部分土壤重金属可见-近红外反射光谱特征及机理研究

测量重金属化合物氯化铬(CrCl₃)、氯化铜(CuCl₂)、氯化锌(ZnCl₂)的可见-近红外反射光谱(VNIRS),将重金属反射光谱与重金属元素的核外电子排布式联系起来,观察重金属化合物的反射光谱特征;结合晶体场理论分析重金属的特征反射峰出现的波段位置和原因。以湖北大冶地区土壤样品为例,向土样中添加不同浓度梯度的CrCl₃,CuCl₂和ZnCl₂并测定其可见-近红外反射光谱,研究不同种类不同浓度的重金属对土壤反射光谱的影响。对样本的反射光谱进行不同光谱预处理,探究重金属浓度与土壤反射光谱之间的线性相关关系及显著相关(p<0.05)波段出现的位置和潜在机理。结果表明,重金属化合物CrCl₃,CuCl₂和ZnCl₂在可见光-短波近红外波段范围内的反射光谱特征与重金属元素3d轨道上的电子填充状态有关。添加入土壤中的重金属化合物影响了土壤的可见-近红外反射光谱,其浓度与土壤反射光谱之间整体呈负相关,最大负相关系数分别为-0.788,-0.880和-0.824。样品反射光谱经不同预处理后,重金属浓度与土壤反射光谱之间的线性相关关系有所变化,显著相关波段信息更加丰富。研究表明,重金属的可见-近红外反射光谱与重金属的电子结构紧密相关,可见-近红外反射光谱技术可以检测到土壤中较高浓度重金属的存在,该技术在快速高效、无损低耗地预测土壤重金属元素含量方面拥有巨大潜力。基于部分重金属化合物的可见-近红外反射光谱特征,结合晶体场理论为土壤重金属的定性和定量反射光谱分析提供了理论依据和实验参考。     

Improved performance of a crystalline silicon solar cell based on ZnO/PS anti-reflection coating layers

A porous silicon (PS) layer was prepared by photoelectrochemical etching (PECE), and a zinc oxide (ZnO) film was deposited on a PS layer using a radio frequency (RF) sputtering system. The surface morphology of the PS and ZnO/PS layers was characterised using scanning electron microscopy (SEM). Nano-pores were produced in the PS layer with an average diameter of 5.7 nm, which increased the porosity to 91%. X-ray diffraction (XRD) of the ZnO/PS layers shows that the ZnO film is highly oriented along the c-axis perpendicular to the PS layer. The average crystallite size of the PS and ZnO/PS layers are 17.06 and 17.94 nm, respectively. The photoluminescence (PL) emission spectra of the ZnO/PS layers present three emission peaks, two peaks located at 387.5 and 605 nm due to the ZnO nanocrystalline film and a third located at 637.5 nm due to nanocrystalline PS. Raman measurements of the ZnO/PS layers were performed at room temperature (RT) and indicate that a high-quality ZnO nanocrystalline film was formed. Optical reflectance for all the layers was obtained using an optical reflectometer. The lowest effective reflectance was obtained for the ZnO/PS layers. The fabrication of crystalline silicon (c-Si) solar cells based on the ZnO/PS anti-reflection coating (ARC) layers was performed. The I–V characteristics of the solar cells were studied under 100 mW/cm² illumination conditions. The ZnO/PS layers were found to be an excellent ARC and to exhibit exceptional light-trapping at wavelengths ranging from 400 to 1000 nm, which led to a high efficiency of the c-Si solar cell of 18.15%. The ZnO/PS ARC layers enhance and increase the efficiency of the c-Si solar cell. In this paper, the fabrication processes of the c-Si solar cell with ZnO/PS ARC layers are an attractive and promising technique to produce high-efficiency and low-cost of c-Si solar cells.     

