CN114034642B - Raman spectrum on-chip detection system and method based on micro-ring resonance array - Google Patents
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Abstract
The invention discloses a Raman spectrum on-chip detection system based on a micro-ring resonance array, which comprises an excitation light emitter, a sensing unit, a filtering unit and a detection unit, wherein the excitation light emitter is connected with the sensing unit; the output end of the excitation light emitter is coupled with the input end of the sensing unit; the output end of the sensing unit is connected with the input end of the filtering unit; the output end of the filtering unit is connected with the input end of the detecting unit; the detection unit comprises a plurality of micro-ring resonance modules and a plurality of detection modules; the micro-ring resonance module comprises a first straight waveguide, a micro-ring waveguide and a second straight waveguide; the micro-ring resonance modules are sequentially connected in series; according to the detection method, inversion processing is carried out according to a transmission matrix obtained after calibrating a plurality of wavelengths and an intensity matrix obtained by detecting molecules to be detected, so as to obtain a Raman information matrix, and further detection and identification of the molecules to be detected are realized. The invention can output less data and realize accurate detection of the molecules to be detected.
Description
Technical Field
The invention relates to the field of molecular spectrum detection, in particular to a Raman spectrum on-chip detection system and method based on a micro-ring resonance array.
Background
The molecules are subjected to spectral detection, so that qualitative and quantitative analysis of the molecules can be realized, and further, the characteristic analysis of the substances is realized. The spectrum detection of the molecules by using the spectrum detector is a common technical means at present, but the detection instrument adopted at present is high in price, large in size and complex in operation, and the detection efficiency is seriously affected.
The existing detection system for detecting molecules by utilizing the Raman scattering principle has the following problems, although the detection system is small in size and convenient to use: the detection system of the array waveguide grating adopts a multichannel design, so that the loss is large, and meanwhile, the footprint of the device is large; a spectrum detection system of on-chip Fourier transform has high power consumption and long test time. Meanwhile, some detection systems do not filter out various impurity lights existing in the raman spectrum, so that the detected spectrum information is not accurate enough.
Disclosure of Invention
Therefore, the invention aims to overcome the defects in the prior art, and provides a Raman spectrum on-chip detection system and method based on a micro-ring resonance array, which can output less data, realize accurate detection of molecules to be detected and ensure the accuracy and reliability of detection.
The Raman spectrum on-chip detection system based on the micro-ring resonance array comprises an excitation light emitter, a sensing unit, a filtering unit and a detection unit;
the output end of the excitation light emitter is coupled with the input end of the sensing unit; the output end of the sensing unit is connected with the input end of the filtering unit; the output end of the filtering unit is connected with the input end of the detecting unit; the upper surface of the sensing unit is attached with molecules to be detected;
the detection unit comprises m micro-ring resonance modules and m detection modules which are in one-to-one correspondence with the micro-ring resonance modules; the micro-ring resonance module comprises a first straight waveguide, a micro-ring waveguide and a second straight waveguide; the radii of the micro-ring waveguides in the m micro-ring resonance modules are all different; the micro-ring waveguide is respectively coupled with the first straight waveguide and the second straight waveguide; the second straight waveguide in the micro-ring resonance module is connected with the detection module;
the first straight waveguide of the 1 st micro-ring resonance module is the input end of the detection unit; the m micro-ring resonance modules are sequentially connected in series according to the following mode:
the first straight waveguides of the 1 st, 2 nd, … th and m-1 st micro-ring resonance modules are connected with the first straight waveguides of the 2 nd, … th and m-th micro-ring resonance modules.
Further, the sensing unit comprises a waveguide structure layer and a surface enhanced Raman layer formed on the upper surface of the waveguide structure layer; the upper surface of the surface-enhanced Raman layer is attached with molecules to be detected;
the output end of the excitation light emitter is coupled with the input end of the waveguide structure layer through a coupler; the output end of the waveguide structure layer is connected with the input end of the filtering unit.
Further, the surface-enhanced raman layer comprises metal nanoparticles; the metal nanoparticle is one of gold nanoparticle, silver nanoparticle and copper nanoparticle.
