CN113251916A - Femtosecond interference scattering microscopic imaging system and measuring method - Google Patents

Femtosecond interference scattering microscopic imaging system and measuring method Download PDF

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CN113251916A
CN113251916A CN202110510123.XA CN202110510123A CN113251916A CN 113251916 A CN113251916 A CN 113251916A CN 202110510123 A CN202110510123 A CN 202110510123A CN 113251916 A CN113251916 A CN 113251916A
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femtosecond
interference
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CN113251916B (en
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康斌
吕品田
徐静娟
陈洪渊
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Beijing Zhuoli Hanguang Analytical Instrument Co ltd
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Nanjing University
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    • G01MEASURING; TESTING
    • G01BMEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B9/00Measuring instruments characterised by the use of optical techniques
    • G01B9/04Measuring microscopes
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    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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Abstract

The invention discloses a femtosecond interference scattering microscopic imaging system and a measuring method, belonging to the technical field of ultrafast optical imaging. The invention combines the ultrafast spectrum technology and the interference scattering microscopic imaging technology, not only has femtosecond time resolution and nanoscale three-dimensional spatial resolution, but also utilizes a partial reflection spatial filter to modulate an interference light field, obviously improves the transient signal intensity, is beneficial to measuring extremely weak transient signals, and further realizes the measurement of carrier relaxation and migration dynamics of a sample. Compared with the traditional ultrafast imaging technology, the method has the advantages of high speed, high flux, large visual field, good compatibility, no need of phase locking, simultaneous measurement of multiple pixels and the like.

Description

Femtosecond interference scattering microscopic imaging system and measuring method
Technical Field
The invention relates to an ultrafast optical imaging technology, in particular to a femtosecond interference scattering microscopic imaging system (Femto-iSAT) and a measuring method.
Background
In the fields of energy, catalysis, sensing and the like, understanding the performance difference and the internal reasons of different materials is helpful for breaking through the key scientific problems and technical bottlenecks. The function and activity of a material is closely related to its internal carrier relaxation and transport. However, the conventional ultrafast spectroscopy is not suitable for measuring different micro-regions of micro-nano particles or materials, because it lacks spatial resolution capability, and can only obtain ensemble average results.
In recent years, the combination of ultrafast spectroscopy and imaging techniques has resulted in a variety of ultrafast imaging techniques, such as ultrafast electron microscopy, ultrafast X-ray diffraction, ultrafast photoemission microscopy, and ultrafast scanning tunneling microscopy. In contrast, the "ultrafast optical microscope" only needs to be combined with the ultrafast spectrum technology and the optical microscope, is easier to implement in a laboratory, and has lower cost. Several types of typical ultrafast imaging methods have been developed in the industry, including confocal scanning and lock-in amplification based transient absorption imaging and wide-field transmission/reflection based ultrafast imaging. Although the above method can obtain the kinetic information of carrier relaxation and migration in time and space at the same time, the obtained transient signal is very weak, usually 10-5An order of magnitude. Point scanning type imaging needs to extract weak transient signals by means of a lock-in amplifier, and instruments are complex; wide field imaging requires long time accumulation of signals to improve signal strength and longer measurement time. However, merely increasing the pump optical energy density to boost the transient signal is also susceptible to interference from thermal effects. In order to overcome the above limitations, a new method for detecting weak signals needs to be sought by breaking through the detection mode of the conventional ultrafast spectrum.
The interference effect can effectively amplify and extract weak optical signals. Imaging methods based on interference effects have been widely used for steady-state detection and sensing of single molecules, single particles, due to their extremely high sensitivity. For example, interferometric scatter Imaging (iSCAT) is a method that utilizes a known reference light field and a sample weak scattered light field to generate interference, can extract a scattering signal of the sample according to the intensity and phase of the interference, and has nanometer-scale spatial resolution in the Z-axis direction. Like transient absorption and reflection, interference effects can also be combined with ultrafast spectroscopy to achieve time-resolved iSAT. By means of interference effect amplification, transient signals under the same pumping condition are expected to be improved by several orders of magnitude compared with the traditional method. Currently, two problems remain to be solved: first, how to improve the temporal resolution of the iSCAT system to the femtosecond level; secondly, how to modulate the interference optical field to maximize the effect of interference effect.
