WO2021093216A1 - 一种使用太赫兹波段石墨烯吸收器的样品信号放大方法 - Google Patents
一种使用太赫兹波段石墨烯吸收器的样品信号放大方法 Download PDFInfo
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- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 claims description 12
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 10
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- XJFIKRXIJXAJGH-UHFFFAOYSA-N 5-chloro-1,3-dihydroimidazo[4,5-b]pyridin-2-one Chemical group ClC1=CC=C2NC(=O)NC2=N1 XJFIKRXIJXAJGH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005945 Chlorpyrifos-methyl Substances 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
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- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
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- HRBKVYFZANMGRE-UHFFFAOYSA-N chlorpyrifos-methyl Chemical compound COP(=S)(OC)OC1=NC(Cl)=C(Cl)C=C1Cl HRBKVYFZANMGRE-UHFFFAOYSA-N 0.000 description 4
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Images
Classifications
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3581—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
- G01N21/3586—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation by Terahertz time domain spectroscopy [THz-TDS]
Definitions
- the invention relates to a terahertz signal amplifying method of a sample, in particular to a sample signal amplifying method using a terahertz wave band graphene absorber.
- spectroscopy technology Due to its fast detection speed and simple operation, the spectroscopy technology has gradually attracted wide attention from scholars at home and abroad. Terahertz spectroscopy, as an emerging spectroscopy technology, has gradually attracted the attention of scholars from all over the world. Because the vibration and rotation energy levels of many macromolecules, and the intermolecular forces are all in the terahertz band, terahertz waves have great potential for realizing sample detection. In fields where terahertz spectroscopy technology has great application prospects, such as security inspection, biology, medicine, agriculture, and material characterization, there is a demand for trace or even ultra trace nondestructive testing.
- the surface of the sample to be tested is usually curved, and it is very necessary to achieve a close fit between the surface of the sample to be tested and the surface of the sensor.
- the metamaterials currently used in sample detection in this subject area can significantly enhance the signal of the sample, it is difficult to achieve close adhesion between the metamaterial and the surface of the tested sample due to the existence of periodic microstructures.
- the technical problem to be solved by the present invention is to overcome the shortcomings of the above-mentioned background technology and provide a sample signal amplification method using a terahertz band graphene absorber.
- the method should have high sensitivity, fast and convenient detection, and be able to bend the surface to be tested. Features of close fit.
- the technical scheme adopted by the present invention includes the following steps:
- the frequency-domain signal is used to calculate the absorbance of the sample point to be measured and the absorbance of the reference sample point, and the absorbance of the sample point to be measured and the reference sample point are calculated
- the intensity change of the absorption peak is calculated according to the intensity value corresponding to the highest point of the absorption peak to realize the amplification of the sample signal.
- the surface result of the graphene absorber is specially used as a sensor for sample signal amplification processing.
- the graphene absorber is made in the following manner:
- the graphene absorber can also be manufactured in the following manner.
- the graphene absorber obtained by the following method is flexible: the production of a flexible graphene absorber with metal as the anti-transmission layer is made of polyimide Thin film, a layer of metal is vapor-deposited on its surface, and graphene is transferred to the other surface after vapor-deposition.
- the graphene absorber can also be manufactured in the following manner.
- the graphene absorber obtained by the following method is flexible: the production of a flexible graphene absorber with a conductive tape as the anti-transmission layer, and polyimide Amine film transfers graphene on one surface, and pastes conductive tape on the other surface after the transfer.
- the thickness of the polyimide tape is 10-100 ⁇ m.
- the graphene is graphene obtained by chemical vapor deposition or mechanical exfoliation, and the number of graphene layers is 1-10 layers.
- the detection area of the sample point to be tested is greater than 1 mm 2 , and the humidity of the measurement environment is less than 0.2%.
- the sample solution uses sample solutions such as chlorpyrifos methyl, lactose, and chlorothalonil.
- sample solutions such as chlorpyrifos methyl, lactose, and chlorothalonil.
- the interaction between the sample and the graphene absorber is chemical doping, and chemical doping can effectively change the Fermi level of graphene .
- the concentration range of the sample solution obtained in the step 2) configuration is between 0.01 mg/L and 100 mg/L; in the step 3), the amount of each drop of the sample solution is 5 to 200 ⁇ L.
- the graphene absorber is cleaned in the following manner: a complete graphene absorber is taken, washed with deionized water, acetone, and deionized water successively, and dried with nitrogen.
- chlorpyrifos methyl of the product number 45396-250MG produced by Sigma can be selected, but it is not limited thereto.
