技术领域technical field
本发明属于光电化学传感与成像技术，具体涉及一种光寻址方波/交流伏安电化学传感系统与方法。The invention belongs to photoelectrochemical sensing and imaging technology, in particular to an optical addressing square wave/AC voltammetry electrochemical sensing system and method.
背景技术Background technique
方波伏安法(square wave voltammetry，SWV)是在快速扫描的阶梯电压上迭加较大振幅的方波电压，记录方波正半周末期与方波负半周末期电流的差值，良好地消除了充电电流，又能在很短时间记录出电流-电势伏安图。交流伏安法(alternating currentvoltammetry，ACV)是在工作电极上施加一个随时间慢扫描的直流电势，并叠加一正弦波交流成分，测量电流的交流成分的幅值和和对应的相角，得到相应的交流伏安图。这两种方法具有多功能、高灵敏和高效能的特点，被广泛应用于物质的定量分析和动力学研究中。但是，常规SWV和ACV电分析法不具备空间分辨率，均以电极测量平均结果反映被测样本整体信息，难以满足高通量、多位点检测及传感需求，也无法对检测样本进行二维成像。Square wave voltammetry (square wave voltammetry, SWV) is to superimpose a large-amplitude square wave voltage on the fast-scanning ladder voltage, and record the difference between the positive half-period of the square wave and the negative half-period of the square wave to eliminate the In addition to the charging current, the current-potential voltammogram can be recorded in a short time. AC voltammetry (alternating current voltammetry, ACV) is to apply a DC potential on the working electrode that is slowly scanned over time, and superimpose a sine wave AC component, measure the amplitude and corresponding phase angle of the AC component of the current, and obtain the corresponding AC voltammogram of . These two methods have the characteristics of multi-function, high sensitivity and high efficiency, and are widely used in the quantitative analysis and kinetic research of substances. However, the conventional SWV and ACV electroanalysis methods do not have spatial resolution, and both use the average electrode measurement results to reflect the overall information of the tested sample, which is difficult to meet the requirements of high-throughput, multi-site detection and sensing, and cannot perform secondary analysis on the tested samples. dimensional imaging.
发明内容Contents of the invention
本发明提出一种可寻址方波/交流伏安电化学传感与成像方法，实现具有空间分辨能力的表面电位和体系阻抗的传感与检测，以克服现有常规电化学检测技术缺乏空间分辨能力的不足。The present invention proposes an addressable square wave/AC voltammetry electrochemical sensing and imaging method to realize the sensing and detection of surface potential and system impedance with spatial resolution, so as to overcome the lack of space in existing conventional electrochemical detection technologies Insufficient resolution.
为达到上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种光寻址方波/交流伏安电化学传感系统，包括激光装置、半导体芯片、检测池装置、电化学检测装置、位移装置和光学成像装置；半导体芯片固定于检测池装置下端，检测池装置上设有通孔容腔，通孔容腔内用于放置检测液，检测液能够与半导体芯片上端面接触，电化学检测装置的对电极和参比电极间隔放置于检测液内，电化学检测装置的工作电极与半导体芯片下端电连接，激光装置和光学成像装置设置于检测池装置上端，光学成像装置的光源和激光装置的激光能够通过通孔容腔照射于半导体芯片上表面，半导体芯片和检测池装置固定于位移装置上。An optical addressing square wave/AC voltammetry electrochemical sensing system, including a laser device, a semiconductor chip, a detection cell device, an electrochemical detection device, a displacement device, and an optical imaging device; the semiconductor chip is fixed at the lower end of the detection cell device, and detects The cell device is provided with a through-hole cavity, and the through-hole cavity is used to place the detection liquid. The detection liquid can be in contact with the upper surface of the semiconductor chip. The counter electrode and the reference electrode of the electrochemical detection device are placed in the detection liquid at intervals. The working electrode of the chemical detection device is electrically connected to the lower end of the semiconductor chip. The laser device and the optical imaging device are arranged on the upper end of the detection pool device. The light source of the optical imaging device and the laser light of the laser device can be irradiated on the upper surface of the semiconductor chip through the through hole cavity. The chip and detection pool device are fixed on the displacement device.
进一步的，电化学检测装置包括电化学工作站、对电极、参比电极和工作电极，对电极与、参比电极和工作电极均与电化学工作站相连，电极采用铂丝，参比电极采用Ag/AgCl参比电极，工作电极连接于半导体芯片。Further, the electrochemical detection device includes an electrochemical workstation, a counter electrode, a reference electrode and a working electrode, the counter electrode, the reference electrode and the working electrode are all connected to the electrochemical workstation, the electrodes are made of platinum wire, and the reference electrode is made of Ag/ The AgCl reference electrode and the working electrode are connected to the semiconductor chip.
进一步的，激光装置包括激光控制器、激光器、准直透镜、分光棱镜和放大物镜，放大物镜设置于检测池装置上端，准直透镜设置于激光器激光发射端，分光棱镜设置于准直透镜和放大物镜之间，激光器连接于激光控制器。Further, the laser device includes a laser controller, a laser, a collimating lens, a dichroic prism and a magnifying objective lens. Between the objective lenses, the laser is connected to the laser controller.
进一步的，光学成像装置包括LED照明光源、场镜和CCD相机，CCD相机连接有计算机，计算机用于获取图像并存储，场镜设置于分光棱镜一侧，场镜、分光棱镜和放大物镜在一条直线上。Further, the optical imaging device includes an LED lighting source, a field mirror and a CCD camera. The CCD camera is connected to a computer, and the computer is used to acquire images and store them. The field mirror is arranged on one side of the beam splitter. in a straight line.
进一步的，半导体芯片采用pH敏感半导体芯片或阻抗敏感半导体芯片。Further, the semiconductor chip is a pH-sensitive semiconductor chip or an impedance-sensitive semiconductor chip.
