Photoluminescent behavior of heat-treated porous alumina films formed in malonic acid

In the present work IR spectroscopy, electron probe microanalysis (EPMA) and photoluminescence (PL) spectral measurements were applied to study the effect of treatment temperature (T) on compositional and luminescent properties of malonic acid alumina films. Our studies have shown that the heat treatment of anodic alumina films at investigated temperatures from 100 up to 700 °C changes their photoluminescence spectra considerably. An increase in T results in the PL intensity growth. When reaching its maximum at 600 °C the luminescence intensity then decreases drastically with further T growth. The films heat-treated at 500 and 600 °C demonstrate asymmetrical PL band with Gaussian peaks at 437 and 502 nm. We proved that the malonic acid species incorporated into the alumina bulk during the film formation are responsible for photoluminescence band with its peak at 437 nm.     

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.     

乙醇对纳米多孔氧化铝薄膜光致发光特性的影响

采用二次阳极氧化法,用乙醇与草酸的混合溶液制备纳米多孔氧化铝薄膜。扫描电子微镜结果显示,乙醇与草酸混合溶液中制备的氧化铝薄膜形貌更规整,有序度更高。光致发光测试结果表明,该混合电解液制备的薄膜的光致发光强度有明显的提高,且随乙醇浓度的增加,发光强度逐渐增大。结合红外反射光谱及X光电子能谱对上述实验现象进行了分析,为多孔氧化铝薄膜掺杂和改善其发光特性提供了新的思路。     

The effect of oxalic and sulfuric ions on the photoluminescence of anodic aluminum oxide formed in a mixture of sulfuric and oxalic acid

Anodic aluminum oxide (AAO) films with highly ordered pore arrays were prepared in sulfuric, oxalic acids and their mixture solutions, respectively. The photoluminescence (PL) measurements show that AAO films formed in the mixture electrolytes have PL bands in the wavelength range of 300–450 nm, which mainly arise from the oxalic impurities incorporated into AAO films. However, the sulfuric ions have a strong effect on the PL bands. With the increase of the concentration of sulfuric ions in the mixture electrolyte, the blueshift of the PL bands occurs from 410 to 345 nm. The reasons of the results are being discussed.     

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。     

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。     

The investigation of photoluminescence centers in porous alumina membranes

To investigate the origin of blue photoluminescence (PL) in porous alumina membrane, we have prepared an anodic aluminum oxide film with a pore diameter of 40 nm in oxalic acid solution by a two-step anodization process. Our results show that the as-prepared alumina membrane is amorphous and exhibits a broad emission band peaking at around 452 nm with two sub-peaks located at 443 nm and 470 nm. As indicated by the PL excitation spectra, there are two excitation peaks which can account for the sub-peaks observed in the PL emission band. We have proposed that the broad emission band with two sub-peaks can be attributed to two luminescence centers in porous alumina membranes, namely, oxygen defects and oxalic impurities. Furthermore, we have rationalized that the two emission centers show similar influence on the PL band in the blue region based on a simple model. PACS 81.07.-b; 81.16.Dn; 79.60.Jv     

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.     

Structure and optical features of silicon carbide nanocrystals confined in alumina matrices

Thin films based on silicon carbide and alumina were synthesized by means of rf-sputtering using a co-deposition process. Several nanostructures were created which consist of thin films (∼200 nm thick) with homogeneous distribution of SiC nanocrystals (∼5 nm mean diameter) in the host alumina matrices. Characterization methods including X-ray photoelectrons spectroscopy (XPS), UV-vis absorption and photoluminescence (PL) were used to identify the involved structures, compositions and optical features of these nanostructures. Thus, XPS investigations were relevant to point out the involved chemical bonding in the core SiC nanocrystals and in the host alumina environments. Additionally, mixed bonding such as Si-O-C was also shown and seems to correlate with the SiC-alumina interfaces. Optical properties of the nanostructures films such as UV-vis absorption and photoluminescence (PL) were measured in representative samples and compared to simulated PL responses obtained by a theoretical model.     

Photoluminescence properties of heat-treated porous alumina films formed in oxalic acid

Photoluminescence and optical properties of as-anodized and heat-treated at 500 °C porous alumina films formed in a 0.3 M oxalic acid at 40 V have been studied. The FTIR indicates that the oxalate ions are embedded in the anodic alumina as chelating bidentate structures and further heating up to 500 °C does not cause any change in ion coordination. The results of time-resolved spectroscopy show the presence of two luminescence centers both in the as-anodized and heat-treated anodic alumina films with lifetimes of about 0.25 and 4.0 ns. The F⁺-centers in anodic alumina are responsible for the luminescence peak at about 420 nm, with a lifetime of about 4.0 ns. The luminescence peak at about 480 nm, with lifetime of about 0.25 ns, can be attributed to the luminescence of carboxylate ions existing in bulk of anodic alumina.     