- the chlorothalonil produced by Sigma company with the product number of 36791-250MG can be selected, but it is not limited to this.
- the lactose with the product number 47287-U produced by Sigma can be selected, but it is not limited thereto.
- Trivial Transfer Graphene produced by ACS Material can be used, but it is not limited to this.
- the preferred polyimide tape and film of the present invention can be used in the specific implementation of the polyimide tape and film produced by Kapton, but it is not limited thereto.
- the metal anti-transmission layer of the present invention can be replaced by silver, copper, aluminum, titanium and the like.
- the polyimide dielectric layer of the present invention can be replaced by photoresist, such as SU-8.
- the graphene layer of the present invention can be replaced by a semi-metal, such as tungsten ditelluride.
- the preferred terahertz time-domain spectroscopy system of the present invention in specific implementation recommends the use of a terahertz time-domain spectroscopy system of model z3 produced by z-omega.
- the terahertz time-domain spectroscopy (Terahertz time-domain spectroscopy, THz-TDS) adopted by the present invention is a detection technology developed and promoted internationally in recent years.
- Terahertz time-domain spectroscopy technology has been used in many fields such as national defense, medicine, chemistry, agriculture and materials.
- Terahertz wave is an electromagnetic wave with a wavelength between microwave and infrared radiation, and its frequency is 0.1-10THz, and fingerprint peaks of many molecules appear in this waveband.
- the graphene absorber of the present invention is a graphene-dielectric material-metal anti-transmission layer structure, which satisfies the impedance matching condition and can absorb electromagnetic waves of a specific waveband.
- the periodic structure on the surface of the metamaterial absorber creates a gap with the surface of the sample to be tested, which affects the sensitivity of detection.
- the outstanding advantage of the present invention is that the graphene absorber has no periodic metal structure. , The surface is flat, suitable for close fit with the curved surface, there is no gap, and the detection sensitivity is improved.
- the present invention utilizes the terahertz graphene absorber technology, which has the following beneficial effects:
- the invention adopts a graphene absorber in the terahertz band, and amplifies the signal of the sample by using the change in chemical properties (change in the Fermi level of graphene) produced by the chemical doping of graphene and the sample.
- the present invention simultaneously utilizes the characteristics of flexibility and smooth surface of the graphene absorber, and the absorber is used for the detection of samples distributed on the curved surface.
- the method of the present invention can greatly improve the detection sensitivity; compared with the metamaterial signal amplification method, the graphene absorber in the method of the present invention has no periodic structure, and the surface is flat, which can realize the integration with the curved surface. Close fit; and this method is simple and fast to operate, which can meet the increasing demand for rapid detection.
- Figure 1 is a schematic diagram of the structure of the graphene absorber of the present invention.
- Fig. 2 is the absorption spectrum obtained by simulation of the graphene absorber of the present invention under the condition of polyimide of different thicknesses.
- Fig. 3 is the absorption spectrum obtained by experiments of the graphene absorber of the present invention under the conditions of polyimide of different thicknesses.
- Fig. 4 is the absorption spectrum obtained by simulation of the graphene absorber of the present invention under graphene conditions of different Fermi levels.
- Figure 5 is the absorption spectrum of the graphene absorber in Example 1 of the present invention with and without methyl chlorpyrifos molecules.
- Example 6 is a graph showing the intensity change of the absorption spectrum of the graphene absorber caused by the chlorpyrifos methyl molecule in Example 1 of the present invention.
- Figure 7 is the absorption spectrum of the graphene absorber in Example 2 of the present invention with and without chlorothalonil molecules.
- Fig. 8 is the absorption spectrum of the graphene absorber in Example 3 of the present invention with and without lactose molecules.
- the transfer of graphene can adopt the following methods:
- Eight concentration gradients of chlorpyrifos methyl solution are respectively configured. In this embodiment, they are 0.01mg/L, 0.02mg/L, 0.05mg/L, 0.10mg/L, 0.20mg/L, 0.30mg/L, 0.40mg/ L, 0.50mg/L.
- the terahertz time-domain spectroscopy system starts to fill with nitrogen, the humidity drops, and the laser can be measured after preheating for half an hour; open the cover of the terahertz time-domain spectroscopy system, Put the graphene absorber into the detection optical path and fix it with a fixture; under the condition of nitrogen gas, the spectrum bandwidth of the terahertz time-domain spectroscopy system is 0.1-3.5THz to collect the sample points to be tested on the same graphene absorber.