进一步的，pH敏感半导体芯片包括由上至下依次堆叠的敏感层、绝缘层、半导体层和欧姆接触层，欧姆接触层与电化学检测装置的工作电极电连接，敏感层与检测池装置内的电解液接触，，阻抗敏感半导体芯片包括上至下依次堆叠的绝缘层、半导体层和欧姆接触层，欧姆接触层与电化学检测装置的工作电极电连接，绝缘层与检测池装置内的电解液接触。Further, the pH-sensitive semiconductor chip includes a sensitive layer, an insulating layer, a semiconductor layer and an ohmic contact layer stacked sequentially from top to bottom, the ohmic contact layer is electrically connected to the working electrode of the electrochemical detection device, and the sensitive layer is connected to the sensor in the detection cell device. Electrolyte contact, the impedance-sensitive semiconductor chip includes an insulating layer, a semiconductor layer and an ohmic contact layer stacked in sequence from top to bottom, the ohmic contact layer is electrically connected to the working electrode of the electrochemical detection device, and the insulating layer is connected to the electrolyte in the detection cell device touch.
进一步的，检测池装置包括检测腔体和电连接片，检测腔体上设有通孔腔体，半导体芯片与检测腔体下端面密封接触，电连接片设置于半导体芯片下端，电连接片与半导体芯片电连接。Further, the detection cell device includes a detection cavity and an electrical connection sheet, the detection cavity is provided with a through-hole cavity, the semiconductor chip is in sealing contact with the lower end surface of the detection cavity, the electrical connection sheet is arranged at the lower end of the semiconductor chip, and the electrical connection sheet is connected to the lower end of the detection cavity. The semiconductor chips are electrically connected.
一种光寻址方波/交流伏安电化学成像方法，包括以下步骤：A light addressing square wave/AC voltammetry electrochemical imaging method, comprising the following steps:
S1、将固定有pH敏感半导体芯片的检测池装置固定于位移装置上，在检测池装置的通孔容腔内加入不同pH值的缓冲盐电解液；将电化学检测装置的对电极和参比电极放入电解液内，将工作电极与pH敏感半导体芯片的欧姆接触层相连；S1. Fix the detection cell device with the pH-sensitive semiconductor chip on the displacement device, add buffer salt electrolytes with different pH values in the through-hole cavity of the detection cell device; connect the counter electrode of the electrochemical detection device and the reference The electrode is placed in the electrolyte, and the working electrode is connected to the ohmic contact layer of the pH-sensitive semiconductor chip;
S2、调节位移装置使激光器产生的激光通过检测池装置的通孔容腔照射在pH敏感半导体芯片上端，并使激光聚焦点位于半导体表面0.8-1.2cm处；S2. Adjust the displacement device so that the laser light generated by the laser is irradiated on the upper end of the pH-sensitive semiconductor chip through the through-hole cavity of the detection cell device, and the laser focus point is located at 0.8-1.2 cm on the semiconductor surface;
S3、采用电化学工作站对不同pH溶液依次进行SWV和ACV电化学测试，获得暗/光电流-电位曲线，从而完成可寻址方波/交流伏安电化学传感检测。S3. Using an electrochemical workstation to sequentially perform SWV and ACV electrochemical tests on solutions with different pHs to obtain dark/photocurrent-potential curves, thereby completing addressable square wave/AC voltammetry electrochemical sensing detection.
一种光寻址方波/交流伏安电化学传感方法，包括以下步骤：A light addressing square wave/AC voltammetry electrochemical sensing method, comprising the following steps:
S1、将固定有阻抗敏感半导体芯片的检测池装置固定于位移装置上，在检测池装置内加入电解液；将电化学检测装置的对电极和参比电极放入电解液内，将工作电极通过电连接片与阻抗敏感半导体芯片的欧姆接触层相连；S1. Fix the detection cell device with the impedance-sensitive semiconductor chip fixed on the displacement device, and add electrolyte solution into the detection cell device; put the counter electrode and reference electrode of the electrochemical detection device into the electrolyte solution, and pass the working electrode through The electrical connection sheet is connected to the ohmic contact layer of the impedance-sensitive semiconductor chip;
S2、调节位移装置，使激光器产生的激光通过检测池装置的通孔容腔照射在阻抗敏感半导体芯片表面，并使激光聚焦点位于半导体芯片表面；S2. Adjust the displacement device so that the laser light generated by the laser is irradiated on the surface of the impedance-sensitive semiconductor chip through the through-hole cavity of the detection cell device, and the laser focus point is located on the surface of the semiconductor chip;
S3、采用电化学工作站依次进行SWV和ACV电化学测试，分别获得测试SWV和ACV的I-V曲线；S3, using the electrochemical workstation to perform the SWV and ACV electrochemical tests in sequence, and obtain the I-V curves of the SWV and ACV tests respectively;
S4、调节位移装置，通过光学成像系统进行观察，使半导体芯片以光刻图案为中心相对于激光在水平面上进行二维扫描，取对应坐标固定电位下SWV光电流大小，从而获得光刻图案的光电流分布图像，即光寻址方波伏安电化学阻抗图；S4. Adjust the displacement device and observe through the optical imaging system, so that the semiconductor chip is scanned two-dimensionally on the horizontal plane with the photolithographic pattern as the center relative to the laser, and the SWV photocurrent at the fixed potential corresponding to the coordinates is taken to obtain the photolithographic pattern. Photocurrent distribution image, that is, photoaddressable square wave voltammetry electrochemical impedance map;
进一步的，调节位移装置，使电半导体芯片相对于激光在水平方位上线性移动，对半导体芯片上的光刻图案边缘进行SWV扫描，从而获得固定电位下电流-位置曲线，对电流-位置曲线进行微分处理，得到半峰宽大小，即为光寻址方波伏安阻抗成像的空间分辨率大小。Further, adjust the displacement device so that the electric semiconductor chip moves linearly in the horizontal direction relative to the laser, and perform SWV scanning on the edge of the photolithographic pattern on the semiconductor chip, so as to obtain the current-position curve at a fixed potential, and carry out the current-position curve The half-peak width is obtained through differential processing, which is the spatial resolution of optical addressing square wave voltammetric impedance imaging.