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.     

Influence of electrolyte composition on photoluminescent properties of anodic aluminum oxide

Luminescent properties of anodic alumina fabricated in anodizing solutions containing oxalic, sulfuric, and phosphoric acids in addition to those modified by thermal annealing are investigated. Comparison of the obtained data shows that F⁺-centers are responsible for the luminescence band at 390 nm. The intense photoluminescence band of porous anodic alumina substrates at 450–500 nm is associated with oxalate anions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 208–212, March–April, 2008.     

Energy transfer in porous anodic alumina/rhodamine 110 nanocomposites

We have used porous anodic alumina (PAA) films as templates for embedding rhodamine 110 (Rh110) molecules and examined their photoluminescence (PL) properties in detail. The analysis of the polarization memory (PM) of PL strongly suggests that there is a significant energy transfer from PAA to Rh110 molecules. The effect of annealing the PAA layer on the PL properties of the nanocomposite has been studied. The results show that the energy transfer becomes more efficient in annealed PAA.     

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.     

8-羟基喹啉铝在多孔铝中的发光研究

利用多孔铝非常高的孔隙率,将8-羟基喹啉铝(Alq3)镶嵌到多孔铝中,得到Alq3/多孔铝镶嵌膜,研究了不同条件下制备的多孔铝镶嵌膜的荧光光谱。实验表明,Alq3在多孔铝中的发光峰位在490 nm左右,比其在固态粉末状态蓝移了许多。Alq3/多孔铝镶嵌膜的发光特性与多孔铝中嵌入Alq3分子的数量及聚集程度有关。当分子数量较多、聚集程度较大时,发光增强,光谱峰位红移,但聚集程度太大时,易发生荧光猝灭现象。数量较多时,由于Alq3分子大多以范德瓦尔斯力结合,聚体较少,所以峰位移动幅度不大。实验中还发现,Alq3因为处在小孔中,光学性质稳定,荧光光谱带宽超过100 nm,比一般染料大得多,这使Alq3/多孔铝镶嵌膜有可能在固体可调谐激光器方面得到新的应用;同时也为探究Alq3/多孔铝镶嵌膜在电致发光器件中的发光特性奠定了基础,为将其进一步推向实用提供了实验依据。     

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.     

Laser damage mechanism of porous Al2O3 films prepared by a two-step anodization method

Pure aluminum films were deposited on a B270 glass by electron beam evaporation technique. These aluminum films, which were used as anode, were put in sulfuric acid and oxalic acid to prepare porous alumina films using a two-step anodization method. The microstructure and laser damage characteristics of the alumina films were then tested. Results show that the microstructure of the alumina films formed in sulfuric acid and oxalic acid were vertical (cylindrical) pores with different diameters. The laser-damaged spot of the porous films was formed by innumerable small damaged pits with no mutual influence. Films prepared in different acids reveal different damage characteristics and reflect different mechanisms.     

Quasi-direct optical transitions in Ge nanocrystals embedded in GeO<Subscript>2</Subscript> matrix

GeO₂ films with germanium nanocrystals (NCs) were deposited from supersaturated GeO vapor with subsequent dissociation on Ge:GeO₂. The films were studied using photoluminescence (PL), Raman scattering, IRspectroscopy techniques. Ge NCs in initial film have sizes about 6–8 nm and have no visible PL signal. The broad green-red PL peak was detected in Ge:GeO₂ films after thermal annealings. According to effective mass approach, maximum of PL signal from such relatively big Ge NCs should be in IR region. The experimentally observed PL signal is presumably originated due to quasi-direct L ₁-L ₃’ optical transitions “folded” in germanium NCs. The article is published in the original.     

Photoluminescence of f-centers in films of anodic alumina

Results are reported from a study of the optical properties of porous alumina films obtained by anodizing in a water solution of sulfuric acid and modified by thermal annealing in air at T ≥ 850°C. A comparative analysis of the data shows that the near-UV and visible photoluminescence of alumina anodized in a sulfuric acid solution is caused primarily by oxygen divacancies (F₂, F₂⁺ _2^{+} , and F₂^{2 +} _2^{2 + } centers), while sulfate ions have little effect on the luminescence properties of anodic alumina in this spectral range.