- Terahertz time-domain spectroscopy with reference sample point put the metal mirror into the detection optical path and fix it with a clamp; under the condition of nitrogen gas, collect the metal reflection in the range of 0.1-3.5THz in the spectrum bandwidth of the terahertz time-domain spectroscopy system
- the terahertz time domain spectrum of the mirror the measurement environment humidity requires ⁇ 0.2%, and the temperature is normal temperature; the above method is used to measure the terahertz time domain spectrum of the sample one by one and save it to obtain the terahertz time of all the sample points to be tested and the reference sample points Domain spectrum data set.
- the fast Fourier transform is used to convert the time domain signal of the terahertz spectrum of the sample to the frequency domain signal, and the frequency domain signal is used to obtain the absorption rate of the sample point to be measured.
- the absorption rate of the graphene absorber can be obtained by the following formula:
- A represents the absorptivity of the graphene absorber
- E represents the electric field intensity of the sample point to be tested or the reference sample point in the reflection mode
- E represents the electric field intensity of the metal mirror in the reflection mode.
- Figure 4 shows the simulated absorption lines of the graphene absorber under graphene conditions of different Fermi levels.
- the transfer of graphene can adopt the following methods:
- the chlorothalonil solution is configured, and the concentration in this embodiment is 0.60 mg/L.
- the terahertz time-domain spectroscopy system starts to fill with nitrogen, the humidity drops, and the laser can be measured after preheating for half an hour; open the cover of the terahertz time-domain spectroscopy system, Put the graphene absorber into the detection optical path and fix it with a fixture; under the condition of nitrogen gas, the spectrum bandwidth of the terahertz time-domain spectroscopy system is 0.1-3.5THz to collect the sample points to be tested on the same graphene absorber.
- Terahertz time-domain spectroscopy with reference sample point put the metal mirror into the detection optical path and fix it with a clamp; under the condition of nitrogen gas, collect the metal reflection in the range of 0.1-3.5THz in the spectrum bandwidth of the terahertz time-domain spectroscopy system
- the terahertz time domain spectrum of the mirror the measurement environment humidity requires ⁇ 0.2%, and the temperature is normal temperature; the above method is used to measure the terahertz time domain spectrum of the sample one by one and save it to obtain the terahertz time of all the sample points to be tested and the reference sample points Domain spectrum data set.
- the fast Fourier transform is used to convert the time domain signal of the terahertz spectrum of the sample to the frequency domain signal, and the frequency domain signal is used to obtain the absorption rate of the sample point to be measured. Find the intensity corresponding to the maximum value of the absorption peak, and subtract the intensity value of the sample point to be tested with the intensity value of the reference sample point to obtain the change in the intensity of the absorption peak.
- the absorption spectrum of the graphene absorber with and without chlorothalonil molecules is shown in Figure 7.
- the transfer of graphene can adopt the following methods:
- the shape of the graphene absorber that needs to be laser engraved is a triangle or a circle.
- the side length of the triangle and the diameter of the circle are both 8mm.
- circular; the laser engraving machine used in this embodiment is a protolaser produced by LPKF, and the laser power is 1.1w.
- the lactose solution is prepared, and the concentration in this embodiment is 5 mg/L.
- the terahertz time-domain spectroscopy system starts to fill with nitrogen, the humidity drops, and the laser can be measured after preheating for half an hour; open the cover for the terahertz time-domain spectroscopy system Put the graphene absorber into the detection light path and fix it with a clamp; under the condition of nitrogen gas, the spectrum bandwidth of the terahertz time-domain spectroscopy system is 0.1-3.5THz to collect the sample points to be tested on the same graphene absorber.
- Terahertz time-domain spectroscopy with reference sample point put the metal mirror into the detection light path and fix it with a fixture; under the condition of nitrogen filling, collect the metal reflection in the range of 0.1-3.5THz in the spectrum bandwidth of the terahertz time-domain spectroscopy system
- the terahertz time domain spectrum of the mirror the measurement environment humidity requires ⁇ 0.2%, and the temperature is normal temperature; the above method is used to measure the terahertz time domain spectrum of the sample one by one and save it to obtain the terahertz time of all the sample points to be tested and the reference sample points Domain spectrum data set.
- the fast Fourier transform is used to convert the time domain signal of the terahertz spectrum of the sample to the frequency domain signal, and the frequency domain signal is used to obtain the absorption rate of the sample point to be measured. Find the intensity corresponding to the maximum value of the absorption peak, and subtract the intensity value of the sample point to be tested with the intensity value of the reference sample point to obtain the change in the intensity of the absorption peak.
- the absorption spectrum of the graphene absorber with and without lactose molecules is shown in Figure 8.