Low-porosity porous silicon nanostructures on monocrystalline silicon solar cells

In this work we present a study of low-porosity porous silicon (PS) nanostructures stain etched on monocrystalline silicon solar cells. The PS layers reduce the reflectance, improve the diffusion of dopants by rapid thermal processes, and increase the homogeneity of the sheet resistance. Some samples were subjected to chemical oxidation in HNO₃ to reduce the porosity of the surface layer. After the diffusion process, deposition of a SiN_x antireflection layer, and screen printing of the samples, an efficiency of 15.5% is obtained for low-porosity PS solar cells, compared with an efficiency of 10.0% for standard PS cells and 14.9% for the reference Cz cells.     

Comparative study of the oxidation of thin porous silicon layers studied by reflectometry, spectroscopic ellipsometry and secondary ion mass spectroscopy

We present a systematic study on ultrathin porous silicon (PS) layers (40–120 nm) of different porosities, formed by electrochemical etching and followed by thermal oxidation treatment (300°C and 600°C) and by electrochemical oxidation. The oxidised and non-oxidised PS layers have been analysed by spectroscopic reflectometry (SR), spectroscopic ellipsometry (SE) and secondary ion mass spectroscopy (SIMS). The SR and SE spectra were fitted by a multiparameter fit program and the composition and the thickness of the PS layers were evaluated by different optical models. PS layers, formed electrochemically in the outermost layer of a p/n⁺ monocrystalline silicon junction were successfully evaluated using a gradient porosity optical model. The non-oxidised PS, formed in p-type silicon, can be well described by a simple optical model (one-layer of two-components, silicon and voids). The spectra of the oxidised PS layers can be fitted better using an optical model with three interdependent components (crystalline-silicon, silicon-dioxide, voids). The SIMS results give a strong support for the optical model used for SR and SE.     

Thermal annealing dependence of some optical properties of plasma-modified porous silicon

The photoluminescence and reflectance of porous silicon (PS) with and without hydrocarbon (CH_x) deposition fabricated by plasma enhanced chemical vapour deposition (PECVD) technique have been investigated. The PS samples were then, annealed at temperatures between 200 and 800 °C. The influence of thermal annealing on optical properties of the hydrocarbon layer/porous silicon/silicon structure (CH_x/PS/Si) was studied by means of photoluminescence (PL) measurements, reflectivity and ellipsometry spectroscopy. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy. Photoluminescence and reflectance measurements were carried out before and after annealing on the carbonized samples for wavelengths between 250 and 1200 nm. A reduction of the reflectance in the ultraviolet region of the spectrum was observed for the hydrocarbon deposited polished silicon samples but an opposite behaviour was found in the case of the CH_x/PS ones. From the comparison of the photoluminescence and reflectance spectra, it was found that most of the contribution of the PL in the porous silicon came from its upper interface. The PL and reflectance spectra were found to be opposite to one another. Increasing the annealing temperature reduced the PL intensity and an increase in the ultraviolet reflectance was observed. These observations, consistent with a surface dominated emission process, suggest that the surface state of the PS is the principal determinant of the PL spectrum and the PL efficiency.     

The Influence of Immersion of Porous Silicon in Aqueous Solutions of Fe(NO<Subscript>3</Subscript>)<Subscript>3</Subscript> on Photoluminescence during Long Storage

The interaction of porous silicon (PS) with aqueous solutions of Fe(NO₃)₃ with different molar (M) concentrations causes introduction of iron ions into silicon pores (PS–Fe), formation of adsorbed iron coatings with different thicknesses, and an increase in the stability of PS layers, which is important for development of device structures based of PS. To treat PS layers with solutions by the immersion method, it is necessary to determine how this affects the spectral composition and intensity of photoluminescence (PL), as well as the kinetics of PL changes during long storage under atmospheric conditions. Upon treatment of freshly prepared PS by immersion into in a Fe(NO₃)₃ aqueous solution, it was found that, after short-term storage (up to 5 days) of the PS samples, the PL intensity increases by 7.5 and 3–3.6 times at low (0.2 M) and high (0.7–0.8 M) concentrations of Fe(NO₃)₃, respectively, compared to the PL intensity of an untreated PS layer. After long-term storage (4 months), the PL intensity of PS–Fe samples with concentrations of 0.1–0.2 and 0.7–0.8 M was observed to considerably increase (by 8–18 times) with unchanged position of the PL peak with respect to untreated PS. However, at the Fe(NO₃)₃ concentration of 0.3 М, the PL intensity decreases and the PL peak shifts to the blue, which is explained by incomplete coverage of the PS surface by an adsorbed iron layer. The kinetics of PL spectra during long-term storage is analyzed, and a model is proposed to explain the PL intensity and spectral composition.     

