CN112763421B - Graphene GH displacement and photothermal effect-based solution detection device and method - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- 238000001514 detection method Methods 0.000 title claims abstract description 53
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 45
- 230000000694 effects Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 39
- 239000010453 quartz Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000012086 standard solution Substances 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 description 11
- -1 graphite alkene Chemical class 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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Abstract
本发明基于石墨烯GH位移和光热效应的溶液检测装置及方法，属于生化检测技术领域；该方法中，石墨烯吸收经过强度调制的泵浦光产生热量并扩散到周围的液态介质中。液态介质的温度发生变化，其折射率也发生微小改变。因为不同种类溶液的折射率随温度的变化不同，利用石墨烯在全反射条件下的GH位移效应对折射率敏感的特点，可实现对不同种类溶液的高灵敏度检测。本发明将石墨烯的光热效应和全发射条件下的GH位移效应相结合，实现了对不同种类液态介质的检测，涉及检测方法具有所需样品体积小、不受外界环境温度变化的影响等优点。
The invention discloses a solution detection device and method based on graphene GH displacement and photothermal effect, and belongs to the technical field of biochemical detection. In the method, graphene absorbs intensity-modulated pump light to generate heat and diffuses it into the surrounding liquid medium. As the temperature of the liquid medium changes, its refractive index also changes slightly. Because the refractive index of different kinds of solutions varies with temperature, high-sensitivity detection of different kinds of solutions can be achieved by utilizing the characteristic that the GH shift effect of graphene is sensitive to the refractive index under the condition of total reflection. The invention combines the photothermal effect of graphene and the GH displacement effect under full emission conditions, and realizes the detection of different kinds of liquid media. .
Description
Technical Field
The invention relates to the technical field of biochemical detection, in particular to a graphene GH displacement and photothermal effect-based solution detection device and method.
Background
GH (Goss Hanchen) displacement was first discovered in 1947, and means that when a finite width (parallel or focused) light beam is reflected from a different type of medium interface under total internal reflection, the reflected light beam is not reflected from the geometrically expected position, but is reflected after being laterally displaced by a small amount. Since the displacement of the GH is generally in the order of magnitude of wavelength, it is difficult to directly measure the displacement and the change of the GH by using a detector in many cases. Therefore, researchers have designed grating structures, multimode waveguide structures, metal microstructures and other technologies to enhance the GH displacement effect. GH displacement is widely used in the fields of temperature sensing, displacement sensing, humidity sensing, and the like. The 2012 Hu et al discovered a great GH displacement enhancement effect on the surface of the waveguide coated with the metal film by using the light beam, and used the GH displacement enhancement effect for sensing the micro displacement. The displacement sensor can realize displacement sensing of 8 pm and is not influenced by laser power change (laser journal, 2012, 32, 10-11). GH displacement and temperature under high-order waveguide mode are explored by Sun et al in 2013Relationship between degree (C:)Opt. Express 2009, 17, 21433-21441). Researchers found that GH displacement increased significantly with increasing temperature. In 2015, Li et al studied the change of GH displacement with temperature on prism and waveguide coupling structure of infrared band (ii)Appl. PhysB2015, 123, 1-8), GH displacement versus temperature was found to be differently linear for different waveguide modes. The GH displacement amount changes when the refractive index of the medium slightly changes, but since the change in GH displacement amount is usually of the wavelength order, the conventional photodetector is difficult to recognize.
Graphene attracts researchers' attention due to its unique optical properties, excellent mechanical strength, and ultra-high carrier mobility. It has been theorized that graphene will produce large (large-scale) GH displacements under total internal reflection. In 2014, Li et al experimentally confirmed that graphene has obvious GH displacement effect for the first time (Opt. Lett. 2014, 39, 5574 and 5577)), researchers use a spectral scanning method to explore GH shifts of graphene with different thicknesses, and find that the polarization direction of incident light has a great influence on the GH shift of the graphene. At present, no device for detecting a solution by using GH displacement of graphene exists.
Disclosure of Invention
The present invention has been made in view of the above problems. The invention aims to provide a solution detection device and method based on graphene GH displacement and photothermal effect, which can realize high-sensitivity detection on different solutions by detecting the change of the refractive index of a liquid medium caused by pumping light.
