Accessory for rapidly measuring time response of photoluminescence spectrum

Abstract

An accessory for rapidly measuring photoluminescence spectrum time response comprises a camera obscura, a reflection concave mirror set, a positioning sleeve, an optical fiber collimating mirror, an optical fiber and an optical fiber spectrometer, the reflection concave mirror set is fixedly arranged in the camera obscura, the optical fiber collimating mirror is arranged in the emergent direction of the reflection concave mirror and located outside the camera obscura, and the optical fiber spectrometer is arranged in the positioning sleeve. The front end of the optical fiber collimating mirror is fixed on the positioning sleeve, the rear end of the optical fiber collimating mirror is connected with an optical fiber, and the optical fiber is connected with the optical fiber spectrometer. The device has good universality, can be matched with a common commercial fluorescence spectrophotometer, and is convenient to use.

Description

Technical Field

[0001] This invention relates to the field of fluorescence spectroscopy measurement technology, and particularly to an accessory for rapidly measuring the time response of photoluminescence spectra. Background Technology

[0002] With the large-scale application of fluorescent materials in fields such as lighting and biomarking, an increasing number of fluorescent substances with diverse morphologies and luminescence mechanisms have been developed. To elucidate the luminescence mechanisms of these fluorescent substances and measure their fluorescence spectra, numerous devices distinct from standardized fluorescence spectrometers have been developed. For example, Ocean University of China developed a fiber optic coupler for commercial fluorescence spectrometers (CN200420098374), enabling the application of fiber optic fluorescence probes. Researchers at Dalian Maritime University developed a fiber optic-based fluorescence detector that allows the probe to be placed close to the microplastic particles being measured to study their fluorescence spectra (CN202410588592), a capability that is impossible with typical commercial spectrometers. Researchers at Beijing Zhuoli Hanguang Analytical Instruments Co., Ltd. combined optical fibers with silicon probes from commercial spectrometers, utilizing the micro-region detection characteristics of optical fibers to develop a multifunctional micro-fluorescence Raman spectrometer (CN202410560537). Furthermore, the portability and ease of assembly of fiber optic spectrometers have led to their increasing application in various fluorescence tests. Recently, researchers at Xi'an Jiaotong University developed a multifunctional spectrometer with a continuous light source based on a fiber optic spectrometer (CN202410585027).

[0003] Among numerous fluorescence assays, the time response of fluorescence spectroscopy is a crucial tool for studying the photoelectron transition dynamics in fluorescent materials. However, standardized fluorescence spectrometers based on silicon probes are generally limited to measuring the fluorescence time response at a single wavelength, such as the afterglow lifetime of the emission peak of some long-afterglow powders. Fiber optic spectrometers, utilizing CCD array detectors, possess the ability to rapidly respond to the entire spectral range.

[0004] Some older spectrometer models are outdated and discontinued, making after-sales service extremely inconvenient. New research methods, such as time response measurement of fluorescence spectroscopy, require additional configuration. Therefore, there is an urgent need to develop a universal accessory that can be matched with general commercial fluorescence spectrometers for rapid measurement of photoluminescence spectral time response, providing convenience for users conducting fluorescence dynamics research. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this utility model provides an accessory for rapidly measuring the time response of photoluminescence spectra. It has good versatility, can be matched with general commercial fluorescence spectrometers, and is easy to use.

[0006] The technical solution adopted by this utility model to solve its technical problem is:

[0007] An accessory for rapidly measuring the time response of photoluminescence spectra includes a dark box, a concave mirror assembly, a positioning sleeve, a fiber optic collimator, an optical fiber, and a fiber optic spectrometer. The concave mirror assembly is fixedly placed inside the dark box. The fiber optic collimator is positioned in the exit direction of the concave mirror and is located outside the dark box. The front end of the fiber optic collimator is fixed to the positioning sleeve, and the rear end of the fiber optic collimator is connected to an optical fiber, which is connected to the fiber optic spectrometer.

[0008] Furthermore, the positioning sleeve is equipped with a front and rear position adjustment component for adjusting the position of the fiber optic collimator and fixing it with positioning screws.

[0009] Furthermore, the fiber optic spectrometer includes a CCD array detector, which receives fiber optic signals.