不同浓度稀土溶液的反射波谱特征研究

波谱吸收特征一般和物质成分具有密切联系,其中描述波谱吸收特征的参数——波谱吸收深度可以作为一种定量评估样品化学组成的参数。 波谱吸收特征及化学特征之间的相关性研究已经在土壤学、 矿物学及植被科学等领域得到了证实,但是针对稀土元素及其化学特征之间的相关性研究目前还未开展相关工作。 为开展此方面的研究,针对赣南稀土矿区采集的10个不同浓度的稀土溶液样品,运用便携式地物波谱仪和等离子质谱仪分别获取了其波谱特征和稀土总浓度,研究结果表明稀土溶液呈现出水体和稀土氧化物的混合波谱特性,在可见光-近红外波段有6个明显的稀土特征吸收谷。 针对这6个特征吸收谷,运用原始波谱与纯水波谱比值的方法计算得出的波谱吸收深度和稀土总浓度进行线性回归分析,表明两者高度线性相关,由此建立了稀土浓度定量评估模型。 这一研究提供了一种间接评估溶液中稀土浓度的新方法,并且为稀土元素高光谱信息提取研究提供了理论基础。     

Thin film polymer photonics: Spin cast distributed Bragg reflectors and chirped polymer structures

Polymer based photonic structures were produced by spin coating up to 50 alternating layers of polystyrene (PS) and poly(vinylpyrrolidone) (PVP) from mutually exclusive (orthogonal) solvents. The resulting thin film multi-layer structures were studied using a simple optical reflectivity apparatus and were shown to have narrow (10-20nm wide) reflectance bands in the visible region. The position of the reflectance bands was controlled by varying the spin speed used during production of the multi-layers and peak reflectance values of 55% were obtained for samples containing 50 layers. The results were shown to be in agreement with modified optical transfer matrix method calculations which include the effects of diffuse polymer interfaces. This modelling approach revealed that the width of the polymer/polymer interfaces formed by spin coating was in the range 15-20nm. Data and calculations were also obtained for chirped polymer photonic structures. These results were also shown to be in good agreement. These experiments demonstrate that simple processing methods such as spin coating can be used to produce organic photonic structures with tailored optical properties.     

土壤氧化铁的高光谱响应研究

通过分析野外采集的13个土种的不同氧化铁含量原始土样和人工配制不同氧化铁含量土样的高光谱特征,研究了氧化铁对土壤反射率、土壤线参数、土壤有机质高光谱特征、土壤反射率光谱曲线形态的影响。研究结果表明,随氧化铁含量的增加,350～570 nm波段反射率降低,570～2 500 nm波段的反射率增加,氧化铁去除量与反射率变化量之间的相关性不明显;氧化铁含量与土壤线斜率呈线性负相关,与截距呈线性正相关,且均达到极显著相关水平,表明利用土壤线参数反演氧化铁含量具有可行性;在622～851 nm波段,氧化铁对有机质的高光谱特征具有明显的抑制作用;通过去包络线和统计F值与光谱角值表明,氧化铁对土壤反射光谱曲线形态有影响。     

Large forbidden band in one-dimensional multi-layered structure containing exponentially graded materials

In the present communication, we have presented band spectra and reflectance properties of one-dimensional multi-layered structure containing dielectric exponentially graded and simple dielectric layers. This study has been performed theoretically by using transfer matrix method. In this paper we have taken the multi-layered structure where refractive index of odd layers is varying continuously along the direction perpendicular to the surface of the layer in exponential form. The effect of the graded profiles are studied and compared with the conventional multi-layered structure of suitable contrast of refractive indices in detail. In this study the materials are considered as non-magnetic and layers other than the graded are taken to be homogeneous and isotropic dielectric medium of constant refractive index. It has been found that the introduction of graded layers enhanced the forbidden band gaps and affects the reflectance of electromagnetic wave spectra significantly. By changing the grading profiles and the contrast, we obtained the forbidden band gaps and the reflectance of such structural change accordingly. Therefore, introducing a graded exponential layer of dielectric in the one-dimensional multi-layered structure provides possible mechanism for enhancing the reflectance as well as the forbidden gap in the optical region. Such multi-layered structure may be useful in the design of a broadband filter.     