与现有技术相比，本发明具有以下有益的技术效果：Compared with the prior art, the present invention has the following beneficial technical effects:
本发明一种光寻址方波/交流伏安电化学传感系统，将半导体芯片固定于检测池装置下端，在检测池装置上设有通孔容腔，使检测液能够与半导体芯片上端面接触形成检测空间，将电化学检测装置的对电极和参比电极间隔放置于检测液内，电化学检测装置的工作电极与半导体芯片下端电连接，激光装置设置于检测池装置上端，激光装置的激光能够通过通孔容腔照射于半导体芯片上表面，半导体芯片和检测池装置固定于位移装置上，利用激光照射结构芯片特定位置，基于电化学工作站的SWV和ACV电分析手段，可实现芯片表面电位和体系阻抗的可寻址检测及对应光学图像的实时获取，结构简单，易于广泛使用。The present invention is an optical addressing square wave/AC voltammetry electrochemical sensing system. The semiconductor chip is fixed on the lower end of the detection pool device, and a through-hole cavity is arranged on the detection pool device, so that the detection liquid can contact with the upper end surface of the semiconductor chip. The detection space is formed by contact, the counter electrode and the reference electrode of the electrochemical detection device are placed in the detection liquid at intervals, the working electrode of the electrochemical detection device is electrically connected to the lower end of the semiconductor chip, the laser device is arranged on the upper end of the detection cell device, and the laser device The laser can be irradiated on the upper surface of the semiconductor chip through the through-hole cavity, the semiconductor chip and the detection cell device are fixed on the displacement device, and the laser is used to irradiate the specific position of the structural chip. Based on the SWV and ACV electrical analysis methods of the electrochemical workstation, the chip surface can be realized. The addressable detection of potential and system impedance and the real-time acquisition of corresponding optical images have a simple structure and are easy to be widely used.
本发明一种光寻址方波/交流伏安电化学传感与成像方法，采用恒定激光照射场效应结构半导体芯片的特定位置，激发产生原位光生载流子，同时，利用电化学工作站的SWV或ACV功能调制半导体芯片外加电压，影响光生载流子的定向迁移和扩散过程，从而在外电路检测得到原位光电流，可实现对溶液pH值的检测和芯片表面阻抗的原位检测及成像，相较于传统的电化学分析方法，本发明具有空间分辨能力，为高通量、多位点的电化学检测提供了一种新的解决方案。An optical addressing square wave/AC voltammetry electrochemical sensing and imaging method of the present invention adopts a constant laser to irradiate a specific position of a semiconductor chip with a field effect structure to excite and generate in-situ photogenerated carriers. At the same time, the electrochemical workstation utilizes The SWV or ACV function modulates the applied voltage of the semiconductor chip, which affects the directional migration and diffusion process of photogenerated carriers, so that the in-situ photocurrent can be detected in the external circuit, which can realize the detection of the pH value of the solution and the in-situ detection and imaging of the chip surface impedance , compared with the traditional electrochemical analysis method, the present invention has the ability of spatial resolution, and provides a new solution for high-throughput, multi-site electrochemical detection.
附图说明Description of drawings
图1为本发明实施例中结构示意图。Fig. 1 is a schematic structural diagram of an embodiment of the present invention.
图2为本发明实施例中检测池装置与半导体芯片安装结构示意图。Fig. 2 is a schematic diagram of the installation structure of the detection cell device and the semiconductor chip in the embodiment of the present invention.
图3为本发明实施例中有光照和无光照情况下pH敏感半导体芯片SWV电流-电位I-V曲线图。Fig. 3 is a graph showing the SWV current-potential I-V curves of the pH-sensitive semiconductor chip with and without light in the embodiment of the present invention.
图4为本发明实施例中有光照和无光照情况下pH敏感半导体芯片ACV电流-电位I-V曲线图。Fig. 4 is an ACV current-potential I-V curve diagram of the pH-sensitive semiconductor chip with and without light in the embodiment of the present invention.
图5为本发明实施例中pH敏感半导体芯片电位扫描SWV曲线图；图5a为分别在pH＝3,4,5,6,7,8,9.2缓冲溶液中的光寻址SWV曲线图，图5b为在-100nA恒定电流下电位随pH变化的线性关系图。Fig. 5 is a pH-sensitive semiconductor chip potential scanning SWV curve diagram in the embodiment of the present invention; Fig. 5 a is the light addressing SWV curve diagram respectively in pH=3,4,5,6,7,8,9.2 buffer solution, Fig. 5b is a linear relationship graph of potential versus pH under a constant current of -100nA.
图6为本发明实施例中pH敏感半导体芯片电位扫描ACV曲线图，图6a为分别在pH＝3,4,5,6,7,8,9.2缓冲溶液中的光寻址ACV曲线图，图6b为在410nA恒定电流下电位随pH变化的线性关系图。Fig. 6 is the pH sensitive semiconductor chip potential scanning ACV curve diagram in the embodiment of the present invention, and Fig. 6 a is respectively in the light addressing ACV curve diagram in pH=3,4,5,6,7,8,9.2 buffer solution, Fig. 6b is a linear relationship graph of potential versus pH under a constant current of 410nA.
图7为本发明实施例中阻抗敏感半导体芯片光寻址SWV在有SU8覆盖区域和无SU8区域的扫描I-V曲线图。7 is a scanning I-V curve diagram of the optical addressing SWV of the impedance-sensitive semiconductor chip in the embodiment of the present invention in the area covered by SU8 and the area without SU8.