[0010] The concave mirror assembly is made by depositing a thin aluminum film on a quartz glass plate with a specific curvature. The concave mirror is used to reflect a 12cm... 2 The fluorescence convergence area is 1 cm 2 The light spot is the size of a laser beam, and its energy focusing efficiency reaches 98%.

[0011] The lens barrel of the fiber collimator can be spirally extended and retracted, thereby changing the coupling efficiency of the fiber. The distance between the fiber collimator and the fiber terminal is 4-10mm, and the fiber coupling efficiency is 20-70%.

[0012] The optical fiber is a single or multiple bundles, with a single bundle diameter of 0.6-1.5 mm.

[0013] The fiber optic spectrometer has a wavelength operating range of 200-1400nm, a wavelength resolution of 1-2nm, and an integration time of 0.5ms-10000ms. The fiber optic spectrometer communicates with a computer signal acquisition unit.

[0014] The main advantages of this invention are: it has good versatility, can be matched with general commercial fluorescence spectrometers, and is easy to use. Attached Figure Description

[0015] Figure 1 This is an attached schematic diagram of the rapid measurement of the time response of photoluminescence spectra;

[0016] Figure 2 This is a schematic diagram of the photoluminescence spectroscopy time response test in a fluorescence spectrometer;

[0017] Figure 3 This is a schematic diagram of the sample holder F;

[0018] Figure 4 It is Ca 1-x Sr xAl2O4:Eu 2+ ,Dy 3+ Time response of long afterglow powder fluorescence spectrum.

[0019] The components include: 1. Dark box; 101. Reflective concave mirror assembly; 2. Positioning sleeve; 201. Positioning screw; 3. Fiber optic collimator; 4. Fiber optic cable; 5. Fiber optic spectrometer; A. Continuous light source; B. Light source monochromator; C. Sample chamber; D. Fluorescence monochromator; E. Fluorescence photodetector; F. Sample holder; G. Filter; 6. Base baffle; 601. Light transmission hole; 602. Clamp; 7. Rotating support; 8. Angle ruler; and 9. Cuvette. Detailed Implementation

[0020] The present invention will now be further described with reference to the accompanying drawings.

[0021] Reference Figures 1-4 An accessory for rapidly measuring the time response of photoluminescence spectra includes a dark box 1, a concave mirror assembly 101, a positioning sleeve 2, a fiber optic collimator 3, an optical fiber 4, and a fiber optic spectrometer 5. The concave mirror assembly 101 is fixedly placed inside the dark box 1. The fiber optic collimator 3 is arranged in the exit direction of the concave mirror 101 and is located outside the dark box 1. The front end of the fiber optic collimator 3 is fixed on the positioning sleeve 2, and the rear end of the fiber optic collimator 3 is connected to the optical fiber 4. The optical fiber 4 is connected to the fiber optic spectrometer 5.

[0022] Furthermore, the positioning sleeve 2 is provided with a front and rear position adjustment component for adjusting the position of the fiber collimator and fixing it with a positioning screw 201.

[0023] Furthermore, the fiber optic spectrometer includes a CCD array detector, which receives fiber optic signals.

[0024] The concave mirror assembly 101 is made by depositing a thin aluminum film on a quartz glass plate with a specific curvature. The concave mirror is used to reflect a 12cm... 2 The fluorescence convergence area is 1 cm 2 The light spot size is [size missing], and the energy focusing efficiency reaches 98%. The lens barrel of the fiber collimator 2 is spirally extendable, thereby changing the coupling efficiency of the fiber. The distance between the fiber collimator and the fiber terminal is adjustable from 4-10mm, and the fiber coupling efficiency is adjustable from 20-70%. The fiber optic cable 4 can be a single bundle or multiple bundles, with a single bundle diameter selectable from 0.6-1.5mm. The fiber optic spectrometer 5 has a wavelength operating range of 200-1400nm, a wavelength resolution of 1-2nm, and an integration time adjustable from 0.5ms-10000ms. The fiber optic spectrometer communicates with a computer signal acquisition unit.