Reconstruction of absorber concentrations in a two-layer structure by use of multidistance time-resolved reflectance spectroscopy

The characterization of a two-layer structure was investigated by use of time-resolved reflectance over a wide spectral range. We exploited the nonlinear dependence of the measured spectra on the upper-and lower-layer properties to formulate an algorithm for the recovery of absorber concentrations in both layers. The method assumes that the spectral features of the key absorbers are known, but it does not rely on a priori knowledge of the layer thickness. Phantom tests confirmed the accuracy of the estimate of the absorber concentrations to within 10% for thickness values ranging from 0.3 to 1.2 cm. Multidistance absorption spectra from 610 to 1000 nm were obtained in vivo from the forearms of human subjects, allowing us to estimate the concentration of key tissue constituents in a two-layer approximation. Good agreement between the reconstructed spectra and the experimental data taken from two volunteers with opposite predominance of adipose and muscular tissues demonstrated the validity of this approach.     

土壤水分去除算法的田间原位光谱反演棉田有机质

田间原位可见-近红外光谱(VIS-NIR)能够有效的提高土壤属性的检测效率,但由于原位土壤中水分因素的影响,土壤属性的预测精度很难达到预期。如何有效去除土壤中的水分对土壤其他属性光谱预测的影响,是利用田间原位光谱高精度预测土壤属性所面临的难题,也是土壤光谱技术由室内转向田间的突破口。该问题的有效解决,可减除土壤样品的采集与室内预处理等过程,实现土壤属性的田间原位光谱测定。以新疆南部地区阿拉尔垦区十二团棉田为研究区,采用网格采样法共采集了116个0～20 cm深度的表层土壤样品,剔除1个异常值样品,得到115个有用样品,利用SR-3500型便携式地物光谱仪采集了231个样点的田间原位光谱数据,土样经风干、研磨和过筛等处理后测定其室内光谱和有机质含量。利用Kennard-Stone算法将115个土样分为69个转换子集及46个预测集,采用外部参数正交化法(EPO)、光谱直接转换法(DS)及光谱间接转换法(PDS)三种去除水分算法结合原位光谱反射率(R)、反射率一阶微分(R′)、反射率对数(LOG(R))以及反射率倒数(1/R)四种数学变换方式,运用随机森林(RF)模型进行不同组合模型的构建及精度评价。结果表明：(1)土壤有机质含量越高,土壤光谱反射率越低。土壤田间原位光谱反射率低于土壤室内光谱反射率;(2)室内光谱反射率与土壤有机质含量之间的相关性大于田间原位光谱,室内光谱经一阶微分变换后与土壤有机质含量之间的相关性显著提升。(3)土壤室内光谱反射率模型预测精度(R2=0.86, RPD=2.08, RMSE=1.55 g·kg-1, MAPE= 0.14)高于田间原位光谱反射率模型(R2=0.71, RPD=1.49, RMSE=2.17 g·kg-1, MAPE=0.20)。在去除水分算法模型中,以EPO一阶微分模型去除水分效果最好,决定系数R2由0.71提高到0.83,RPD由1.49提高到2.04,RMSE由2.17 g·kg-1降低至1.58 g·kg-1,MAPE由0.20降低至0.14。本研究实现了去除土壤水分因素的影响,提高了田间原位光谱预测土壤有机质的精度,为南疆棉田大尺度土壤有机质的预测及土壤肥力的评价提供了重要的参考。     