Disclosure of Invention
The invention aims to provide a Femto-iSCAT (Femto-iSCAT) system and a measuring method aiming at the defects of the prior art, which not only has Femto-second time resolution and nanometer three-dimensional spatial resolution, but also obviously improves the transient signal intensity by utilizing a partial reflection spatial filter to carry out interference light field modulation, and realizes the measurement of extremely weak transient signals.
In order to achieve the purpose, the invention provides the following technical scheme:
a femtosecond interference scattering microscopic imaging system comprises a femtosecond laser, a first spectroscope, an excitation module, a detection module, an objective lens, a sample stage, a second spectroscope, an imaging module and a control and processing module;
the femtosecond laser generates femtosecond laser pulses, the femtosecond laser pulses are divided into reflected beams and transmitted beams by a first spectroscope, the reflected beams pass through an excitation module, wide-field pumping light spots are generated on a sample at the sample stage, and the sample in a pumping area is excited; the transmitted light passes through a detection module and a second spectroscope to generate a wide-field detection light spot on a sample at a sample stage, a signal of the excited state sample is detected, and the signal forms an image through an imaging module; the control and processing module is used for acquiring and processing images.
According to one embodiment of the present application, the excitation module includes: the device comprises an optical parametric amplifier, a first variable diaphragm, a first light intensity regulator, a chopper, a first half-wave plate, a first optical filter, a first convex lens and a dichroic mirror; in the excitation module, the reflected light is used as pump light after the wavelength of the reflected light is adjusted by the optical parametric amplifier, the pump light sequentially passes through the first variable diaphragm, the first light intensity adjuster, the chopper, the first half-wave plate and the first optical filter, the light beam is converged by the first convex lens, is reflected by the dichroic mirror and partially transmitted by the second dichroic mirror and then is focused on a rear focal plane of an objective lens, a wide-field pump light spot is generated on a sample at a sample stage, and the sample is excited.
According to an embodiment of the present application, wherein the detection module comprises: the optical lens comprises a total reflection mirror, an optical delay line, a second variable diaphragm, a second light intensity regulator, a second half-wave plate, a super-continuous white light generator, a third light intensity regulator and a second convex lens;
in the detection module, after the transmitted light is reflected by the full-reflecting mirror and sequentially passes through the optical delay line, the second variable diaphragm, the second light intensity regulator and the second half-wave plate, the supercontinuum white light generator generates supercontinuum white light to serve as detection light; the detection light passes through the third light intensity adjuster, is converged by the second convex lens, is partially reflected by the second beam splitter and then is focused on the rear focal plane of the objective lens, and a wide-field detection light spot is generated on a sample at the sample stage to detect a signal of the excited-state sample.
According to one embodiment of the application, the super-continuous white light generator is used for converting femtosecond laser into super-continuous white light as detection light, and the spectrum range is from near ultraviolet to near infrared bands.
According to one embodiment of the present application, a super-continuous white light generator may intercept monochromatic light from the super-continuous white light as probe light. Wherein the imaging module comprises: the device comprises a partial reflection spatial filter, a second optical filter, an imaging lens and a CMOS camera.
According to one embodiment of the present application, an imaging module includes: the device comprises a partial reflection spatial filter, a second optical filter, an imaging lens and a CMOS camera; the pump light reflected by the sample at the sample stage is partially transmitted through the second spectroscope and filtered by the dichroic mirror and the second optical filter; the detection light reflected by the sample at the sample stage is partially transmitted by the second spectroscope, then is transmitted by the dichroic mirror, is subjected to interference light field modulation by the partially-reflective spatial filter, passes through the second optical filter, and is converged by the imaging lens to be imaged on the image plane of the CMOS camera.