图8为本发明实施例中阻抗敏感半导体芯片光寻址ACV在有SU8覆盖区域和无SU8区域的扫描I-V曲线图。FIG. 8 is a scanning I-V curve diagram of the optical addressing ACV of the impedance-sensitive semiconductor chip in the embodiment of the present invention in the area covered by SU8 and the area without SU8.
图9为本发明实施例中聚焦激光在SU8图案上做二维扫描结果，图9a为光学成像系统拍摄的光学图；图9b为-0.8V电位下扫描SWV获得的光电流二维分布图。Fig. 9 is the result of two-dimensional scanning of the focused laser on the SU8 pattern in the embodiment of the present invention. Fig. 9a is an optical image taken by the optical imaging system; Fig. 9b is a two-dimensional photocurrent distribution diagram obtained by scanning SWV at -0.8V potential.
图10为本发明实施例中聚焦激光在SU8图案边缘做线性扫描结果，图10a为得到的-0.8V电位下SWV电流-位置(I-x)曲线图；图10b为基于SWV电流-位置(I-x)曲线图评估空间分辨率的结果。Figure 10 is the result of linear scanning of the focused laser on the edge of the SU8 pattern in the embodiment of the present invention, and Figure 10a is the obtained SWV current-position (I-x) curve at -0.8V potential; Figure 10b is based on the SWV current-position (I-x) The graph evaluates the results of the spatial resolution.
其中，1、激光装置；2、半导体芯片；3、检测池装置；4、电化学检测装置；5、位移装置；6、对电极；7、参比电极；8、工作电极；9、敏感层；10、绝缘层；11、半导体层；12、欧姆接触层；13、检测腔体；14、电连接片；15、密封圈；16、螺栓组；17、电化学工作站；18、光学成像装置；19、激光控制器；20、激光器；21、准直透镜；22、分光棱镜；23、放大物镜；24、LED照明光源；25、场镜；26、计算机；27、CCD相机。Among them, 1. Laser device; 2. Semiconductor chip; 3. Detection cell device; 4. Electrochemical detection device; 5. Displacement device; 6. Counter electrode; 7. Reference electrode; 8. Working electrode; 9. Sensitive layer ;10, insulating layer; 11, semiconductor layer; 12, ohmic contact layer; 13, detection cavity; 14, electrical connection piece; 15, sealing ring; 16, bolt group; 17, electrochemical workstation; ;19, laser controller; 20, laser; 21, collimating lens; 22, beam splitting prism; 23, magnifying objective lens; 24, LED lighting source;
具体实施方式Detailed ways
下面结合附图对本发明做进一步详细描述：The present invention is described in further detail below in conjunction with accompanying drawing:
如图1所示，一种光寻址方波/交流伏安电化学传感系统，包括激光装置1、半导体芯片2、检测池装置3、电化学检测装置4、位移装置5和光学成像装置18；半导体芯片2固定于检测池装置3下端，检测池装置3上设有通孔容腔，通孔容腔内用于放置检测液，检测液能够与半导体芯片2上端面接触，电化学检测装置4的对电极6和参比电极7间隔放置于检测液内，电化学检测装置4的工作电极8与半导体芯片2下端电连接，激光装置1和光学成像装置设置于检测池装置3上端，光学成像装置的光源和激光装置1的激光能够通过通孔容腔照射于半导体芯片2上表面，激光装置1和光学成像装置2形成共焦系统，半导体芯片2和检测池装置3固定于位移装置5上。As shown in Figure 1, an optical addressable square wave/AC voltammetry electrochemical sensing system includes a laser device 1, a semiconductor chip 2, a detection cell device 3, an electrochemical detection device 4, a displacement device 5 and an optical imaging device 18. The semiconductor chip 2 is fixed on the lower end of the detection pool device 3. The detection pool device 3 is provided with a through-hole cavity, and the through-hole cavity is used to place a detection liquid. The detection liquid can be in contact with the upper surface of the semiconductor chip 2 for electrochemical detection. The counter electrode 6 and the reference electrode 7 of the device 4 are placed at intervals in the detection solution, the working electrode 8 of the electrochemical detection device 4 is electrically connected to the lower end of the semiconductor chip 2, the laser device 1 and the optical imaging device are arranged at the upper end of the detection cell device 3, The light source of the optical imaging device and the laser light of the laser device 1 can be irradiated on the upper surface of the semiconductor chip 2 through the cavity of the through hole, the laser device 1 and the optical imaging device 2 form a confocal system, and the semiconductor chip 2 and the detection cell device 3 are fixed on the displacement device 5 on.
电化学检测装置4包括电化学工作站17、对电极6、参比电极7和工作电极8。对电极、参比电极和工作电极与电化学工作站相连，用于SWV和ACV电化学检测；本申请对电极采用铂丝，参比电极采用Ag/AgCl参比电极，工作电极连接于半导体芯片。The electrochemical detection device 4 includes an electrochemical workstation 17 , a counter electrode 6 , a reference electrode 7 and a working electrode 8 . The counter electrode, reference electrode and working electrode are connected to the electrochemical workstation for electrochemical detection of SWV and ACV; in this application, the counter electrode uses platinum wire, the reference electrode uses Ag/AgCl reference electrode, and the working electrode is connected to the semiconductor chip.
