CN111912524A - Raman spectrum imaging method and imaging device - Google Patents
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- 239000002070 nanowire Substances 0.000 claims description 19
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 238000001069 Raman spectroscopy Methods 0.000 claims description 12
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 2
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- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/2823—Imaging spectrometer
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
- G01J3/0208—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using focussing or collimating elements, e.g. lenses or mirrors; performing aberration correction
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- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
- G01J3/4412—Scattering spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B13/00—Optical objectives specially designed for the purposes specified below
- G02B13/001—Miniaturised objectives for electronic devices, e.g. portable telephones, webcams, PDAs, small digital cameras
- G02B13/0015—Miniaturised objectives for electronic devices, e.g. portable telephones, webcams, PDAs, small digital cameras characterised by the lens design
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Abstract
The invention relates to a Raman spectrum imaging device, which belongs to the technical field of spectrum imaging, wherein in the prior art, corresponding objective lenses are not specially designed for different substrates; the method has wide application, can be selected according to the characteristics of the detection object, and can also be used for scientific research by comparison.
Description
Technical Field
The invention relates to the technical field of spectral imaging, in particular to a Raman spectral imaging device.
Background
Raman spectroscopy is a scattering spectrum, found by indian scientist c.v. raman. Based on the Raman scattering effect, the scattering spectrum with different frequency from the incident light is analyzed to obtain the information of molecular vibration and rotation, and the method has great value when being applied to molecular structure research.
However, the raman scattering effect is a very weak process, so that the raman signal is very weak, and almost all raman spectroscopy studies on surface adsorbed species use some kind of enhancement effect. In the prior art, the most common surface enhanced raman spectroscopy effect is the substrate of the surface enhanced raman spectroscopy, which is a key technology, and generally, there are nanoparticle substrates, nanowire substrates and the like, and there are significant differences between different substrates between the enhancement mechanism and the enhancement effect, and the prior art does not provide an optical system for the differences.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a raman spectroscopy imaging method, which is characterized in that: the method comprises the following steps:
respectively placing detection objects on a nanowire substrate and a nanoparticle substrate;
when the nanowire array substrate is selected, light emitted by a light source sequentially passes through the nanowire array substrate, a first objective lens and a spectrum analysis unit; when the nanoparticle substrate is selected, light emitted by the light source sequentially passes through the nanoparticle substrate, the second objective lens and the imaging unit;
the imaging unit transmits the image information to an upper computer for comparison and analysis;
the first objective lens comprises a first cemented lens consisting of a first lens with positive diopter and a second lens with negative diopter, a second cemented lens consisting of a third lens with positive diopter and a fourth lens with negative diopter and a fifth lens with negative diopter in sequence from the object space to the image space;
and satisfy d1/TTL>0.45, wherein d1TTL is the optical total length of the first objective lens and is the radius of the first lens;
the second objective lens sequentially comprises a third cemented lens consisting of a sixth lens with positive diopter and a seventh lens with negative diopter, a fourth cemented lens consisting of an eighth lens with positive diopter and a ninth lens with negative diopter and a tenth lens with negative diopter from the object side to the image side;
the field angle theta of the second objective lens satisfies that 110 DEG theta is larger than 70 DEG, and the numerical aperture NA of the second objective lens is larger than 0.6.
Preferably, the first objective lens satisfies the following condition: 1.2>f1/f40>1.9；
3.7>f1/f2>1.1；
5.1>f1/f3>2.4；
Wherein the focal length of the first cemented lens is f1The focal length of the second cemented lens is f2A focal length f of the fifth lens3The total focal length of the first objective lens is f40。
Preferably, the second objective lens satisfies the following condition: 1.7>f5/f60>1.3；
2.7>f6/f60>1.5；
-1.2>f7/f60>-1.6；
Wherein the third cemented lens has a focal length f5The focal length of the fourth cemented lens is f6A focal length of the tenth lens is f7The total focal length of the second objective lens is f60。
The invention also provides a Raman spectrum imaging device, which is characterized in that: the device comprises a laser light source, a contrast selection unit, a first substrate, a first objective lens, a second substrate, a second objective lens and a spectrum analysis unit;
when the contrast selection unit selects the first substrate, the light emitted by the light source sequentially passes through the first substrate, the first objective lens and the spectrum analysis unit; wherein the first substrate is a nanowire array substrate;
when the contrast selection unit selects a second substrate, light emitted by the light source sequentially passes through the second substrate, the second objective lens and the spectrum analysis unit; wherein the second substrate is a nanoparticle substrate;
the first objective lens comprises a first cemented lens consisting of a first lens with positive diopter and a second lens with negative diopter, a second cemented lens consisting of a third lens with positive diopter and a fourth lens with negative diopter and a fifth lens with negative diopter in sequence from the object space to the image space;
and satisfy d1/TTL>0.45, wherein d1TTL is the optical total length of the first objective lens and is the radius of the first lens;
the second objective lens sequentially comprises a third cemented lens consisting of a sixth lens with positive diopter and a seventh lens with negative diopter, a fourth cemented lens consisting of an eighth lens with positive diopter and a ninth lens with negative diopter and a tenth lens with negative diopter from the object side to the image side;
the field angle theta of the second objective lens satisfies that 110 DEG theta is larger than 70 DEG, and the numerical aperture NA of the second objective lens is larger than 0.6.