According to an embodiment of the application, the first convex lens is installed in a turnover mirror bracket, and the first convex lens can be placed in an optical path, so that the pump light is focused on a back focal plane of the objective lens, thereby expanding a pump light spot on a sample at a sample stage and realizing wide-field pumping; the first convex lens can also be moved out of the optical path, so that the pumping light is focused on a sample at the sample stage by the objective lens after being reflected by the dichroic mirror and partially transmitted by the second dichroic mirror, and the focusing point pumping is realized.
According to an embodiment of the application, wherein the partially reflective spatial filter is a metal film plated on a transparent substrate. The method is used for implementing spatial modulation on the interference light field, controlling the amplitude of a reference light field reaching the CMOS camera, amplifying interference scattering signals and improving the image contrast.
According to an embodiment of the application, the super-continuous white light generator is used for converting femtosecond laser into super-continuous white light as detection light, and the spectrum range is from near ultraviolet to near infrared bands. The super-continuous white light generator can also intercept monochromatic light from the super-continuous white light to serve as detection light.
According to one embodiment of the application, the control and processing module is used for controlling the time sequence of the chopper, the optical delay line and the CMOS camera and processing images to obtain transient interference scattering signals, and automatic image acquisition and processing are achieved.
The invention also provides a measuring method of the second interference scattering microscopic imaging system, which comprises the following steps:
(1) generating femtosecond laser pulse by a femtosecond laser, and dividing the femtosecond laser pulse into a reflected beam and a transmitted beam by a first spectroscope;
(2) the reflected light passes through an excitation module, and a wide-field pumping light spot is generated on a sample at the sample stage to excite the sample in a pumping area; the transmitted light passes through a detection module and a second spectroscope to generate a wide-field detection light spot on a sample at the sample stage, and a signal of the excited-state sample is detected;
(3) inputting the detected signal of the sample in the excited state into an imaging module to form an image;
(4) and the control and processing module (26) collects and processes the image to obtain a transient interference scattering signal.
Compared with the prior art, the invention has the advantages that:
firstly, a back reflection/scattering type imaging light path is adopted to measure interference scattering signals, and more sample types can be compatible, wherein the sample types comprise transparent/opaque substrates, two-dimensional materials, photoelectric interfaces, micro-nano particles and the like;
secondly, the device has femtosecond time resolution and nanoscale three-dimensional space resolution, and can measure the carrier relaxation dynamics in time and the spatial migration and distribution of carriers;
thirdly, based on interference signal amplification and wide field detection, the transient signal intensity is remarkably improved, and the method has the advantages of high speed, high flux, large visual field, no need of phase locking, simultaneous measurement of multiple pixels and the like.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Fig. 2 is a schematic structural diagram of a partial reflection spatial filter and a diagram of spatial modulation effect of an interference optical field according to the present invention. Fig. 2(a) is a schematic structural diagram of a partially reflective spatial filter, and fig. 2(b) is a comparison graph of the spatial modulation effect of the partially reflective spatial filter on the interference optical field of the femtosecond interference scattering signal of the focused point-pumped silicon wafer sample and the spatial modulation effect of the partially reflective spatial filter when the partially reflective spatial filter is not modulated.
FIG. 3 is a graph showing the effect of femtosecond interference scattering microscopy imaging (left) and ultrafast kinetic measurement (right) on gold particles with a particle size of 80nm according to the present invention.
FIG. 4 shows CsPbBr in the present invention3And (5) performing femtosecond interference scattering microscopic imaging on the crystal.
Detailed Description
The present invention is further illustrated by the following examples, which are to be construed as merely illustrative and not limitative of the remainder of the disclosure, and by no means limitative of the remainder of the disclosure, the scope of the disclosure is to be determined by the remainder of the disclosure in question, and by any modification of the remainder of the disclosure that follows in accordance with the remainder of the disclosure.