- the present invention uses the interaction between the graphene and the sample to change the absorption peak of the graphene absorber, thereby amplifying the sample signal, the method has high detection sensitivity, simple and fast operation, and can meet the ever-increasing demand for rapid detection.
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Abstract
一种使用太赫兹波段石墨烯吸收器的样品信号放大方法。通过蒸镀金属、转移石墨烯等步骤制作石墨烯吸收器，配置不同浓度的样品溶液，在石墨烯吸收器表面滴加样品溶液后常温下晾干，采集石墨烯吸收器表面所有待测样品点与参考样品点的太赫兹时域信号，由太赫兹时域信号计算所有待测样品点与参考样品点的吸收率，并根据吸收峰最高点对应的强度值计算得到吸收峰的强度变化。利用石墨烯与样品间相互作用改变石墨烯吸收器的吸收峰，进而放大样品信号，检测灵敏度高，操作简便快速，能满足日益增长的快速检测需求。
Description
本发明涉及一种样品的太赫兹信号放大方法，尤其涉及一种使用太赫兹波段石墨烯吸收器的样品信号放大方法。
波谱技术由于其检测速度快，操作简单的特点逐渐引起了国内外学者的广泛关注。太赫兹波谱作为一种新兴的波谱技术已逐渐引起各国学者的重视。由于许多大分子的振动、转动能级，分子间作用力等均在太赫兹波段，太赫兹波对实现样品的检测具有巨大的潜力。在太赫兹波谱技术具有较大应用前景的领域，例如安检、生物、医药、农业和材料表征等方面，存在微量甚至是超微量的无损检测需求。并且，在实际检测应用中，被测样品的表面通常是弯曲的，实现被测样品表面与传感器表面的紧密贴合是非常有必要的。然而，目前该学科领域在样品检测时所使用的超材料虽然能显著增强样品信号，但是由于周期性微结构的存在，难以实现超材料与被测样品表面的紧密贴合。
发明内容
本发明所要解决的技术问题是克服上述背景技术的不足，提供一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，该方法应具有灵敏度性高、检测快速方便、可与弯曲待测表面紧密贴合的特点。
本发明采用的技术方案包括如下步骤：
1)石墨烯吸收器的制作：制作从上到下依次包含有石墨烯、聚酰亚胺、金属防透射层的石墨烯吸收器；
2)配置不同浓度的样品溶液；
3)石墨烯吸收器表面滴加样品溶液：将样品溶液滴加在一清洗过的石墨烯吸收器表面，每个浓度滴加至少三次，每次滴加量相同，并任意设置三个参考样品点，参考样品点均与待测样品点位置不同，滴加后常温下晾干；
4)采集石墨烯吸收器表面所有待测样品点与参考样品点的太赫兹时域信号：在充氮气氛围下，在波谱频宽为0.1-10THz区间分别采集同一石墨烯吸收器上待测样品点与参考样品点的太赫兹时域信号；
5)由太赫兹时域信号得到石墨烯吸收器吸收峰的强度变化：
利用快速傅里叶变换将太赫兹波谱时域信号转换到频域信号，由频域信号计算得到待测样品点的吸收率和参考样品点吸收率，将待测样品点与参考样品点吸收率的差值作为检测信号，进而根据吸收峰最高点对应的强度值计算得到吸收峰的强度变化，实现对样品信号的放大。
本发明特殊利用石墨烯吸收器表面结果作为传感器进行样品信号放大处理。
所述步骤1)中石墨烯吸收器采用以下方式制作：
1.1)硅片或石英片表面金属的蒸镀；
取洗净的硅片或石英片，在其表面先后蒸镀厚度10nm的钛和厚度100-200nm的金；
1.2)粘贴聚酰亚胺胶带；
在蒸镀好金属的硅片或石英片的表面缓慢粘贴聚酰亚胺胶带或通过匀胶的方式在金属表面增加一层聚酰亚胺薄层；
1.3)最后在聚酰亚胺薄层上转移一层石墨烯。
所述步骤1)中石墨烯吸收器还可采用以下方式制作，以以下方法得到的石墨烯吸收器是柔性的：以金属为防透射层的柔性石墨烯吸收器的制作，取聚酰亚胺薄膜，在其表面蒸镀一层金属，蒸镀结束后在另一个表面转移石墨烯。
