminescence excitation spectra and the second, by two-band spectra. An analysis of the two-band photoluminescence excitation (PLE) spectra in the range of 470–510 nm shows that the position of the narrow short-wavelength PLE spectrum near 272 nm is independent of the type of acid used in the anodization process. The position and shape of the other PLE spectral bands depend both on the type of acid used and on the processing of the alloy or alumina surfaces. It is assumed that defect-free alumina centers are responsible for the 272 nm PLE band, while the other photoluminescence bands are caused primarily by different divacancies of oxygen (F₂⁺ {F_2^+} , F ₂, and F₂⁺² {F_2^{+2}} centers) whose origin is governed by the type of electrolyte.     

Influence of excitation light wavelength on the photoluminescence properties for ZnO films prepared by magnetron sputtering

Highly orientated polycrystalline ZnO films were deposited on sapphire, silicon and quartz substrates at room temperature by r.f. magnetron sputtering. Different photoluminescence (PL) spectra were observed when excited with different wavelength light. A UV emission peak (356 nm) and a blue peak (446 nm) were generated for the films on sapphire, silicon and quartz substrates, and only the 446 nm blue emission appeared for the films on glass substrates when the wavelength of the excitation light was 270 nm. With increasing the wavelength of the excitation light up to 300 and 320 nm, the UV emission disappeared for films on various substrates and the wavelength of the PL peaks increased up to 488 and 516 nm, respectively. When the wavelength of the excitation light increased to 398 nm, the PL spectrum becomes a wide band that is consistent with three emission peaks.     

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 properties of anodic alumina membranes with ordered nanopore arrays

Photoluminescence (PL) of anodic alumina membranes (AAMs) with ordered nanopore arrays fabricated in oxalic acid has been investigated under different annealing temperatures. The PL intensity firstly increases, and at 500 °C reaches a maximum value, then decreases. The structural transition from amorphous to γ-Al₂O₃ in AAMs has been confirmed by X-ray diffraction. Thermogravimetric analysis results and electron paramagnetic resonance measurements revealed that the PL band of alumina membranes could be attributed to the oxygen-related defect centers (F⁺ centers) rather than the luminescent centers transformed from oxalic impurities.