Further, the filtering unit includes a rayleigh filter; the Rayleigh filter is used for filtering Rayleigh light and excitation light.
Further, the detection module comprises a detector; the detector is used for detecting Raman optical signals with various wavelengths.
A Raman spectrum on-chip detection method based on a micro-ring resonance array comprises the following steps:
s1, inputting n center wavelength points to be marked into a detection unit for calibration to obtain a micro-ring resonance transmission matrix S m×n The method comprises the steps of carrying out a first treatment on the surface of the Wherein m is the number of micro-ring resonance modules;
s2, detecting molecules to be detected by using the detection systemMeasuring to obtain an intensity matrix D of the molecules to be measured m×1 ；
S3, presetting a Raman spectrum information matrix P n×1 And calculates a micro-ring resonance transmission matrix S m×n And raman spectrum information matrix P n×1 Is multiplied by (D) to obtain a multiplied matrix D' m×1 ；
S4, adjusting a matrix P n×1 The parameter values in (a) are such that matrix D' m×1 And intensity matrix D m×1 Identical, and matrix D' m×1 And intensity matrix D m×1 When the same, matrix P is set n×1 As a target matrix;
s5, respectively corresponding each element in the target matrix with n center wavelengths one by one to obtain Raman spectra of molecules to be detected;
s6, comparing Raman characteristic peaks of the Raman spectrum of the molecule to be detected with a Raman spectrum library, and identifying fingerprint spectral lines of the molecule to be detected.
Further, in the step S4, the size P is minimized according to the formula n×1 || 2 Adjusting matrix P n×1 The parameter value of (a) is such that D m×1 -S m×n P n×1 =0, thereby obtaining a target matrix; wherein the values of all elements in the target matrix are more than or equal to 0.
The beneficial effects of the invention are as follows: according to the Raman spectrum on-chip detection system and method based on the micro-ring resonance array, the molecules are rapidly detected through the integrated design of the sensing part and the detection part, detection errors caused by a single micro-ring resonance module are avoided through the arrangement of the micro-ring resonance array, the detection reliability is ensured, meanwhile, under the condition that the detection reliability is far smaller than Nyquist sampling, the spectrum to be detected can be accurately reconstructed by utilizing less data output by the system, and compared with a spectrum reconstruction system with the same performance, the Raman spectrum on-chip detection system has a smaller device assembly and a higher integration degree.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is a schematic diagram of a detection system according to the present invention;
FIG. 2 is a schematic diagram of a sensor unit according to the present invention;
FIG. 3 is a schematic representation of the response of a plurality of detectors of the present invention to various wavelengths;
wherein, 1: a grating coupler; 2: a sensing unit; 3: a Rayleigh filter; 4: a first straight waveguide; 5: a micro-ring waveguide; 6: a second straight waveguide; 7: a detector; 2-1: a waveguide structure layer; 2-2: metal nanoparticles; 2-3: a probe molecule 1;2-4: a probe molecule 2;2-5: probe molecule 3.
Detailed Description
The invention is further described with reference to the accompanying drawings, in which:
the Raman spectrum on-chip detection system based on the micro-ring resonance array comprises an excitation light emitter, a sensing unit 2, a filtering unit and a detection unit;
the output end of the excitation light emitter is coupled with the input end of the sensing unit 2; the output end of the sensing unit 2 is connected with the input end of the filtering unit; the output end of the filtering unit is connected with the input end of the detecting unit; the upper surface of the sensing unit 2 is attached with molecules to be detected; the exciting light emitter adopts an existing laser and is used for outputting exciting light;
the detection unit comprises m micro-ring resonance modules and m detection modules which are in one-to-one correspondence with the micro-ring resonance modules; the micro-ring resonance module comprises a first straight waveguide 4, a micro-ring waveguide 5 and a second straight waveguide 6; the radii of the micro-ring waveguides 5 in the m micro-ring resonance modules are all different; the micro-ring waveguide 5 is respectively coupled with the first straight waveguide 4 and the second straight waveguide 6; the second straight waveguide 6 in the micro-ring resonance module is connected with the detection module; the first straight waveguide 4 and the second straight waveguide 6 are all straight-through optical waveguides, and compared with a bent waveguide, the straight-through optical waveguides have smaller transmission loss, so that the spectral characteristic performance of the output of the micro-ring resonance module is ensured; the m micro-ring resonance modules form a micro-ring resonance array; the m detection modules form a detection array; the micro-ring waveguides with different radiuses are arranged, so that the free spectrum ranges obtained by each micro-ring resonance module are different, and the peak value corresponding to the central wavelength of each micro-ring resonance module is also different, so that the spectrum signals detected by the detection module are different, the effect is shown in figure 3, and the follow-up detection and identification of molecules to be detected are facilitated.