Preferably, the first base and the second base are both located on a sample stage, the sample stage can replace the first base and the second base by rotating, and the sample stage can also be finely adjusted in X, Y, Z three directions.
Compared with the prior art, the invention at least has the following invention points and corresponding beneficial effects:
(1) according to the invention, two groups of objective lenses are designed in a targeted manner according to different characteristics of the nanowire substrate and the nanoparticle substrate, and a user can select or compare the two groups of objective lenses according to different characteristics of an object and the substrate, so that the device has a wide application range. In contrast to the prior art, the present invention specifically designs the objective lens for the comparison of nanowires and nanoparticles. This design includes a change of objective lenses for both targets, using a rotating mechanism adapted for fast switching. The rotation mechanism can be quickly switched to the objective lens required by the second substrate after the detection of the first substrate is completed, which is very important in the detection of nanowires and nanoparticles. Because the detection needs to be completed quickly after the preparation of the nanowires and the nanoparticles is completed, the time is long, and the risk of introducing impurities before the packaging is caused, so that the detection precision is influenced. The need for upper detection is thus met by using, for example, a rotating mechanism, with which the required objective can be quickly switched.
(2) The design and specific parameters of the specific lens of the first objective lens group can maximize the advantage of large effective aperture of the nanowire substrate.
(3) The design and specific parameters of the specific lens of the second objective lens group aim at the defects of the nanoparticle substrate, so that the resolution is improved as much as possible, and the defects of the substrate are inhibited.
It should be noted that this objective lens is specially designed for raman spectroscopy and is not replaced by objective lenses in other fields. This is because raman spectroscopy has its own features, which require a wide range of wavelengths to be accommodated, while still meeting imaging requirements. In addition, the raman scattering angle is large, and the numerical aperture of the objective lens is also required to be large. The above features, but not limited to the above, determine that the objective lens needs to be specially customized, and not a general objective lens that can fulfill the substrate inspection requirements.
Drawings
FIG. 1 is a block diagram of a Raman spectroscopy imaging apparatus provided by the present invention;
FIG. 2 is a block diagram of a first objective lens group of the present invention;
FIG. 3 is a field curvature and distortion plot of a first objective lens of the present invention;
FIG. 4 is a chromatic aberration diagram of a first objective lens of the present invention;
FIG. 5 is a block diagram of a second objective lens assembly of the present invention;
FIG. 6 is a field curvature and distortion plot for a second objective lens of the present invention;
FIG. 7 is a second objective chromatic aberration diagram of the present invention;
in the figure: 1. the laser imaging device comprises a laser light source, 2, a contrast selection unit, 3, a first substrate, 4, a first objective lens, 5, a second substrate, 6, a second objective lens, 7, a monochromator, 8, a CCD imaging unit, 9, an upper computer, 11, a first objective lens first lens, 12, a first objective lens second lens, 13, a first objective lens third lens, a first objective lens 21, a first objective lens fourth lens, 3, a first objective lens fifth lens, 51, a second objective lens first lens, 52, a second objective lens second lens, 61, a second objective lens third lens, 62, a second objective lens fourth lens, 7 and a second objective lens fifth lens.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
In the present embodiment, as shown in fig. 1, the raman spectrum imaging device includes a laser light source 10, a contrast selection unit 20, a first substrate 30, a first objective lens 40, a second substrate 50, a second objective lens 60, a CCD imaging unit 70, and an upper computer 80.