其中激光装置1包括激光控制器19、激光器20、准直透镜21、分光棱镜22和放大物镜23，放大物镜23设置于检测池装置3上端，准直透镜21设置于激光器20激光发射端，分光棱镜22设置于准直透镜21和放大物镜23之间，激光器连接于激光控制器，产生波长为405nm的激光，激光通过准直透镜21、分光棱镜22和放大物镜23及通孔容腔照射于半导体芯片上表面，光斑直径在聚焦时约为10μm；放大物镜23放大倍数为10倍。Wherein the laser device 1 comprises a laser controller 19, a laser device 20, a collimating lens 21, a beam splitting prism 22 and an enlarging objective lens 23, the enlarging objective lens 23 is arranged on the upper end of the detection cell device 3, and the collimating lens 21 is arranged on the laser emitting end of the laser device 20 to split the light The prism 22 is arranged between the collimating lens 21 and the magnifying objective lens 23, and the laser device is connected to the laser controller to generate laser light with a wavelength of 405nm. On the upper surface of the semiconductor chip, the diameter of the light spot is about 10 μm when focusing; the magnification of the magnifying objective lens 23 is 10 times.
光学成像装置包括LED照明光源24、场镜25和CCD相机27，CCD相机连接有计算机26，计算机26用于获取图像并存储，场镜25设置于分光棱镜22一侧，场镜25、分光棱镜22和放大物镜23在一条直线上，LED照明光通过通孔容腔照射于半导体芯片上表面，其反射光经过放大物镜23、分光棱镜、场镜至CCD相机获得光学图像。Optical imaging device comprises LED illumination light source 24, field lens 25 and CCD camera 27, and CCD camera is connected with computer 26, and computer 26 is used to obtain image and store, and field lens 25 is arranged on dichroic prism 22 one sides, and field lens 25, dichroic prism 22 and the magnifying objective lens 23 are on a straight line, and the LED illumination light is irradiated on the upper surface of the semiconductor chip through the through-hole cavity, and the reflected light passes through the magnifying objective lens 23, the beam splitting prism, and the field lens to the CCD camera to obtain an optical image.
半导体芯片2采用pH敏感半导体芯片或阻抗敏感半导体芯片；pH敏感半导体芯片包括由上至下依次堆叠的敏感层9、绝缘层10、半导体层11和欧姆接触层12，欧姆接触层12与电化学检测装置4的工作电极8电连接，形成良好的接触，以导通电流，敏感层9与检测池装置3内的电解液接触。阻抗敏感半导体芯片包括上至下依次堆叠的绝缘层10、半导体层11和欧姆接触层12，欧姆接触层12与电化学检测装置4的工作电极8电连接，绝缘层10与检测池装置3内的电解液接触，绝缘层表面制备有SU8光刻胶图案。The semiconductor chip 2 adopts a pH-sensitive semiconductor chip or an impedance-sensitive semiconductor chip; the pH-sensitive semiconductor chip includes a sensitive layer 9, an insulating layer 10, a semiconductor layer 11 and an ohmic contact layer 12 stacked sequentially from top to bottom, and the ohmic contact layer 12 and the electrochemical The working electrode 8 of the detection device 4 is electrically connected to form a good contact to conduct current, and the sensitive layer 9 is in contact with the electrolyte in the detection cell device 3 . The impedance-sensitive semiconductor chip includes an insulating layer 10, a semiconductor layer 11 and an ohmic contact layer 12 stacked in sequence from top to bottom. The ohmic contact layer 12 is electrically connected to the working electrode 8 of the electrochemical detection device 4. contact with the electrolyte, and the surface of the insulating layer is prepared with a SU8 photoresist pattern.
如图2所示，检测池装置3包括检测腔体13和电连接片14，检测腔体13上设有通孔腔体，半导体芯片2与检测腔体13下端面接触，电连接片14设置于半导体芯片2下端，电连接片14与半导体芯片2电连接；半导体芯片2与检测腔体13通过螺栓组16固定连接，将半导体芯片2夹持于电连接片14与检测腔体13之间；具体的，半导体芯片2的欧姆接触层12与电连接片14接触。As shown in Figure 2, the detection cell device 3 includes a detection cavity 13 and an electrical connection piece 14, the detection cavity 13 is provided with a through-hole cavity, the semiconductor chip 2 is in contact with the lower end surface of the detection cavity 13, and the electrical connection piece 14 is provided At the lower end of the semiconductor chip 2, the electrical connection piece 14 is electrically connected to the semiconductor chip 2; the semiconductor chip 2 and the detection cavity 13 are fixedly connected by a bolt group 16, and the semiconductor chip 2 is clamped between the electrical connection piece 14 and the detection cavity 13 Specifically, the ohmic contact layer 12 of the semiconductor chip 2 is in contact with the electrical connecting sheet 14 .
半导体芯片2与检测腔体13下端面之间设有密封圈15，所述密封圈采用硅橡胶密封圈。所述检测腔体13采用有机玻璃体。电连接片14采用铝片。A sealing ring 15 is provided between the semiconductor chip 2 and the lower end surface of the detection cavity 13, and the sealing ring is a silicon rubber sealing ring. The detection cavity 13 is made of organic glass. The electrical connecting sheet 14 adopts an aluminum sheet.
pH敏感半导体芯片用于溶液pH测试，本申请采用pH敏感半导体芯片具体结构为：(50nm Si3N4)-绝缘层(100nm SiO2)-半导体层(p-Si,100,1-10Ωcm)-欧姆接触(30nm Cr,150nm Au)，其中Si3N4和欧姆接触是利用磁控溅射方法制备，SiO2是利用热氧化方法生长。The pH-sensitive semiconductor chip is used for solution pH testing. The specific structure of the pH-sensitive semiconductor chip used in this application is: (50nm Si3 N4 )-insulating layer (100nm SiO2 )-semiconductor layer (p-Si,100,1-10Ωcm) - Ohmic contact (30nm Cr, 150nm Au), where Si3 N4 and ohmic contact are prepared by magnetron sputtering method and SiO2 is grown by thermal oxidation method.