In order to solve the technical problems, the invention adopts the technical scheme that: a solution detection device based on graphene GH displacement and photothermal effect comprises a detection light source, a prism with graphene, a balance detector, a lock-in amplifier, a pumping light source and a CCD camera, wherein the detection light source generates detection light which sequentially passes through a polaroid and a half-wave plate and then is reflected by a reflector, the emitted light passes through a focusing objective lens and then is incident to an incident surface of the prism with graphene at a full reflection angle, the light emitted from an emergent surface of the detection light sequentially passes through the focusing objective lens and a beam splitting prism and then is divided into two detection light beams with the same intensity and enters the balance detector, the balance detector is used for measuring the light intensity difference of the two detection light beams, the lock-in amplifier is connected with the balance detector, and the lock-in amplifier is connected with a computer;
the pump light source generates pump light, the pump light sequentially passes through the adjustable attenuator and the light intensity modulation unit and then is reflected by the reflector, the emitted light is incident to the reflecting surface of the prism with the graphene through the focusing objective lens, and the CCD camera is used for observing light spots formed by coincidence of the detection light and the pump light on the reflecting surface of the prism with the graphene.
Further, the prism with the graphene comprises a right-angle prism, a quartz plate, the graphene and a microflow channel, the quartz plate is coupled on the reflecting surface of the right-angle prism through refractive index matching liquid, the microflow channel is bonded on the quartz plate, the microflow channel is of a groove structure with a rectangular cross section, liquid inlets are arranged at two ends of the microflow channel, the graphene is prepared on the quartz plate through a high-temperature reduction method, and the graphene is bonded with the microflow channel.
Further, the wavelength of the pump light is 980-1100 nm.
Further, the light intensity modulation unit is a chopper or an acousto-optic modulator.
Further, the probe light ispPolarized light.
A graphene GH displacement and photothermal effect-based solution detection method comprises the following steps:
preparing graphene by a high-temperature reduction method, wherein a substrate of the graphene is a quartz plate, the graphene is coupled to a reflecting surface of a right-angle prism through refractive index matching fluid, and a microfluidic channel is bonded on the upper surface of the graphene;
pumping light is loaded with certain intensity frequency through a light intensity modulation unit, passes through an adjustable attenuator, a reflector and a focusing objective lens and then is vertically incident to the surface of the graphene;
the detection light is changed into a detection light through a polaroid and a half-wave platepPolarized light is incident into the right-angle prism at a full reflection angle through the focusing objective lens and interacts with graphene, and totally reflected light is divided into two beams of light with the same intensity by the beam splitting prism and enters the balance detector respectively;
adjusting the position of the reflector to enable the detection light and the pump light to be completely overlapped, and observing light spots after the detection light and the pump light are overlapped through a CCD camera;
injecting a standard solution into the microfluidic channel, performing heat exchange between the standard solution and the graphene, and adjusting the position of the right-angle prism to enable a differential signal of two beams of detection light output by the balance detector to be zero;
injecting different solutions into the microfluidic channels respectively, wherein the refractive index of the solution is changed due to heat generated by pumping light, so that the GH displacement of the graphene is changed, the output voltage signal of the balanced detector is changed, the amplitude and time of the voltage change are stored, and the corresponding relation between the amplitude and time of the voltage change and the different solutions is obtained;
and injecting the solution to be detected into the microfluidic channel, and obtaining the type of the detected solution according to the corresponding relation between the amplitude and time of voltage change and different types of solutions.
Further, the standard solution is water.
Compared with the prior art, the invention has the following beneficial effects.
The method utilizes the characteristic that the large-size GH displacement of the graphene under the total reflection condition is sensitive to the refractive index of the medium on the surface of the graphene to detect the change of the refractive index of the liquid medium caused by the pump light. The invention can realize high-sensitivity detection of different solutions. In addition, due to the introduction of the pumping light, the intensity frequency is loaded to the pumping light, the signal generated by the balance detector is also the same as the frequency of the pumping light, and the signal caused by the external temperature change does not have a specific frequency, so that the interference of the external environment temperature change can be avoided.
Drawings
Fig. 1 is a schematic structural diagram of a solution detection device based on graphene GH displacement and photothermal effect according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a quartz plate, graphene and a microfluidic channel according to an embodiment of the present invention.
Fig. 3 is an optical micrograph of graphene prepared by a high-temperature reduction method after bonding with a microfluidic channel.
Fig. 4 shows the photo-thermal signal variation of graphene corresponding to the different solutions injected into the solution detection device.
In the figure, 1-detection light source, 2-polaroid, 3-half-wave plate, 4-reflector, 5-focusing objective, 6-prism with graphene, 7-beam splitter prism, 8-balance detector, 9-phase-locked amplifier, 10-pumping light source, 11-adjustable attenuator, 12-chopper, 13-CCD camera, 61-quartz plate, 62-graphene and 63-microfluidic channel.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
As shown in fig. 1-3, the solution detection device based on graphene GH displacement and photothermal effect of the present invention includes a detection light source 1, a prism 6 with graphene, a balance detector 8, a lock-in amplifier 9, a pump light source 10 and a CCD camera 13, wherein the detection light generated by the detection light source 1 sequentially passes through a polarizer 2 and a half-wave plate 3 and then is reflected by a reflector 4, the emitted light passes through a focusing objective 5 and enters an incident surface of the prism 6 with graphene at a full reflection angle, the light emitted from an emergent surface of the detection light sequentially passes through the focusing objective 5 and a splitting prism 7 and then is divided into two detection lights with the same intensity and enters the balance detector 8, the balance detector 8 is used for measuring the light intensity difference of the two detection lights, the lock-in amplifier 9 is connected with the balance detector 8, and the lock-in amplifier 9 is connected with a computer. The probe light is generated by the polarizing plate 2pPolarized light.