所述步骤1)中石墨烯吸收器还可采用以下方式制作，以以下方法得到的石墨烯吸收器是柔性的：以导电胶布为防透射层的柔性石墨烯吸收器的制作，取聚酰亚胺薄膜，在一个表面转移石墨烯，转移结束后在另一个表面粘贴导电胶布。
所述的聚酰亚胺胶带厚度为10-100μm。
所述步骤1)中石墨烯为通过化学气相沉积或者机械剥离方法得到的石墨烯，石墨烯的层数为1-10层。
所述步骤4)中采集太赫兹时域信号时，待测样品点的检测面积大于1mm
2，测量环境的湿度<0.2％。
所述的样品溶液采用甲基毒死蜱、乳糖和百菌清等样品溶液，样品与石墨烯吸收器之间的相互作用属于化学掺杂，并且通过化学掺杂可有效改变石墨烯的费米能级。
所述步骤2)配置得到的样品溶液的浓度范围均在0.01mg/L～100mg/L之间；所述步骤3)中样品溶液的每次滴加量为5～200μL。
所述步骤3)中石墨烯吸收器采用以下方式清洗：取一块完整的石墨烯吸收器，先后用去离子水，丙酮和去离子水清洗，并用氮气吹干。
优选的本发明甲基毒死蜱具体实施中可选用Sigma公司生产的货号为45396-250MG的甲基毒死蜱，但不限于此。
优选的本发明百菌清具体实施中可选用Sigma公司生产的货号为36791-250MG的百菌清，但不限于此。
优选的本发明乳糖具体实施中可选用Sigma公司生产的货号为47287-U的乳糖，但不限于此。
优选的本发明石墨烯具体实施中可选用ACS Material公司生产的Trivial Transfer Graphene，但不限于此。
优选的本发明聚酰亚胺胶带和薄膜具体实施中可选用Kapton公司生产的聚酰亚胺胶带和薄膜，但不限于此。
本发明金属防透射层可用银、铜、铝、钛等代替。
本发明的聚酰亚胺介质层可用光刻胶，如SU-8代替。
本发明的石墨烯层可用半金属，如二碲化钨代替。
具体实施中优选的本发明的太赫兹时域波谱系统推荐采用z-omega公司生产的型号为z3的太赫兹时域波谱系统。
本发明采用的太赫兹时域波谱技术(Terahertz time-domain spectroscopy，THz-TDS)，是国际上近年来发展并推广的一项检测技术。太赫兹时域波谱技术已在国防、医药、化学、农业和材料等领域有诸多应用。太赫兹波是一种波长介于微波与红外辐射之间的电磁波，其频率为0.1-10THz，并且许多分子的指纹峰出现在该波段。
本发明的石墨烯吸收器是一种石墨烯-介电材料-金属防透射层结构，该结构满足阻抗匹配条件，可吸收特定波段的电磁波。与太赫兹波段超材料吸收器相比，超材料吸收器表面的周期性结构会与待测样品表面产生间隙，影响检测的灵敏度，本发明的突出优势在于石墨烯吸收器没有周期性的金属结构，表面平整，适合与弯曲表面进行紧密的贴合，没有间隙，提高了检测灵敏度。
由此本发明利用太赫兹石墨烯吸收器技术，其具有的有益效果是：
本发明采用太赫兹波段的石墨烯吸收器，利用石墨烯与样品发生化学掺杂作用产生的化学性质的改变(石墨烯费米能级的变化)放大样品信号。
本发明同时利用石墨烯吸收器柔性和表面平整的特性，将该吸收器用于分布在弯曲表面的样品检测。
与传统的压片技术相比，本发明方法能大大提高检测灵敏度；与超材料信号放大方法相比，本发明方法中石墨烯吸收器没有周期性的结构，表面平整，可实现与弯曲表面的紧密贴合；并且本方法操作简便快速，能满足日益增长的 快速检测需求。
图1为本发明石墨烯吸收器的结构示意图。
图2为本发明石墨烯吸收器在不同厚度的聚酰亚胺条件下模拟得到的吸收谱线。
图3为本发明石墨烯吸收器在不同厚度的聚酰亚胺条件下实验得到的吸收谱线。
图4为本发明石墨烯吸收器在不同费米能级的石墨烯条件下模拟得到的吸收谱线。
图5为本发明实施例1中石墨烯吸收器在有/无甲基毒死蜱分子情况下的吸收谱线。
图6为本发明实施例1中甲基毒死蜱分子引起石墨烯吸收器吸收谱线的强度变化图。
图7为本发明实施例2中石墨烯吸收器在有/无百菌清分子情况下的吸收谱线。
图8为本发明实施例3中石墨烯吸收器在有/无乳糖分子情况下的吸收谱线。
下面结合实施实例对本发明作进一步说明，但本发明并不限于以下实施例。
本发明的实施例如下：