阻抗敏感半导体芯片用于阻抗成像，本申请采用阻抗敏感半导体芯片具体结构为：绝缘层自组装机单分子膜(self-assembled organic monolayers,SAMs)-半导体层(p-Si,100,1-10Ωcm)-欧姆接触(30nm Cr,150nm Au)，其中SAMs为使用热诱导硅烷化法生长的十一碳烯酸膜，厚度为1nm，相较于传统氧化硅绝缘层，可显著增加体系的阻抗灵敏度。电化学检测时半导体芯片敏感层朝上，作为工作电极与电解液接触，绝缘层表面制备有厚度约为5μm的SU8 2005光刻胶图案。The impedance-sensitive semiconductor chip is used for impedance imaging. The specific structure of the impedance-sensitive semiconductor chip used in this application is: insulating layer self-assembled machine monolayers (self-assembled organic monolayers, SAMs)-semiconductor layer (p-Si, 100, 1-10Ωcm )-ohmic contact (30nm Cr, 150nm Au), in which SAMs are undecylenic acid films grown by thermally induced silylation with a thickness of 1nm, which can significantly increase the impedance sensitivity of the system compared with traditional silicon oxide insulating layers . During the electrochemical detection, the sensitive layer of the semiconductor chip faces up, and is used as a working electrode in contact with the electrolyte, and a SU8 2005 photoresist pattern with a thickness of about 5 μm is prepared on the surface of the insulating layer.
位移装置5采用三维电动位移系统，检测池装置3固定于位移系统XY平面上。The displacement device 5 adopts a three-dimensional electric displacement system, and the detection pool device 3 is fixed on the XY plane of the displacement system.
一种光寻址方波/交流伏安电化学传感方法，包括以下步骤：A light addressing square wave/AC voltammetry electrochemical sensing method, comprising the following steps:
S1、半导体芯片清洁、组装：S1. Semiconductor chip cleaning and assembly:
步骤1、将半导体芯片依次在丙酮、异丙醇和纯水中超声清洗各15min，用氮气枪吹干备用。Step 1. Ultrasonic clean the semiconductor chip in acetone, isopropanol and pure water for 15 minutes each, and dry it with a nitrogen gun for later use.
步骤2、将清洗过的半导体芯片敏感层朝上置于铝片上，再将有机玻璃腔体放置于半导体芯片上，使通孔腔体位于芯片上方，利用螺栓组16将半导体芯片2与检测腔体13固定，在半导体芯片2与检测腔体13通过密封圈15密封；Step 2. Place the cleaned semiconductor chip with the sensitive layer facing up on the aluminum sheet, then place the plexiglass cavity on the semiconductor chip so that the through-hole cavity is located above the chip, and use the bolt group 16 to connect the semiconductor chip 2 to the detection cavity. The body 13 is fixed, and the semiconductor chip 2 and the detection cavity 13 are sealed by a sealing ring 15;
步骤3、将组装有半导体芯片的检测池装置3固定在位移装置5上，调节位移装置，使激光装置1产生的激光照射在半导体芯片上。Step 3. Fix the detection cell device 3 assembled with the semiconductor chip on the displacement device 5, and adjust the displacement device so that the laser light generated by the laser device 1 is irradiated on the semiconductor chip.
S2、光电流响应测试：S2. Photocurrent response test:
调节位移装置5的Z向高度，使检测池装置3上的半导体芯片位于激光装置1产生的激光焦点位置0.8-1.2cm处，即非聚焦状态，将激光关闭或开启，本申请使用CHI 660E电化学工作站在pH 7缓冲液中分别进行SWV和ACV电化学测试，获得暗/光电流-电位I-V曲线。Adjust the height of the displacement device 5 in the Z direction so that the semiconductor chip on the detection cell device 3 is located at the focal point of the laser light generated by the laser device 1 at 0.8-1.2 cm, that is, in a non-focused state. Turn the laser off or on. This application uses a CHI 660E electric The chemical workstation performed SWV and ACV electrochemical tests in pH 7 buffer solution to obtain dark/photocurrent-potential I-V curves.
使用pH敏感半导体芯片连接工作电极，银/氯化银参比电极作为参比电极，铂丝作为对电极构成三电极体系；其中SWV的电压扫描范围为：0.4～-1.2V，振幅为0.05V，扫描频率为1KHz；ACV的电压扫描范围为：0.1～-1.5V，振幅为0.02V，扫描频率为200Hz。Use a pH-sensitive semiconductor chip to connect the working electrode, a silver/silver chloride reference electrode as the reference electrode, and a platinum wire as the counter electrode to form a three-electrode system; the voltage scanning range of SWV is: 0.4～-1.2V, and the amplitude is 0.05V , the scanning frequency is 1KHz; the voltage scanning range of ACV is: 0.1～-1.5V, the amplitude is 0.02V, and the scanning frequency is 200Hz.
S3、pH敏感性测试：S3. pH sensitivity test:
调节位移装置5的Z向高度，使检测池装置3上的半导体芯片位于激光装置1产生的激光焦点位置0.8-1.2cm处，即非聚焦状态，考察pH敏感半导体芯片对溶液pH的敏感性。分别将2ml不同(pH值pH:3～9.2)，0.1M NaCl的缓冲液加入检测腔中，依此测试SWV和ACV所对应的I-V曲线。其中SWV的电压扫描范围为：0.4～-1.2V，振幅为0.05V，扫描频率为1KHz；ACV的电压扫描范围为：0.1～-1.5V，振幅为0.02V，扫描频率为200Hz。Adjust the height of the displacement device 5 in the Z direction so that the semiconductor chip on the detection cell device 3 is located at the focal point of the laser light generated by the laser device 1 at 0.8-1.2 cm, that is, in a non-focused state, and investigate the sensitivity of the pH-sensitive semiconductor chip to the pH of the solution. Add 2ml of different (pH: 3-9.2), 0.1M NaCl buffer solutions into the detection chamber, and test the I-V curves corresponding to SWV and ACV accordingly. The voltage scanning range of SWV is: 0.4～-1.2V, the amplitude is 0.05V, and the scanning frequency is 1KHz; the voltage scanning range of ACV is: 0.1～-1.5V, the amplitude is 0.02V, and the scanning frequency is 200Hz.