The first straight waveguide 4 of the 1 st micro-ring resonance module is the input end of the detection unit; the m micro-ring resonance modules are sequentially connected in series according to the following mode:
the first straight waveguides 4 of the 1 st, 2 nd, … th and m-1 st micro-ring resonator modules are connected with the first straight waveguides 4 of the 2 nd, … th and m-th micro-ring resonator modules. As shown in fig. 1, the value of m is N, where N is a positive integer not less than 1.
Through the structure, the integration of the waveguide sensing system and the detection system is realized, the rapid detection is further realized, the detection error caused by a single micro-ring resonance module is avoided by arranging the micro-ring resonance array, the detection reliability is ensured, meanwhile, the compression sensing is realized, the spectrum to be detected can be accurately reconstructed by utilizing less data output by the system under the condition of being far smaller than Nyquist sampling, and compared with a spectrum reconstruction system with the same performance, the detection system provided by the invention has a smaller device assembly and higher integration degree.
In this embodiment, the sensing unit 2 includes a waveguide structure layer 2-1 and a surface enhanced raman layer formed on the upper surface of the waveguide structure layer 2-1; the upper surface of the surface-enhanced Raman layer is attached with molecules to be detected; the surface enhanced Raman layer is used for enhancing the electromagnetic field of the surface and improving the Raman excitation efficiency of the molecules to be detected;
the output end of the excitation light emitter is coupled and connected with the input end of the waveguide structure layer 2-1 through a coupler; the output end of the waveguide structure layer 2-1 is connected with the input end of the filtering unit; the coupler is a grating coupler 1, and the grating coupler 1 couples excitation light into the waveguide structure layer 2-1 for Raman sensing; the waveguide structure layer 2-1 is Si with the thickness of 300nm 3 N 4 A layer.
In this embodiment, the surface-enhanced raman layer includes metal nanoparticles 2-2; the metal nanoparticle 2-2 is one of gold nanoparticle, silver nanoparticle and copper nanoparticle. Wherein the surface enhancement effect of the surface enhanced Raman layer is achieved by using the metal in the metal nanostructure. The principle of surface enhancement of metals in the metal nanostructure is described below by taking silver Ag as an example:
when Ag particles are subjected to electromagnetic interference, free electrons on the surface of the Ag particles collectively oscillate, and when the oscillation frequency of the electrons is the same as that of incident light waves, resonance is generated to form LSPR (localized surface plasmon resonance). And the three IB group metals of Au/Ag/Cu can avoid the occurrence of interband transition under the proper excitation wavelength to convert the energy of absorbed light into heat, thereby realizing more efficient LSPR.
In this embodiment, the filtering unit includes a rayleigh filter 3; the rayleigh filter 3 is used for filtering rayleigh light and excitation light. The Rayleigh light and the excitation light returning to the waveguide exist in the sensing unit 2, and the Rayleigh filter 3 filters the Rayleigh light and the excitation light which are higher in relative Raman light intensity in the sensing unit 2, so that the Raman light of the sensing unit 2 enters the detection unit after passing through the filtering unit, and the accuracy and the reliability of spectrum reconstruction are ensured. As shown in fig. 2, the probe molecules are molecules to be detected, and raman spectra generated by each probe molecule in the waveguide sensing area are filtered by a filter and then enter the detection unit for raman spectrum reconstruction.