As shown in fig. 1, the present embodiment provides a femtosecond interference scattering microscopy imaging system (Femto-iSCAT), which includes a femtosecond laser 1, a first beam splitter 2, an optical parametric amplifier 3, a first iris 4, a first light intensity adjuster 5, a chopper 6, a first half-wave plate 7, a first optical filter 8, a first convex lens 9, an all-reflecting mirror 10, an optical delay line 11, a second iris 12, a second light intensity adjuster 13, a second half-wave plate 14, a supercontinuum white light generator 15, a third light intensity adjuster 16, a second convex lens 17, a sample stage 18, an objective lens 19, a second beam splitter 20, a dichroic mirror 21, a partially reflecting spatial filter 22, a second optical filter 23, an imaging lens 24, a CMOS camera 25, and a control and processing module 26.
In this embodiment, the femtosecond laser 1 generates femtosecond laser pulses, and the first beam splitter 2 splits the laser pulses into two beams, one beam being reflected light and the other beam being transmitted light. The reflected light is used as pumping light after the wavelength of the reflected light is adjusted by the optical parametric amplifier 3, sequentially passes through the first variable diaphragm 4, the first light intensity adjuster 5, the chopper 6, the first half wave plate 7 and the first optical filter 8, is converged by the first convex lens 9, is reflected by the dichroic mirror 21, is partially transmitted by the second dichroic mirror 20 and then is focused on the focal plane behind the objective lens 19, a wide-field pumping light spot is generated on a sample at the sample stage 18, the sample in a pumping area is excited, and the pumping light reflected by the sample at the sample stage 18 is partially transmitted by the second dichroic mirror 20 and is filtered by the dichroic mirror 21 and the second optical filter 23. The transmitted light is reflected by the total reflection mirror 10, passes through the optical delay line 11, the second variable diaphragm 12, the second light intensity regulator 13 and the second half-wave plate 14 in sequence, and then is used as detection light by the super-continuous white light generator 15 to generate super-continuous white light. The detection light passes through the third light intensity adjuster 16, the light beam is converged by the second convex lens 17, the light beam is partially reflected by the second beam splitter 20 and then focused on the rear focal plane of the objective lens 19, a wide-field detection light spot is generated on a sample at the sample stage 18, a signal of an excited-state sample is detected, the detection light reflected by the sample at the sample stage 18 is partially transmitted by the second beam splitter 20 and transmitted by the dichroic mirror 21, interference light field modulation is performed by the partial reflection spatial filter 22, and the detection light passes through the second optical filter 23 and is converged on the image plane of the CMOS camera 25 by the imaging lens 24 to form an image. The control and processing module 26 is used to control the system to automatically acquire and process images.
In this embodiment, the femtosecond laser pulse output by the femtosecond laser 1 has a center wavelength of 800nm, a pulse width of 100fs, and a repetition frequency of 1kHz, and is divided into two beams by the first beam splitter 2, one beam is reflected light, the other beam is transmitted light, and the intensity of the reflected light and the intensity of the transmitted light are 6: 4. The reflected light passes through the optical parametric amplifier 3 to generate any monochromatic light within the spectral range of 200-2600nm as the pump light. The beam diameter, light intensity, pulse frequency and polarization direction of the pump light can be adjusted.
In this embodiment, the first convex lens 9 is installed in a flip lens holder, and the first convex lens 9 can be placed in the optical path, so that the pump light is focused on the back focal plane of the objective lens 19, thereby expanding the pump light spot on the sample at the sample stage 18 and realizing wide-field pumping; the first convex lens 9 can also be moved out of the optical path, so that the pump light is reflected by the dichroic mirror 21 and partially transmitted by the second dichroic mirror 20, and then is focused on a sample at the sample stage 18 by the objective lens 19, thereby realizing the focus type point pumping.
In this embodiment, the optical delay line 11 is used to adjust the optical path of the probe light, control the time delay between the probe light pulse and the pump light pulse, the minimum delay step is 0.67fs, and the moving mode is performed according to the setting requirement of the control and processing module 26.
In this embodiment, the super-continuous white light generator 15 is configured to convert the femtosecond laser into super-continuous white light as the detection light, and the spectral range is 500-. The spectral range of the super-continuous white light can be adjusted in the range from near ultraviolet to near infrared by changing the intensity of incident laser, the type of nonlinear medium and the like. The beam diameter, the light intensity and the polarization direction of the detection light can be adjusted.