Positive and Negative Pulse Etching Method of Porous Silicon Fabrication

We present a new method in which both positive and negative pulses are used to etch silicon for fabrication of porous silicon （PS） monolayer. The optical thickness and morphology of PS monolayer fabricated with different negative pulse voltages are investigated by means of reflectance spectra, scanning electron microscopy and photoluminescence spectra. It is found that with this method the PS monolayer is thicker and more uniform. The micropores also appear to be more regular than those made by common positive pulse etching. This phenomenon is attributed to the vertical etching effect of the PS monolayer being strengthened while lateral etching process is restrained. The explanation we propose is that negative pulse can help the hydrogen cations （H^＋） in the electrolyte move into the micropores of PS monolayer. These H^＋ ions combine with the Si atoms on the wall of new-formed micropores, leading to formation of Si-H bonds. The formation of Silt bonds results in a hole depletion layer near the micropore wall surface, which decreases hole density on the surface, preventing the micropore wall from being eroded laterally by F^- anions. Therefore during the positive pulse period the etching reaction occurs exclusively only at the bottom of the micropores where lots of holes are provided by the anode.     

基于反射光谱特性的土壤分类研究

选取中国松嫩平原吉林省农安县主要土壤(黑土、黑钙土、草甸土、风砂土、冲积土)室内光谱反射率作为研究对象,利用去包络线方法提取反射光谱特征指标,作为输入变量建立BP神经网络模型,进行土壤分类研究,探索利用表层土壤反射光谱特性进行土壤分类的可行性。结果表明:(1)包络线去除后的曲线使土壤可见光近红外波段的吸收特征显著增强;农安县不同土壤在400～2500nm范围内主要有5个光谱吸收谷,前2个吸收谷主要是由于土壤有机质、铁及土壤机械组成引起的,后3个是土壤水分吸收光谱能量引起的;不同土壤类型反射光谱的差异主要表现在前2个吸收谷。(2)由于输入变量的选取客观准确,基于前2个吸收谷形状特征的BP神经网络模型的土壤分类精度显著优于以反射率或5个吸收谷形状特征为输入变量的模型,可以用于土壤分类。     

Optical properties of a stack of layers of a cholesteric liquid crystal and an isotropic medium

Optical properties of a stack consisting of layers of a cholesteric liquid crystal (CLC) and an isotropic medium are investigated. The problem is solved using the modified Ambartsumyan layer-summation method. Particular features of reflectance spectra of this system are studied. It is shown that, in contrast to a single CLC layer, this system exhibits multiple photonic band gaps. There are two types of photonic band gaps: selective and nonselective with respect to polarization of the incident light. It is shown that eigenpolarizations in the system generally coincide with quasi-orthogonal quasi-circular polarizations, except for regions that are selective with respect to polarization of the diffractive reflection. It is shown that, for an even number of layers, the system under consideration is nonreciprocal and can function as an optical diode. The influence of thickness of CLC sublayers, angle of incidence, local dielectric anisotropy of CLC layers, refractive indices and thicknesses of layers of an isotropic media on reflectance spectra and other optical characteristics of the system is investigated.     

Spinodal wrinkling in thin-film poly(ethylene oxide)/polystyrene bilayers

Optical microscopy and atomic force microscopy were used to study a novel roughness-induced wrinkling instability in thin-film bilayers of poly(ethylene oxide) (PEO) and polystyrene (PS). The observed wrinkling morphology is manifested as a periodic undulation at the surface of the samples and occurs when the bilayers are heated above the melting temperature of the semi crystalline PEO (T_m = 63 ) layer. During the wrinkling of the glassy PS capping layers the system selects a characteristic wavelength that has the largest amplitude growth rate. This initial wavelength is shown to increase monotonically with increasing thickness of the PEO layer. We also show that for a given PEO film thickness, the wavelength can be varied independently by changing the thickness of the PS capping layers. A model based upon a simple linear stability analysis was developed to analyse the data collected for the PS and PEO film thickness dependences of the fastest growing wavelength in the system. The predictions of this theory are that the strain induced in the PS layer caused by changes in the area of the PEO/PS interface during the melting of the PEO are sufficient to drive the wrinkling instability. A consideration of the mechanical response of the PEO and PS layers to the deformations caused by wrinkling then allows us to use this simple theory to predict the fastest growing wavelength in the system.     