[0025] like Figure 1As shown, a concave mirror assembly 101 is fixedly placed inside the main dark box 1 of the accessory. This concave mirror assembly is made of aluminum film coated on a quartz glass plate with a specific curvature, achieving an energy focusing efficiency of 98%. The main function of this concave mirror is to collect the fluorescence of the sample, allowing it to couple more efficiently into the optical fiber. After being focused by the concave mirror, the fluorescence enters the fiber collimator 3, whose front end is fixed to the positioning sleeve 2. Since the fluorescence still has a certain divergence angle after focusing, the size and position of the light spot are related. By adjusting the position of the fiber collimator by moving the sleeve back and forth and fixing it with the positioning screw 201, the light spot can be completely entered into the barrel of the fiber collimator, minimizing light loss. The barrel of the fiber collimator can be spirally extended and retracted to change the distance between the fiber terminal and the collimator lens, which is adjustable within the range of 4-10 mm. The fiber coupling efficiency is adjustable from 20-70%. The purpose of adjusting the fiber coupling efficiency is to prevent the light intensity entering the CCD detector in the fiber optic spectrometer 5 from saturating the detector and affecting the detection accuracy. The optical fiber 4 of this invention can be a single bundle or multiple bundles, with a single bundle diameter selectable from 0.6-1.5mm. The wavelength operating range of the optical fiber spectrometer used is 200-1100nm, the wavelength resolution is 1-2nm, the scanning time is adjustable from 0.5ms to 10000ms, and it can communicate with a computer signal acquisition unit.

[0026] Figure 2 This is a schematic diagram of the accessory installed on a commercial fluorescence spectrometer. The light source A of a commercial fluorescence spectrometer is typically a xenon lamp. The light passes through the monochromator B and enters the sample chamber C. The monochromatic excitation light illuminates the sample on the rotatable sample holder F. Since this accessory is a universal device compatible with most commercial fluorescence spectrometers, it must not disrupt the original functionality of the fluorescence spectrometer. The sample holder is designed to output fluorescence to either the spectrometer's original fluorescence photodetector or a fiber optic spectrometer. If the sample holder faces left (reflection direction), the excited fluorescence is output to the left onto the photoluminescence time-response accessory. If the sample holder faces right (reflection direction), the excited fluorescence is output to the right, passes through the fluorescence monochromator D, and illuminates the spectrometer's original fluorescence photodetector E.

[0027] like Figure 3 As shown, the rotatable sample holder F consists of a base baffle 6, a rotating support 7, an angle scale 8, and a cuvette 9. The base baffle has a light-transmitting hole 601. The base baffle is connected to the rotating support by fastening screws. The rotating support has an angle scale and can rotate 360° with an angle scale accuracy of 5-10°, used to adjust the fluorescence output direction. When measuring the fluorescence spectrum time response, as... Figure 2 As shown, the fluorescence diverges to the left. After passing through the filter G and the concave mirror assembly, the concave mirror reflects the fluorescence at a distance of 12cm. 2 The fluorescence convergence area is 1 cm 2A light spot of a certain size illuminates the fiber optic collimator. The final fluorescence intensity is then detected by the CCD detector of the fiber optic spectrometer. When the fiber optic spectrometer is set to a scanning time of Δt and continuously scanned, it outputs a fluorescence spectrum of 200-1100 nm every Δt, thus obtaining a fluorescence spectral time response map with a time resolution of Δt. Analyzing the speed of the spectral response can provide kinetic information related to photoelectron transitions and emission in the fluorescent material.

[0028] In this embodiment, the time response of the photoluminescence spectrum is divided into excitation response and decay response. This embodiment of the invention uses a Fluoro Max-4 commercial fluorescence spectrometer to measure Ca. 1-x Sr x Al2O4:Eu 2+ ,Dy 3+ The decay response of the photoluminescence spectrum of long-afterglow powder, the test structure is as follows Figure 2 As shown in the attached document. Figure 1 As shown, the rotatable sample holder is as follows Figure 3 As shown.