实施例1
(1)石墨烯吸收器的制作；
取硅片或石英片，先后在丙酮、异丙醇和水中各超声清洗10min，氮气吹干，在表面通过蒸镀的方法先后蒸镀10nm的钛和200nm的金作为防透射层，在金表面粘贴聚酰亚胺胶带(厚度为50-100μm)，聚酰亚胺胶带与金属防透射层之间不能存在气泡，结束后在聚酰亚胺胶带上转移一层石墨烯，石墨烯吸收器结构示意图如图1所示。
其中，石墨烯的转移可采用以下方式；
将购买的石墨烯释放至水中至少2小时，用镊子夹住贴有聚酰亚胺胶带的硅片或石英片去贴合水中的石墨烯，调整至合适位置后将石墨烯捞出水面，竖直放置3min使得多余水分流出后静置晾干30min，然后在烘箱中以100℃烘 干20min，静置至常温后加入丙酮浸泡10min左右，去除表面的PMMA保护层，取出石墨烯吸收器用去离子水洗净并用氮气吹干。
(2)甲基毒死蜱溶液的配置；
分别配置八个浓度梯度的甲基毒死蜱溶液，本实施实例中为0.01mg/L，0.02mg/L，0.05mg/L，0.10mg/L，0.20mg/L，0.30mg/L，0.40mg/L，0.50mg/L。
(3)石墨烯吸收器表面滴加甲基毒死蜱溶液；
取10μL甲基毒死蜱溶液，滴加在清洗过的石墨烯吸收器表面，每个浓度滴加三次，并设置三个参考样品点(没有任何样品)，常温下晾干，待测样品点的检测面积约为4mm
2。
(4)采集石墨烯吸收器表面所有待测样品点、参考样品点和金属反射镜的太赫兹时域波谱；
打开激光，电脑，控制器以及氮气阀门，此时太赫兹时域波谱系统内开始充进氮气，湿度下降，激光预热半小时后方可进行测量；打开太赫兹时域波谱系统测量用的盖子，并将石墨烯吸收器放进检测光路中，用夹具固定；充氮气情况下，在太赫兹时域波谱系统的波谱频宽为0.1-3.5THz区间分别采集同一石墨烯吸收器上待测样品点与参考样品点的太赫兹时域波谱；将金属反射镜放入检测光路中，用夹具固定；充氮气情况下，在太赫兹时域波谱系统的波谱频宽为0.1-3.5THz区间采集金属反射镜的太赫兹时域波谱；其中测量环境湿度要求<0.2％，温度为常温；用以上方法逐个测量样本的太赫兹时域波谱并保存，获得所有待测样品点与参考样品点的太赫兹时域波谱数据组。
(5)计算所有待测样品点的吸收率，并寻找吸收峰对应的强度；
利用快速傅里叶变换将样品的太赫兹波谱时域信号转换到频域信号，利用频域信号得到待测样品点的吸收率。
由于存在金属防透射层，石墨烯吸收器的透过率为0，因此，石墨烯吸收器的吸收率可由以下公式得到：
A＝|1-(E
(sample)/E
(metal))
2|*100％
上述公式中，A表示石墨烯吸收器的吸收率，E
(sample)表示反射模式下待测样品点或参考样品点的电场强度，E
(reference)表示反射模式下金属反射镜的电场强度。
石墨烯吸收器在不同厚度的聚酰亚胺条件下模拟及实验得到的吸收谱线分别如图2、3所示。
石墨烯吸收器在不同费米能级的石墨烯条件下模拟得到的吸收谱线如图4所示。
寻找吸收峰最大值对应的强度，并将待测样品点的该强度值与参考样品点的该强度值相减，得到吸收峰强度的变化。石墨烯吸收器在有/无甲基毒死蜱分子情况下的吸收谱线如图5所示；甲基毒死蜱分子引起石墨烯吸收器吸收谱线的强度变化图如图6所示。
实施例2
(1)柔性石墨烯吸收器的制作；
取厚度为50μm聚酰亚胺薄膜，先后在丙酮、异丙醇和水中各超声清洗10min，氮气吹干，在表面通过蒸镀的方法先后蒸镀10nm的钛和150nm的金作为防透射层，然后在聚酰亚胺胶带上转移一层石墨烯。
其中，石墨烯的转移可采用以下方式；
将购买的石墨烯释放至水中至少2小时后，用镊子夹住聚酰亚胺薄膜，斜着放入水中，必要时可用另一个镊子将聚酰亚胺薄膜压入水中；用未镀金的那一面贴合水中的石墨烯，调整至合适位置后将石墨烯捞出水面，竖直放置3min使得多余水分流出后静置晾干30min，再在烘箱中以100℃烘干20min，静置至常温后加入丙酮浸泡10min左右，去除表面的PMMA保护层，取出石墨烯吸收器用去离子水洗净并用氮气吹干。
(2)百菌清溶液的配置；
配置百菌清溶液，本实施实例中浓度为0.60mg/L。
(3)苹果表面滴加百菌清溶液；