When the contrast selection unit 20 selects the first substrate 30 to bear a sample, light emitted by the laser source 10 passes through the first substrate 30, then passes through the first objective lens 40 in sequence, finally reaches the CCD imaging unit through the light, and transmits image information to the upper computer for storage;
when the comparison selection unit 20 selects the second substrate 50 to carry a sample, light emitted by the laser source 10 passes through the second substrate 50, then passes through the second objective lens 60 in sequence, finally reaches the CCD imaging unit, and transmits image information to the upper computer for storage.
It should be noted that after the detection of the first substrate 30 is completed, the objective lens switching from the first objective lens 40 to the second objective lens 60 can be quickly completed by using an objective lens switching device such as a rotating mechanism, which is particularly suitable for the substrate that needs to be quickly detected just prepared. This avoids the risk of introducing impurities into the substrate material before packaging, which would otherwise result from waiting for the second objective lens 60 to be debugged.
The comparison selection unit 20 can select the first objective lens 40 or the second objective lens 60 according to the specific properties of the material to be detected and the characteristics of the nanowire substrate and the nanoparticle substrate, or can perform detection under the first objective lens 40 and the second objective lens 60 by using the same sample, so as to perform further scientific research on the object to be detected and the substrate material.
The first substrate 30 is a high-quality metal nanowire array formed on a silicon substrate, wherein the metal can be gold, silver or copper; the nano wire is in a regular periodic structure, when the wavelength of the adopted laser light source is slightly larger than the period of the nano wire, the energy of the incident point light source is coupled to the surface plasma wave, and the emergent effective aperture diaphragm is obviously increased.
The first objective lens 40 is specifically designed as follows corresponding to the first substrate 30: the lens comprises a first lens 11 with positive refractive index, a second lens 12 with negative refractive index, a third lens 21 with positive refractive index, a fourth lens 22 with negative refractive index and a fifth lens 3 with negative refractive index in sequence from the object side to the image side; wherein the first lens 11 and the second lens 12 are cemented lenses, and the third lens 21 and the fourth lens 22 are cemented lenses, wherein chromatic aberration is minimized by a cemented lens in which two positive and negative lenses are combined; the lens parameters were as follows:
table one: nanowire substrate objective lens parameters
As shown in fig. 3, the field curvature and distortion maps of the first objective lens of the present invention;
as shown in fig. 4, a chromatic aberration diagram of the first objective lens of the present invention;
the lens radii of the first lens 11 and the second lens 12 are d1, and the total optical system length of the first objective lens is TTL, d1/TTL>0.45, so that the first objective lens has a larger effective aperture, in this embodiment, the lens radii d of the first lens 11 and the second lens 121The total length of the optical system is TTL of 9mm when the thickness is 5 mm;
the focal length of the cemented lens composed of the first lens 11 and the second lens 12 in the first objective lens is f1The focal length of the cemented lens composed of the third lens 21 and the fourth lens 22 is f2The focal length of the fifth lens 3 is f3The total focal length of the first objective lens is f40The above focal lengths satisfy the following relationship:
1.2>f1/f40>1.9；
3.7>f1/f2>1.1；
5.1>f1/f3>2.4。
wherein the second substrate 50 is a high-quality nano-particle film formed on a silicon substrate, wherein the metal can be gold, silver or copper; due to the small size of the nanoparticles, it may happen that only electric dipole resonance mode occurs, with a single SPR peak appearing on the spectrum, which is red-shifted as the size of the particles increases, with new high-order SPR peaks appearing in the short-wave region, but in general, these have a considerable spectral width, overlapping each other, with a fraction of each being indistinguishable.
