Influence of Measurement Geometry and Blank on Absolute Measurements of Photoluminescence Quantum Yields of Scattering Luminescent Films

IF 6.7 1区 化学 Q1 CHEMISTRY, ANALYTICAL Analytical Chemistry Pub Date : 2025-03-07 DOI:10.1021/acs.analchem.4c06726
Florian Frenzel, Saskia Fiedler, Ahmad Bardan, Arne Güttler, Christian Würth, Ute Resch-Genger
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Abstract

For a series of 500 μm-thick polyurethane films containing different concentrations of luminescent and scattering YAG:Ce microparticles, we systematically explored and quantified pitfalls of absolute measurements of photoluminescence quantum yields (Φf) for often employed integrating sphere (IS) geometries, where the sample is placed either on a sample holder at the bottom of the IS surface or mounted in the IS center. Thereby, the influence of detection and illumination geometry and sample position was examined using blanks with various scattering properties for measuring the number of photons absorbed by the sample. Our results reveal that (i) setup configurations where the scattering sample is mounted in the IS center and (ii) transparent blanks can introduce systematic errors in absolute Φf measurements. For strongly scattering, luminescent samples, this can result in either an under- or overestimation of the absorbed photon flux and hence an under- or overestimation of Φf. The size of these uncertainties depends on the scattering properties of the sample and instrument parameters, such as sample position, IS size, wavelength-dependent reflectivity of the IS surface coating, and port configuration. For accurate and reliable absolute Φf measurements, we recommend (i) a blank with scattering properties closely matching those of the sample to realize similar distributions of the diffusely scattered excitation photons within the IS, and (ii) a sufficiently high sample absorption at the excitation wavelength. For IS setups with center-mounted samples, measurement geometries should be utilized that prevent the loss of excitation photons by reflections from the sample out of the IS.

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测量几何形状和空白对散射发光薄膜光致发光量子产率绝对测量的影响
对于一系列500 μm厚的聚氨酯薄膜,其中含有不同浓度的发光和散射YAG:Ce微粒,我们系统地探索和量化了通常采用积分球(IS)几何形状的光致发光量子产率的绝对测量陷阱(Φf),其中样品放置在IS表面底部的样品架上或安装在IS中心。因此,检测和照明几何形状和样品位置的影响进行了研究,使用具有不同散射特性的空白来测量被样品吸收的光子数。我们的研究结果表明:(i)散射样品安装在is中心的设置配置和(ii)透明空白会在绝对Φf测量中引入系统误差。对于强散射的发光样品,这可能导致吸收光子通量的低估或高估,从而导致Φf的低估或高估。这些不确定性的大小取决于样品的散射特性和仪器参数,如样品位置、IS尺寸、IS表面涂层的波长相关反射率和端口配置。为了精确可靠的绝对Φf测量,我们建议(i)具有与样品散射特性密切匹配的空白,以实现IS内扩散散射的激发光子的相似分布,以及(ii)在激发波长处具有足够高的样品吸收率。对于中心安装样品的IS设置,应使用测量几何形状,以防止样品反射出IS而损失激发光子。
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来源期刊
Analytical Chemistry
Analytical Chemistry 化学-分析化学
CiteScore
12.10
自引率
12.20%
发文量
1949
审稿时长
1.4 months
期刊介绍: Analytical Chemistry, a peer-reviewed research journal, focuses on disseminating new and original knowledge across all branches of analytical chemistry. Fundamental articles may explore general principles of chemical measurement science and need not directly address existing or potential analytical methodology. They can be entirely theoretical or report experimental results. Contributions may cover various phases of analytical operations, including sampling, bioanalysis, electrochemistry, mass spectrometry, microscale and nanoscale systems, environmental analysis, separations, spectroscopy, chemical reactions and selectivity, instrumentation, imaging, surface analysis, and data processing. Papers discussing known analytical methods should present a significant, original application of the method, a notable improvement, or results on an important analyte.
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