The pump light source 10 generates pump light, the pump light sequentially passes through the adjustable attenuator 11 and the light intensity modulation unit and is reflected by the reflector 4, the emitted light is incident to the reflecting surface of the prism 6 with graphene through the focusing objective lens 5, and the CCD camera 13 is used for observing light spots formed by coincidence of the detection light and the pump light on the reflecting surface of the prism 6 with graphene. The light intensity modulation unit is a chopper 12 or an acousto-optic modulator. The wavelength of the pump light is 980-1100 nm. The light intensity modulation unit loads intensity frequency to the pumping light, the signal generated by the balance detector 8 and the pumping light have the same frequency, and the signal caused by the external temperature change does not have specific frequency, so that the interference of the external environment temperature can be avoided. The lock-in amplifier 9 is capable of detecting a specific frequency and the computer is used for data acquisition and display.
Prism 6 with graphite alkene includes right angle prism, quartz plate 61, graphite alkene 62 and miniflow channel 63, quartz plate 61 passes through the coupling of index of refraction matching fluid on right angle prism's plane of reflection, miniflow channel 63 bonding is on quartz plate 61, miniflow channel 63 is a cross section and is the groove structure of rectangle, the both ends of miniflow channel 63 are equipped with the inlet, the material of miniflow channel 63 is PDMS (polydimethylsiloxane), graphite alkene 62 is prepared on quartz plate 61 through the high temperature reduction method, graphite alkene 62's upper surface and miniflow channel 63 bonding.
A graphene GH displacement and photothermal effect-based solution detection method comprises the following steps:
The pumping light is loaded with certain intensity frequency through the light intensity modulation unit, passes through the adjustable attenuator 11, the reflector 4 and the focusing objective 5, and then is vertically incident to the surface of the graphene.
The detection light becomes through the polarizing plate 2 and the half-wave plate 3pPolarized light is incident into the right-angle prism through the focusing objective 5 at a full reflection angle to interact with the graphene 62, and the totally reflected light is divided into two beams of light with the same intensity by the beam splitter prism 7 and respectively enters the balance detector; when the incident detection light ispPolarized light, the incident angle is the critical angle, under this condition, the GH displacement of graphene is most sensitive to the refractive index change.
The position of the reflector 4 is adjusted to ensure that the detection light and the pump light are completely overlapped, and the light spot after the detection light and the pump light are overlapped is observed through the CCD camera 13; the reflecting mirror 4 is fixed on the three-dimensional displacement table, and the position of the reflecting mirror 4 is changed by adjusting the three-dimensional displacement table.
A standard solution, such as water or a phosphate buffer solution, is injected into the microfluidic channel 63, and the standard solution exchanges heat with the graphene 62, so that the differential signal of the two beams of detection light output by the balanced detector 8 is zero by adjusting the position of the right-angle prism.
Different solutions are respectively injected into the microfluidic channels 63, the refractive indexes of the different solutions are different due to heat generated by pump light, and it can be found that when the different solutions are injected into the microfluidic channels, the voltage amplitudes output by the balance detector are different, so that the graphene GH displacement is changed, the voltage signal output by the balance detector 8 is changed, the amplitude and the time of the voltage change are stored, and the corresponding relation between the amplitude and the time of the voltage change and the different solutions is obtained. As shown in fig. 4, the correspondence between the amplitude of the voltage change and the time of the voltage change of water, 1% NaCl, 1% alcohol, and 1% glucose water is exemplarily given.
And injecting the solution to be detected into the microfluidic channel 63, and obtaining the type of the detected solution according to the corresponding relation between the amplitude and time of voltage change and different types of solutions.
In summary, according to the method provided by the present invention, the graphene absorbs the pump light with modulated intensity to generate heat and diffuse the heat into the surrounding liquid medium. The temperature of the liquid medium changes and its refractive index changes slightly. Because the refractive indexes of different solutions are different along with the change of temperature, the high-sensitivity detection of the different solutions can be realized by utilizing the characteristic that the GH displacement effect of the graphene under the total reflection condition is sensitive to the refractive index.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (6)
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