近红外波段二类水体悬浮物生物光学反演模型研究

通过野外高光谱仪对二类混浊水体进行光谱测量,分析了400～1 200 nm范围内的水体光谱特性。显示高浓度悬浮物含量对水体总的反射率贡献较大,在近红外波段处的808和1 067 nm存在较为明显的悬浮物反射峰。基于对水体固有光学特性参数在近红外波段范围内的简化条件,建立了反演悬浮物浓度的生物光学模型经验公式,并通过与线性和指数反演公式的对比,进行了模型反演精度评价。分析结果表明,基于近红外波段的生物光学模型反演精度较高,可有效地提取二类混浊水体的悬浮物浓度信息。     

Hyperspectral estimation of soil organic matter based on different spectral preprocessing techniques

In this study, the potentiality of visible and near-infrared reflectance spectroscopy to estimate soil organic matter was assessed. Six preprocessing methods were implemented to process the original spectra. The partial least-squares regression approach was also applied to construct predictive models and evaluate the optimal spectral preprocessing method. The significant wavelengths of soil organic matter were determined by using the correlation analysis and the partial least-squares regression analysis. The results were: (i) visible and near-infrared reflectance spectroscopy was proved to be an ideal approach in the soil organic matter estimation; (ii) different preprocessed spectra could improve their correlation with soil organic matter; the combination of first-order derivative and Savitzky–Golay smoothing method outperformed other preprocessing methods; (iii) the soil organic matter predictive models based on spectra processed by derivatives and Savitzky–Golay smoothing together presented a satisfactory accuracy, yielding the determination coefficient and root mean square error values of 0.986 and 0.077, respectively, for first-order derivative; and 0.973 and 0.105, respectively, for second-order derivative. The combination of first-order derivative and Savitzky–Golay smoothing was ultimately recommended the preferable preprocessing method; and (iv) the wavelengths of 417, 1853, 1000, and 2412?nm were determined as the significant wavelengths associated with soil organic matter. The study will provide a reference for the site specific management of agricultural inputs by using the visible and near-infrared reflectance spectroscopy technology.     

InAs/GaAs表面量子点的压电调制反射光谱研究

运用压电调制反射光谱(PzR)方法测量了在以GaAs(311)B为衬底的In_0.35Ga_0.65As模板上生长的InAs表面量子点结构的反射谱.在77K温度下，观察到了来自样品各个组成结构(包括表面量子点本身、被覆盖层覆盖的量子点、In_0.35Ga_0.65As模板以及GaAs衬底等)的调制信号.来自表面量子点本身的调制信号是多个清晰的调制峰.用一阶和三阶微分洛伦兹线形对PzR谱中对应结构的实验数据进行了拟合，精确确定了与样品的各个组成结构相对应的调制峰的能量位置.对不同样品PzR谱的差异进行了定性的说明. 关键词： 压电调制光谱 InAs/GaAs 表面量子点 洛伦兹线形拟合     

Effect of contact with air on the photoluminescence spectrum of porous silicon

A study has been made of the transformation of photoluminescence (PL) spectra of porous silicon (PS) induced by its ageing, including the early stages of contact with air. The sample was prepared under conditions that minimized this contact, and spectral measurements were carried out in a high vacuum or in liquid nitrogen. The PS PL spectra obtained under continuous measurement in high vacuum are always dominated by one emission band of PS nanoelements, which shifts toward shorter wavelengths with ageing by 150 nm. At 80 K, the band intensity is considerably higher than at 300 K, and this difference grows with ageing. Exposure of a sample to air for a few tens of seconds is long enough to strongly transform its time-resolved PL spectra, which is evidence of a change in the sample surface. The effect of immersion of PS samples in liquid nitrogen on PL spectra is associated not only with their cooling, but also with the field of adsorbed nitrogen molecules, whose influence becomes weaker with increasing thickness of the oxidized near-surface layer. The variation of the spectral properties and kinetics of the long-wavelength PS PL band with temperature, medium (liquid nitrogen or vacuum), and exposure time suggest that these factors affect carrier migration between silicon nanoelements.