In this embodiment, the detection module includes a detector 7; the detector 7 is used for detecting raman optical signals of various wavelengths. As shown in fig. 3, the number of the detectors 7 is N, 5-1 in fig. 3 is the correspondence of the first detector to each wavelength, 5-2 in fig. 3 is the correspondence of the second detector to each wavelength, and 5-N in fig. 3 is the correspondence of the nth detector to each wavelength; each detector 7 detects the raman light of each wavelength and outputs a detection intensity value, thereby realizing the reconstruction of the raman spectrum. The detector 7 adopts a technology, and is not described herein.
The detection method for detecting the molecules to be detected by using the detection system comprises the following steps:
s1, n are divided into nThe center wavelength point to be marked is input into a detection unit for marking to obtain a micro-ring resonance transmission matrix S m×n The method comprises the steps of carrying out a first treatment on the surface of the Wherein m is the number of micro-ring resonance modules; when in calibration, each time of input is a narrow-band Gaussian beam with a known center wavelength, and one narrow-band Gaussian beam corresponds to a point to be calibrated with the center wavelength; the micro-ring resonance transmission matrix S m×n A transmission matrix of the micro-ring resonant array to the spectrum;
s2, detecting the molecules to be detected by using the detection system to obtain an intensity matrix D of the molecules to be detected m×1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, after the excitation light passes through the sensing unit 2, a raman spectrum of the molecule to be detected is obtained, the raman spectrum is the spectrum to be detected, the spectrum to be detected enters the detection unit after being filtered, and finally a detection array intensity information matrix D is obtained according to the intensity information output by the m detectors 7 m×1 ；
S3, presetting a Raman spectrum information matrix P n×1 And calculates a micro-ring resonance transmission matrix S m×n And raman spectrum information matrix P n×1 Is multiplied by (D) to obtain a multiplied matrix D' m×1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein according to the matrix S m×n Matrix D m×1 Is arranged with a matrix P of n rows and 1 columns n×1 ；
S4, adjusting a matrix P n×1 The parameter values in (a) are such that matrix D' m×1 And intensity matrix D m×1 Identical, and matrix D' m×1 And intensity matrix D m×1 When the same, matrix P is set n×1 As a target matrix;
s5, respectively corresponding each element in the target matrix with n center wavelengths one by one to obtain Raman spectra of molecules to be detected; wherein, n central wavelengths respectively correspond to one element value in the target matrix of n rows and 1 columns, namely, one central wavelength corresponds to one Raman spectrum information value, thereby obtaining the Raman spectrum of the molecule to be detected; and the obtained Raman spectrum of the molecule to be detected is further normalized, so that the analysis and comparison of the spectrum are facilitated.
S6, comparing Raman characteristic peaks of the Raman spectrum of the molecule to be detected with a Raman spectrum library, and identifying fingerprint spectral lines of the molecule to be detected. The Raman spectrum database is an existing Raman spectrum database, raman characteristic peaks of the detected Raman spectrum of the molecules to be detected are compared with those of the existing Raman spectrum database, raman spectra matched with the Raman spectra of the molecules to be detected in the Raman spectrum database are obtained, the molecules corresponding to the matched Raman spectra are used as target molecules, and the types and the characteristics of the target molecules are the types and the characteristics of the molecules to be detected, so that the molecules to be detected are identified and detected.