取100μL百菌清溶液，滴加在清洗过的苹果表面，用柔性石墨烯吸收器贴合至滴有百菌清溶液的苹果表面，收集百菌清溶液，常温下晾干，以上步骤重复三次，获得三个待测样品点，每个待测样品点的检测面积约为10mm
2；并设置三个参考样品点(仅柔性石墨烯吸收器，没有任何样品)。
(4)采集柔性石墨烯吸收器表面所有待测样品点、参考样品点和金属反射镜的太赫兹时域波谱；
打开激光，电脑，控制器以及氮气阀门，此时太赫兹时域波谱系统内开始充进氮气，湿度下降，激光预热半小时后方可进行测量；打开太赫兹时域波谱系统测量用的盖子，并将石墨烯吸收器放进检测光路中，用夹具固定；充氮气情况下，在太赫兹时域波谱系统的波谱频宽为0.1-3.5THz区间分别采集同一石墨烯吸收器上待测样品点与参考样品点的太赫兹时域波谱；将金属反射镜放入检测光路中，用夹具固定；充氮气情况下，在太赫兹时域波谱系统的波谱频宽为0.1-3.5THz区间采集金属反射镜的太赫兹时域波谱；其中测量环境湿度要求<0.2％，温度为常温；用以上方法逐个测量样本的太赫兹时域波谱并保存，获 得所有待测样品点与参考样品点的太赫兹时域波谱数据组。
(5)计算所有待测样品点的吸收率，并寻找吸收峰对应的强度；
利用快速傅里叶变换将样品的太赫兹波谱时域信号转换到频域信号，利用频域信号得到待测样品点的吸收率。寻找吸收峰最大值对应的强度，并将待测样品点的该强度值与参考样品点的该强度值相减，得到吸收峰强度的变化。石墨烯吸收器在有/无百菌清分子情况下的吸收谱线如图7所示。
实施例3
(1)石墨烯吸收器的制作；
取硅片或石英片，先后在丙酮、异丙醇和水中各超声清洗10min，氮气吹干，在表面通过蒸镀的方法先后蒸镀10nm的钛和100nm的金作为防透射层，在金表面粘贴聚酰亚胺胶带(厚度为50-100μm)，聚酰亚胺胶带与金属防透射层之间不能存在气泡，然后在聚酰亚胺胶带上转移一层石墨烯。
其中，石墨烯的转移可采用以下方式；
将购买的石墨烯释放至水中至少2小时后，用镊子夹住贴有聚酰亚胺胶带的硅片或石英片去贴合水中的石墨烯，调整至合适位置后将石墨烯捞出水面，竖直放置3min使得多余水分流出后静置晾干30min，再在烘箱中以100℃烘干20min，静置至常温后加入丙酮浸泡10min左右，去除表面的PMMA保护层，取出石墨烯吸收器用去离子水洗净并用氮气吹干。
(2)带有图案形状的石墨烯吸收器的制作；
画好需要进行激光雕刻的石墨烯吸收器的形状，本实施实例中为三角形，圆形，其中三角形的边长和圆形的直径均为8mm，使用激光雕刻方法将石墨烯吸收器雕刻成三角形或者圆形；本实施实例中采用的激光雕刻机为LPKF公司生产的protolaser，激光功率为1.1w。
(2)乳糖溶液的配置；
配置乳糖溶液，本实施实例中浓度为5mg/L。
(3)石墨烯吸收器表面滴加乳糖溶液；
取10μL乳糖溶液，滴加在清洗过的石墨烯吸收器表面，每个浓度滴加三次，并设置三个参考样品点(没有任何样品)，常温下晾干，待测样品点的检测面积约为4mm
2。
(4)采集石墨烯吸收器表面所有待测样品点、参考样品点和金属反射镜的太赫兹时域波谱；
打开激光，电脑，控制器以及氮气阀门，此时太赫兹时域波谱系统内开始充进氮气，湿度下降，激光预热半小时后方可进行测量；打开太赫兹时域波谱 系统测量用的盖子，并将石墨烯吸收器放进检测光路中，用夹具固定；充氮气情况下，在太赫兹时域波谱系统的波谱频宽为0.1-3.5THz区间分别采集同一石墨烯吸收器上待测样品点与参考样品点的太赫兹时域波谱；将金属反射镜放入检测光路中，用夹具固定；充氮气情况下，在太赫兹时域波谱系统的波谱频宽为0.1-3.5THz区间采集金属反射镜的太赫兹时域波谱；其中测量环境湿度要求<0.2％，温度为常温；用以上方法逐个测量样本的太赫兹时域波谱并保存，获得所有待测样品点与参考样品点的太赫兹时域波谱数据组。
(5)计算所有待测样品点的吸收率，并寻找吸收峰对应的强度；
利用快速傅里叶变换将样品的太赫兹波谱时域信号转换到频域信号，利用频域信号得到待测样品点的吸收率。寻找吸收峰最大值对应的强度，并将待测样品点的该强度值与参考样品点的该强度值相减，得到吸收峰强度的变化。石墨烯吸收器在有/无乳糖分子情况下的吸收谱线如图8所示。