In this embodiment, as shown in fig. 2(a), the partially reflective spatial filter 22 is a metal film plated on a transparent substrate, and is used to spatially modulate the interference light field, amplify the interference scattering signal, and improve the image contrast. Fig. 2(b) shows that when the focused point-pumped silicon wafer sample is used, after the interference optical field is modulated by the partial reflection spatial filter 22, the intensity of the interference scattering signal is increased by 50% compared with that when the interference optical field is not modulated. The modulation effect of the partially reflective spatial filter 22 on the optical field can be adjusted by changing the kind, shape, size, thickness, and the like of the metal film.
In this embodiment, the control and processing module 26 is used to control the timing of the chopper 6, the optical delay line 11, and the CMOS camera 25, and process the image to obtain a transient interference scattering signal, so as to realize automatic image acquisition and processing.
On the basis of the above embodiment, as shown in fig. 3, taking femtosecond interference scattering microscopy imaging of gold particles with a particle size of 80nm as an example, a pumping light wavelength of 532nm, a pulse energy of 50pJ, and a pulse frequency of 10Hz, the first convex lens 9 is placed in the light path, and wide-field pumping is performed. The supercontinuum white light is used as the detection light, and the polarization direction of the detection light is the same as that of the pump light. The interference scatter image of the carriers on the 80nm gold particles is acquired by the CMOS camera 25 via optical field modulation by the partially reflective spatial filter 22. The interference scattering image under the condition of pump light/no pump light is collected under different time delays, and the transient interference scattering image and the ultrafast dynamic curve of a single gold particle can be obtained through image processing.
Based on the above embodiment, as shown in FIG. 4, CsPbBr is used3For example, the femtosecond interference scattering microscopic imaging of the crystal is performed, wherein the pumping light wavelength is 470nm, the pulse energy is 50pJ, and the pulse frequency is 10Hz, and the first convex lens 9 is moved out of the optical path to perform focusing point pumping. The supercontinuum white light is used as the detection light, and the polarization direction of the detection light is the same as that of the pump light. Light field modulation, CsPbBr, by partially reflecting spatial filter 223An interference scatter image of the carriers on the crystal is acquired by the CMOS camera 25. The interference scattering image under the condition of pump light/no pump light is collected under different time delays, and the transient interference scattering image of the sample excited state carrier can be obtained through image processing, wherein the transient interference scattering image contains information of carrier relaxation and migration dynamics.
Compared with the traditional method, the femtosecond interference scattering microscopic imaging system (Femto-iSCAT) and the measuring method provided by the invention realize interference signal amplification through the partial reflection spatial filter, improve the transient signal intensity of the sample by two to three orders of magnitude, and reach 10-3-10-2An order of magnitude. Meanwhile, the method has the advantages of high speed, high flux, large visual field, good compatibility, no need of phase locking, simultaneous measurement of multiple pixels and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.

Claims (10)

1. The femtosecond interference scattering microscopic imaging system is characterized by comprising a femtosecond laser (1), a first spectroscope (2), an excitation module, a detection module, an objective lens (19), a sample table (18), a second spectroscope (20), an imaging module and a control and processing module (26);
the femtosecond laser (1) generates femtosecond laser pulses, the femtosecond laser pulses are divided into a reflected beam and a transmitted beam by the first beam splitter (2), the reflected beam passes through the excitation module, a wide-field pumping light spot is generated on a sample at the sample stage (18), and the sample in a pumping area is excited; the transmitted light generates a wide-field detection light spot on a sample at the sample stage through a detection module and a second spectroscope (20), a signal of the excited state sample is detected, and the signal forms an image through an imaging module; the control and processing module (26) is used for acquiring and processing images.