The second objective lens 60 is specifically designed as follows corresponding to the second substrate 50:
the specially designed second objective lens is as follows: the lens comprises a first lens 51 with a positive refractive index, a second lens 52 with a negative refractive index, a third lens 61 with a positive refractive index, a fourth lens 62 with a negative refractive index and a fifth lens 7 with a negative refractive index in sequence from the object side to the image side; wherein the first lens 51 and the second lens 52 are cemented lenses, and the third lens 61 and the fourth lens 62 are cemented lenses, wherein chromatic aberration is minimized by a cemented lens in which two positive and negative lenses are combined; the lens parameters were as follows:
table two: nanoparticle-based objective lens parameters
As shown in fig. 6, the field curvature and distortion map of the second objective lens of the present invention;
as shown in fig. 7, a chromatic aberration diagram of the second objective lens of the present invention;
wherein the field angle theta of the second objective lens satisfies that 110 DEG > theta >70 DEG, and the numerical aperture NA of the second objective lens is >0.6, so that the lens group has high resolution;
the focal length of the cemented lens composed of the first lens 51 and the second lens 52 in the second objective lens is f5The focal length of the cemented lens composed of the third lens 61 and the fourth lens 62 is f6The focal length of the fifth lens 7 is f7The total focal length of the second objective lens is f60The above focal lengths satisfy the following relationship:
1.7>f5/f60>1.3；
2.7>f6/f60>1.5；
-1.2>f7/f60>-1.6。
in the above spectral imaging apparatus, the first base and the second base are both located on a sample stage (not shown in the figure), the sample stage can replace the first base and the second base by rotating, and the sample stage can be finely adjusted in X, Y, Z three directions according to the needs of a user so as to deal with different focal lengths of different objective lenses and/or align and adjust the angles of the detection samples.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (5)
1. A method of raman spectroscopic imaging, characterized by: the method comprises the following steps:
respectively placing detection objects on a nanowire substrate and a nanoparticle substrate;
when the nanowire array substrate is selected, light emitted by a light source sequentially passes through the nanowire array substrate, a first objective lens and a spectrum analysis unit; when the nanoparticle substrate is selected, light emitted by the light source sequentially passes through the nanoparticle substrate, the second objective lens and the imaging unit;
the imaging unit transmits the image information to an upper computer for comparison and analysis;
the first objective lens comprises a first cemented lens consisting of a first lens with positive diopter and a second lens with negative diopter, a second cemented lens consisting of a third lens with positive diopter and a fourth lens with negative diopter and a fifth lens with negative diopter in sequence from the object space to the image space;
and satisfy d1/TTL>0.45, wherein d1TTL is the optical total length of the first objective lens and is the radius of the first lens;
the second objective lens sequentially comprises a third cemented lens consisting of a sixth lens with positive diopter and a seventh lens with negative diopter, a fourth cemented lens consisting of an eighth lens with positive diopter and a ninth lens with negative diopter and a tenth lens with negative diopter from the object side to the image side;
the field angle theta of the second objective lens satisfies 110o > theta >70 degrees, and the numerical aperture NA of the second objective lens is > 0.6.
2. The method of claim 1, wherein: the first objective lens satisfies the following condition:
1.2>f1/f40>1.9；
3.7>f1/f2>1.1；
5.1>f1/f3>2.4；
wherein the focal length of the first cemented lens is f1The focal length of the second cemented lens is f2A focal length f of the fifth lens3The total focal length of the first objective lens is f40。
3. The method of claim 1, wherein: the second objective lens satisfies the following conditions:
1.7>f5/f60>1.3；
2.7>f6/f60>1.5；
-1.2>f7/f60>-1.6；
wherein the third cemented lens has a focal length f5The focal length of the fourth cemented lens is f6A focal length of the tenth lens is f7The total focal length of the second objective lens is f60。
4. A raman spectral imaging device characterized by: the device comprises a laser light source, a contrast selection unit, a first substrate, a first objective lens, a second substrate, a second objective lens and a spectrum analysis unit;
when the contrast selection unit selects the first substrate, the light emitted by the light source sequentially passes through the first substrate, the first objective lens and the spectrum analysis unit; wherein the first substrate is a nanowire array substrate;
when the contrast selection unit selects a second substrate, light emitted by the light source sequentially passes through the second substrate, the second objective lens and the spectrum analysis unit; wherein the second substrate is a nanoparticle substrate;
the first objective lens comprises a first cemented lens consisting of a first lens with positive diopter and a second lens with negative diopter, a second cemented lens consisting of a third lens with positive diopter and a fourth lens with negative diopter and a fifth lens with negative diopter in sequence from the object space to the image space;
and satisfy d1/TTL>0.45, wherein d1TTL is the optical total length of the first objective lens and is the radius of the first lens;
the second objective lens sequentially comprises a third cemented lens consisting of a sixth lens with positive diopter and a seventh lens with negative diopter, a fourth cemented lens consisting of an eighth lens with positive diopter and a ninth lens with negative diopter and a tenth lens with negative diopter from the object side to the image side;
the field angle theta of the second objective lens satisfies that 110 DEG theta is larger than 70 DEG, and the numerical aperture NA of the second objective lens is larger than 0.6.
5. The apparatus of claim 4, wherein: the first base and the second base are both located on a sample stage, the sample stage can replace the first base and the second base through rotation, and the sample stage can be finely adjusted in X, Y, Z three directions.
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