由此上述实施可见，本发明利用石墨烯与样品间相互作用改变石墨烯吸收器的吸收峰，进而放大样品信号，方法检测灵敏度高，操作简便快速，能满足日益增长的快速检测需求。
上述具体实施方式用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明做出的任何修改和改变，都落入本发明的保护范围。
Claims (10)
- 一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于包括如下步骤：1)石墨烯吸收器的制作：制作从上到下依次包含有石墨烯、聚酰亚胺、金属防透射层的石墨烯吸收器；2)配置不同浓度的样品溶液；3)石墨烯吸收器表面滴加样品溶液：将样品溶液滴加在一清洗过的石墨烯吸收器表面，每个浓度滴加至少三次，每次滴加量相同，并任意设置三个参考样品点，参考样品点均与待测样品点位置不同，滴加后常温下晾干；4)采集石墨烯吸收器表面所有待测样品点与参考样品点的太赫兹时域信号：在充氮气氛围下，在波谱频宽为0.1-10THz区间分别采集同一石墨烯吸收器上待测样品点与参考样品点的太赫兹时域信号；5)由太赫兹时域信号得到石墨烯吸收器吸收峰的强度变化：利用快速傅里叶变换将太赫兹波谱时域信号转换到频域信号，由频域信号计算得到待测样品点的吸收率和参考样品点吸收率，将待测样品点与参考样品点吸收率的差值作为检测信号，实现对样品信号的放大。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于：所述步骤1)中石墨烯吸收器采用以下方式制作：1.1)硅片或石英片表面金属的蒸镀；取洗净的硅片或石英片，在其表面先后蒸镀厚度10nm的钛和厚度100-200nm的金；1.2)粘贴聚酰亚胺胶带；在蒸镀好金属的硅片或石英片的表面缓慢粘贴聚酰亚胺胶带或通过匀胶的方式在金属表面增加一层聚酰亚胺薄层；1.3)最后在聚酰亚胺薄层上转移一层石墨烯。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于：所述步骤1)中石墨烯吸收器采用以下方式制作，以以下方法得到的石墨烯吸收器是柔性的：以金属为防透射层的柔性石墨烯吸收器的制作，取聚酰亚胺薄膜，在其表面蒸镀一层金属，蒸镀结束后在另一个表面转移石墨烯。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放 大方法，其特征在于：所述步骤1)中石墨烯吸收器采用以下方式制作，以以下方法得到的石墨烯吸收器是柔性的：以导电胶布为防透射层的柔性石墨烯吸收器的制作，取聚酰亚胺薄膜，在一个表面转移石墨烯，转移结束后在另一个表面粘贴导电胶布。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于：所述的聚酰亚胺胶带厚度为10-100μm。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于：所述步骤1)中石墨烯为通过化学气相沉积或者机械剥离方法得到的石墨烯，石墨烯的层数为1-10层。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于：所述步骤4)中采集太赫兹时域信号时，待测样品点的检测面积大于1mm 2，测量环境的湿度<0.2％。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于：所述的样品溶液采用甲基毒死蜱、乳糖和百菌清等样品溶液。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于：所述步骤2)配置得到的样品溶液的浓度范围均在0.01mg/L～100mg/L之间；所述步骤3)中样品溶液的每次滴加量为5～200μL。
- 根据权利要求1所述的一种使用太赫兹波段石墨烯吸收器的样品信号放大方法，其特征在于：所述步骤3)中石墨烯吸收器采用以下方式清洗：取一块完整的石墨烯吸收器，先后用去离子水，丙酮和去离子水清洗，并用氮气吹干。
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