[0029] First, adjust the light intensity. For example... Figure 3 As shown, the fluorescent powder is first loaded into a fused-bonded cuvette 9 (45mm long, 12.5mm wide, and 3mm thick). The cuvette is clamped between the base baffle 6 and the clamp 602, and the entire assembly is placed on the rotating support 7 and secured with screws. The corner scale 8 has an accuracy of 5°. Rotating the sample holder to a 60° left-facing position avoids direct reflection of the excitation light into the optical fiber. A 390nm high-pass filter is used to filter out the influence of the incident light. The scanning time of the fiber optic spectrometer is set to 0.5ms, and the scanning wavelength range is 500-800nm. Before measurement, the sample is kept dark in the sample chamber for 24 hours. The powder sample is irradiated with 350nm blue light generated by a xenon lamp and monochromator, and the fluorescence spectrum is scanned using the fiber optic spectrometer. Figure 4 The strongest peak in the spectrum can be seen at 593 nm. Adjusting the position of the fiber collimator, i.e., adjusting the fiber coupling efficiency, ensures that the light intensity at the 593 nm peak reaches 90% of the fiber optic spectrometer's saturation value. In this embodiment, this value is approximately 55,000 counts. After adjustment, continue illumination for about 5 minutes, then close the excitation slit and immediately begin saving the spectral data for each scan at 0.5 ms intervals. Figure 4 As shown, the spectrometer outputs a set of fluorescence spectra every 0.5 ms. It can be observed that Ca3Ti2O7:Pr 3+The long-afterglow powder emits orange fluorescence, with a main peak at 593 nm and a "shoulder" at a longer wavelength. This "shoulder" red-shifts over time. Gaussian peak analysis reveals that the emission spectrum actually contains two large fluorescence peaks, corresponding to photoelectron transitions at two primary energy levels. The main peak at 593 nm remains constant over time, while the secondary peak red-shifts. This indicates that the structures of these two primary energy levels are necessarily different, leading to significant differences in the number and behavior of charge carriers at these levels. This provides a basis for the study of Ca3Ti2O7:Pr 3+ The luminescence mechanism of long-afterglow powders provides important data.

Claims

1. An accessory for rapidly measuring the time response of a photoluminescence spectrum, characterized in that, The accessories include a dark box, a concave mirror assembly, a positioning sleeve, a fiber optic collimator, an optical fiber, and a fiber optic spectrometer. The concave mirror assembly is fixedly placed inside the dark box. The fiber optic collimator is positioned in the exit direction of the concave mirror and is located outside the dark box. The front end of the fiber optic collimator is fixed to the positioning sleeve, and the rear end of the fiber optic collimator is connected to an optical fiber, which is connected to the fiber optic spectrometer.

2. The accessory for rapidly measuring the time response of a photoluminescence spectrum as described in claim 1, characterized in that, The positioning sleeve is equipped with a front and rear position adjustment component for adjusting the position of the fiber optic collimator and fixing it with positioning screws.

3. An accessory for rapidly measuring the time response of a photoluminescence spectrum as described in claim 1 or 2, characterized in that, The fiber optic spectrometer includes a CCD array detector, which receives fiber optic signals.

4. An accessory for rapidly measuring the time response of a photoluminescence spectrum as described in claim 1 or 2, characterized in that, The concave mirror assembly is made by depositing a thin aluminum film on a quartz glass plate with a specific curvature. The concave mirror is used to reflect a 12cm... 2 The fluorescence convergence area is 1 cm 2 The light spot is the size of a laser beam, and its energy focusing efficiency reaches 98%.

5. An accessory for rapidly measuring the time response of a photoluminescence spectrum as described in claim 1 or 2, characterized in that, The lens barrel of the fiber collimator can be spirally extended and retracted, thereby changing the coupling efficiency of the fiber. The distance between the fiber collimator and the fiber terminal is 4-10mm, and the fiber coupling efficiency is 20-70%.

6. An accessory for rapidly measuring the time response of a photoluminescence spectrum as described in claim 1 or 2, characterized in that, The optical fiber is a single or multiple bundles, with a single bundle diameter of 0.6-1.5 mm.

7. An accessory for rapidly measuring the time response of a photoluminescence spectrum as described in claim 1 or 2, characterized in that, The fiber optic spectrometer has a wavelength operating range of 200-1400nm, a wavelength resolution of 1-2nm, and an integration time of 0.5ms-10000ms. The fiber optic spectrometer communicates with a computer signal acquisition unit.

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