In this embodiment, in the step S4, the size P is minimized according to the formula n×1 || 2 Adjusting matrix P n×1 The parameter value of (a) is such that D m×1 -S m×n P n×1 =0, thereby obtaining a target matrix; wherein the values of all elements in the target matrix are more than or equal to 0. Wherein matrix D' m×1 ＝S m×n P n×1 。S m×n P n×1 Representing a micro-ring resonant transmission matrix S m×n And raman spectrum information matrix P n×1 Is a product of (a) and (b). Through the steps, a more accurate target matrix can be obtained, and accurate identification of molecules to be detected is facilitated.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (6)
1. A Raman spectrum on-chip detection system based on a micro-ring resonance array is characterized in that: the device comprises an excitation light emitter, a sensing unit, a filtering unit and a detection unit;
the output end of the excitation light emitter is coupled with the input end of the sensing unit; the output end of the sensing unit is connected with the input end of the filtering unit; the output end of the filtering unit is connected with the input end of the detecting unit; the upper surface of the sensing unit is attached with molecules to be detected;
the detection unit comprises m micro-ring resonance modules and m detection modules which are in one-to-one correspondence with the micro-ring resonance modules; the micro-ring resonance module comprises a first straight waveguide, a micro-ring waveguide and a second straight waveguide; the radii of the micro-ring waveguides in the m micro-ring resonance modules are all different; the micro-ring waveguide is respectively coupled with the first straight waveguide and the second straight waveguide; the second straight waveguide in the micro-ring resonance module is connected with the detection module;
the first straight waveguide of the 1 st micro-ring resonance module is the input end of the detection unit; the m micro-ring resonance modules are sequentially connected in series according to the following mode:
the first straight waveguides of the 1 st, 2 nd, … th and m-1 st micro-ring resonance modules are connected with the first straight waveguides of the 2 nd, … th and m-th micro-ring resonance modules;
the detection system detects the molecules to be detected, and comprises the following steps:
s1, inputting n center wavelength points to be marked into a detection unit for calibration to obtain a micro-ring resonance transmission matrix S m×n The method comprises the steps of carrying out a first treatment on the surface of the Wherein m is the number of micro-ring resonance modules;
s2, detecting the molecules to be detected by using the detection system to obtain an intensity matrix D of the molecules to be detected m×1 ；
S3, presetting a Raman spectrum information matrix P n×1 And calculates a micro-ring resonance transmission matrix S m×n And raman spectrum information matrix P n×1 Is multiplied by (D) to obtain a multiplied matrix D' m×1 ；
S4, adjusting a matrix P n×1 The parameter values in (a) are such that matrix D' m×1 And intensity matrix D m×1 Identical, and matrix D' m×1 And intensity matrix D m×1 When the same, matrix P is set n×1 As a target matrix;
s5, respectively corresponding each element in the target matrix with n center wavelengths one by one to obtain Raman spectra of molecules to be detected;
s6, comparing Raman characteristic peaks of the Raman spectrum of the molecule to be detected with a Raman spectrum library, and identifying fingerprint spectral lines of the molecule to be detected.
2. The micro-ring resonator array based raman spectroscopy on-chip detection system according to claim 1, wherein: the sensing unit comprises a waveguide structure layer and a surface-enhanced Raman layer formed on the upper surface of the waveguide structure layer; the upper surface of the surface-enhanced Raman layer is attached with molecules to be detected;
the output end of the excitation light emitter is coupled with the input end of the waveguide structure layer through a coupler; the output end of the waveguide structure layer is connected with the input end of the filtering unit.
3. The micro-ring resonator array based raman spectroscopy on-chip detection system according to claim 2, wherein: the surface-enhanced Raman layer comprises metal nano particles; the metal nanoparticle is one of gold nanoparticle, silver nanoparticle and copper nanoparticle.
4. The micro-ring resonator array based raman spectroscopy on-chip detection system according to claim 1, wherein: the filtering unit comprises a Rayleigh filter; the Rayleigh filter is used for filtering Rayleigh light and excitation light.
5. The micro-ring resonator array based raman spectroscopy on-chip detection system according to claim 1, wherein: the detection module comprises a detector; the detector is used for detecting Raman optical signals with various wavelengths.
6. The micro-ring resonator array based raman spectroscopy on-chip detection system according to claim 1, wherein: in the step S4, the value of the minimum P is calculated according to the formula n×1 || 2 Adjusting matrix P n×1 The parameter value of (a) is such that D m×1 -S m×n P n×1 =0, thereby obtaining a target matrix; wherein the values of all elements in the target matrix are more than or equal to 0.
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