S4、阻抗原位检测与成像：S4. Impedance in-situ detection and imaging:
步骤1、调节位移装置5的Z向高度，使激光聚焦在阻抗敏感半导体芯片表面，考察光寻址方波/交流伏安法的阻抗原位检测功能。具体的，采用标准光刻技术在半导体芯片表面制备SU8 2005图案，光刻胶厚度为5μm，图案为边长为100μm的正方形。通过位移装置5调节阻抗敏感半导体芯片相对于激光的位置，使激光正好照射到光刻胶覆盖或无光刻胶覆盖区域，分别测试SWV和ACV I-V曲线。其中SWV的电压扫描范围为-0.4～-0.8V，振幅为0.05V，扫描频率为100Hz；ACV电位扫描范围为-0.3～-0.55V，电位振幅为0.1V，扫描频率为10Hz。Step 1. Adjust the height of the displacement device 5 in the Z direction to focus the laser light on the surface of the impedance-sensitive semiconductor chip, and investigate the impedance in-situ detection function of the optical addressing square wave/AC voltammetry. Specifically, a SU8 2005 pattern was prepared on the surface of the semiconductor chip by standard photolithography technology, the thickness of the photoresist was 5 μm, and the pattern was a square with a side length of 100 μm. Adjust the position of the impedance-sensitive semiconductor chip relative to the laser through the displacement device 5, so that the laser just irradiates the photoresist-covered or non-photoresist-covered area, and test the SWV and ACV I-V curves respectively. The voltage scanning range of SWV is -0.4～-0.8V, the amplitude is 0.05V, and the scanning frequency is 100Hz; the potential scanning range of ACV is -0.3～-0.55V, the potential amplitude is 0.1V, and the scanning frequency is 10Hz.
步骤2、基于步骤1中得到的SWV I-V曲线结果，在-0.8V电位下对SU8图案进行二维扫描获得SWV光电流图，并与光学成像系统拍摄的光学图进行比较。通过位移装置在x和y方向的二维扫描(步长：4μm，停滞时间：2.3s，扫描范围：200μm×200μm)，对图案进行SWV测试(-0.78～-0.8V，振幅0.05V，扫描频率100Hz)，即位移装置每移动到一点，便采集此点在-0.8V下SWV电流大小，从而获得光电流二维图像。Step 2. Based on the result of the SWV I-V curve obtained in step 1, two-dimensionally scan the SU8 pattern at the potential of -0.8V to obtain a SWV photocurrent map, and compare it with the optical map taken by the optical imaging system. Through the two-dimensional scanning of the displacement device in the x and y directions (step size: 4μm, dwell time: 2.3s, scanning range: 200μm×200μm), the SWV test (-0.78～-0.8V, amplitude 0.05V, scanning Frequency 100Hz), that is, every time the displacement device moves to a point, it collects the SWV current at -0.8V at this point, so as to obtain a two-dimensional image of the photocurrent.
采用标准光刻技术在半导体芯片表面制备SU8 2005图案，光刻胶厚度为5μm，图案为边长为100μm的正方形。The SU8 2005 pattern was prepared on the surface of the semiconductor chip by standard photolithography technology, the thickness of the photoresist was 5 μm, and the pattern was a square with a side length of 100 μm.
步骤3)在-0.8V电位下检测光寻址SWV阻抗成像的分辨率大小：通过位移装置x方向的线性移动(步长：2μm，停滞时间：2.3s)，对图案边缘进行SWV扫描(-0.78～-0.8V，振幅0.05V，扫描频率100Hz)，即位移装置每移动到一点，便采集此点在-0.8V下SWV电流大小，从而获得光电流-位置(I-x)曲线，对曲线进行微分处理，得到半峰宽大小，即为光寻址SWV阻抗成像的空间分辨率大小。Step 3) Detect the resolution of light-addressed SWV impedance imaging at -0.8V potential: through the linear movement of the displacement device in the x direction (step size: 2μm, dwell time: 2.3s), perform SWV scanning on the pattern edge (- 0.78～-0.8V, amplitude 0.05V, scanning frequency 100Hz), that is, every time the displacement device moves to a point, it collects the magnitude of the SWV current at -0.8V at this point, so as to obtain the photocurrent-position (I-x) curve. The half-peak width is obtained through differential processing, which is the spatial resolution of the light-addressed SWV impedance imaging.
针对上述用于表面电位传感和阻抗成像，检测结果如下：For the above-mentioned surface potential sensing and impedance imaging, the detection results are as follows:
当电位扫描范围为0.4～-1.2V，电位振幅为0.05V，扫描频率为1KHz时，pH敏感半导体芯片的SWV I-V曲线如图3所示，由图3可知，光电流随电位呈“s”曲线变化趋势：当电位较正时(0.4～-0.1V)，SWV电流较低且变化较小，对应场效应结构特异I-V曲线的累积层；随着电位的不断降低，光电流绝对值逐渐增加，对应场效应结构的耗尽层；电位-1.2V时电流达到饱和，对应场效应结构反型层。When the potential scanning range is 0.4～-1.2V, the potential amplitude is 0.05V, and the scanning frequency is 1KHz, the SWV I-V curve of the pH-sensitive semiconductor chip is shown in Figure 3. It can be seen from Figure 3 that the photocurrent is "s" with the potential Curve change trend: when the potential is relatively positive (0.4～-0.1V), the SWV current is low and the change is small, corresponding to the accumulation layer of the field-effect structure-specific I-V curve; as the potential continues to decrease, the absolute value of the photocurrent increases gradually , corresponding to the depletion layer of the field effect structure; when the potential is -1.2V, the current reaches saturation, corresponding to the inversion layer of the field effect structure.