2. The femtosecond interference scatter microscopy imaging system according to claim 1,
the excitation module comprises: the device comprises an optical parametric amplifier (3), a first variable diaphragm (4), a first light intensity regulator (5), a chopper (6), a first half-wave plate (7), a first optical filter (8), a first convex lens (9) and a dichroic mirror (21);
in the excitation module, the reflected light is used as pump light after the wavelength of the reflected light is adjusted by the optical parametric amplifier (3), the pump light sequentially passes through the first variable diaphragm (4), the first light intensity adjuster (5), the chopper (6), the first half wave plate (7) and the first optical filter (8), the light beam is converged by the first convex lens (9), the light beam is reflected by the dichroic mirror (21), is partially transmitted by the second dichroic mirror (20) and then is focused on a rear focal plane of an objective lens, a wide-field pump light spot is generated on a sample at a sample stage, and the sample is excited.
3. The femtosecond interference scatter microscopy imaging system according to claim 2, wherein the detection module comprises: the device comprises a total reflection mirror (10), an optical delay line (11), a second variable diaphragm (12), a second light intensity regulator (13), a second half-wave plate (14), a super-continuous white light generator (15), a third light intensity regulator (16) and a second convex lens (17);
in the detection module, the transmitted light is reflected by a total reflection mirror (10), then passes through the optical delay line (11), the second variable diaphragm (12), the second light intensity adjuster (13) and the second half-wave plate (14) in sequence, and the super-continuous white light generator (15) generates super-continuous white light as detection light; the detection light passes through the third light intensity adjuster (16), is converged by the second convex lens to form a light beam (17), is partially reflected by the second beam splitter (20) and then is focused on the rear focal plane of the objective lens (19), and generates a wide-field detection light spot on a sample at the sample stage (18) to detect a signal of an excited-state sample.
4. The femtosecond interference scattering microscopy imaging system according to claim 3, wherein the supercontinuum white light generator is configured to convert femtosecond laser light into supercontinuum white light as probe light, the spectral range being from near ultraviolet to near infrared band.
5. The femtosecond interference scattering microscopy imaging system according to claim 3, wherein the supercontinuum white light generator can intercept monochromatic light from the supercontinuum white light as probe light.
6. The femtosecond interference scatter microscopy imaging system according to claim 3, wherein the imaging module comprises: a partially reflective spatial filter (22), a second filter (23), an imaging lens (24), and a CMOS camera (25);
the pump light reflected by the sample at the sample stage (18) is partially transmitted through the second spectroscope (20) and is filtered by the dichroic mirror (21) and the second optical filter (23); the detection light reflected by the sample at the sample stage (18) is partially transmitted by a second spectroscope (20), then is transmitted by a dichroic mirror (21), is subjected to interference light field modulation by a partial reflection spatial filter (22), passes through a second optical filter (23), and is focused by an imaging lens (24) to be imaged on an image plane of a CMOS camera (25).
7. The femtosecond interference scattering microscopic imaging system according to claim 2, characterized in that the first convex lens (9) is installed in a flip frame, and the first convex lens (9) can be placed in the optical path to realize wide-field pumping; the first convex lens (9) can also be moved out of the optical path to realize focused point pumping.
8. The femtosecond interference scattering microscopy imaging system according to claim 6, characterized in that the partially reflective spatial filter (22) is a metal film plated on a transparent substrate.
9. The femtosecond interference scattering microscopy imaging system according to claim 6, wherein the control and processing module (26) is used for controlling the timing sequence of a chopper, an optical delay line and a CMOS camera and processing images to obtain transient interference scattering signals, and realizing automatic image acquisition and processing.
10. A measurement method based on the femtosecond interference scattering microscopy imaging system as set forth in any one of claims 1 to 9, characterized by comprising the steps of:
(1) generating femtosecond laser pulse by a femtosecond laser, and dividing the femtosecond laser pulse into a reflected beam and a transmitted beam by a first spectroscope;
(2) the reflected light passes through an excitation module, and a wide-field pumping light spot is generated on a sample at the sample stage to excite the sample in a pumping area; the transmitted light passes through a detection module and a second spectroscope (20) to generate a wide-field detection light spot on a sample at a sample stage, and a signal of an excited-state sample is detected;
(3) inputting the detected signal of the sample in the excited state into an imaging module to form an image;
(4) and the control and processing module (26) collects and processes the image to obtain a transient interference scattering signal.
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