当电位扫描范围为0.1～-1.5V，振幅为0.02V，扫描频率为200Hz时，pH敏感半导体芯片的ACV光电流曲线如图4所示。由图4可知，光电流随电位亦呈“s”曲线变化趋势：当电位较正时0.1～-0.1V，电流相对较低且变化较小；随着电位的不断降低，光电流逐渐增加，直到-1.2V左右达到饱和。When the potential scanning range is 0.1-1.5V, the amplitude is 0.02V, and the scanning frequency is 200Hz, the ACV photocurrent curve of the pH-sensitive semiconductor chip is shown in Figure 4. It can be seen from Figure 4 that the photocurrent also exhibits an "s" curve change trend with the potential: when the potential is relatively positive at 0.1 to -0.1V, the current is relatively low and the change is small; as the potential continues to decrease, the photocurrent gradually increases. Until it reaches saturation around -1.2V.
当电位扫描范围为0.4～-1.2V，电位振幅为0.05V，扫描频率为1KHz时，pH敏感半导体芯片在不同pH溶液中测试的光寻址SWV曲线如图5a所示；随着溶液pH的增加，I-V曲线逐渐向负电位方向偏移；如图5b所示，在-100nA的恒定光电流下，pH灵敏度为55.9mV/pH。When the potential scanning range is 0.4～-1.2V, the potential amplitude is 0.05V, and the scanning frequency is 1KHz, the optical addressing SWV curves of the pH-sensitive semiconductor chip tested in different pH solutions are shown in Figure 5a; Increase, the I-V curve gradually shifts to the negative potential direction; as shown in Figure 5b, at a constant photocurrent of -100nA, the pH sensitivity is 55.9mV/pH.
当电位扫描范围为0.3～-0.8V，振幅为0.02V，扫描频率为200Hz时，pH敏感半导体芯片在不同pH溶液中测试的光寻址ACV曲线如图6a所示。随着溶液pH的增加，I-V曲线亦逐渐向负电位方向偏移。如图6b所示，在405nA的恒定光电流下，pH灵敏度为46.7mV/pH。When the potential scanning range is 0.3-0.8V, the amplitude is 0.02V, and the scanning frequency is 200Hz, the optical addressing ACV curves of the pH-sensitive semiconductor chip tested in different pH solutions are shown in Figure 6a. As the pH of the solution increases, the I-V curve gradually shifts to the negative potential direction. As shown in Figure 6b, the pH sensitivity was 46.7 mV/pH at a constant photocurrent of 405 nA.
当电位扫描范围为-0.4～-0.8V，电位振幅为0.05V，扫描频率为100Hz时，聚焦激光在阻抗敏感半导体芯片上SU8光刻胶覆盖区域和无覆盖区域扫描的SWV曲线如图7所示。由于SU8光刻胶会原位增加芯片表面的阻抗，因此，在电流饱和区域，即反型层，芯片表面有SU8覆盖部位的光电流绝对值比无SU8部位显著降低。When the potential scanning range is -0.4～-0.8V, the potential amplitude is 0.05V, and the scanning frequency is 100Hz, the SWV curves of the focused laser scanning on the SU8 photoresist-covered and non-covered areas on the impedance-sensitive semiconductor chip are shown in Figure 7. Show. Since the SU8 photoresist will increase the impedance of the chip surface in situ, in the current saturation region, that is, the inversion layer, the absolute value of the photocurrent on the chip surface covered with SU8 is significantly lower than that without SU8.
当电位扫描范围为-0.3～-0.55V，电位振幅为0.1V，扫描频率为10Hz时，聚焦激光在阻抗敏感半导体芯片上SU8光刻胶覆盖的区域和无覆盖的区域的ACV曲线如图8所示，由于SU8光刻胶会原位增加芯片表面的阻抗，因此，在反型层，芯片表面有SU8覆盖部位的光电流比无SU8的显著降低。When the potential scanning range is -0.3～-0.55V, the potential amplitude is 0.1V, and the scanning frequency is 10Hz, the ACV curves of the focused laser on the area covered by the SU8 photoresist and the area not covered on the impedance-sensitive semiconductor chip are shown in Figure 8 As shown, since the SU8 photoresist will increase the impedance of the chip surface in situ, in the inversion layer, the photocurrent of the chip surface covered with SU8 is significantly lower than that without SU8.
以SU8图案为中心，使用光学成像系统拍摄光学图像如图9a所示。以SU8图案为中心，通过位移装置进行xy方向的二维扫描(步长：4μm，停滞时间：2.3s，扫描范围：200μm×200μm)，同时进行SWV测试(-0.78～-0.8V，振幅0.05V，扫描频率100Hz)，取对应位置坐标-0.8V下SWV电流大小，获得SWV光电流二维图像如图9b所示。由于SU8光刻胶会原位增加芯片表面的阻抗，因此，有光刻胶覆盖区域光电流明显较低。SWV光电流图像与光学图像能较好对应。Taking the SU8 pattern as the center, an optical image was taken using an optical imaging system as shown in Fig. 9a. With the SU8 pattern as the center, two-dimensional scanning in the xy direction (step size: 4μm, dwell time: 2.3s, scanning range: 200μm×200μm) is performed through the displacement device, and the SWV test (-0.78～-0.8V, amplitude 0.05 V, scanning frequency 100Hz), take the SWV current magnitude at the corresponding position coordinate -0.8V, and obtain a two-dimensional image of the SWV photocurrent as shown in Figure 9b. Since the SU8 photoresist will increase the impedance of the chip surface in situ, the photocurrent in the area covered by the photoresist is significantly lower. The SWV photocurrent image corresponds well to the optical image.
通过位移装置x方向的线性移动(步长：2μm，停滞时间：2.5s，扫描范围：90μm)，对阻抗敏感半导体芯片SU8图案边缘处进行光寻址SWV扫描-0.78～-0.8V，振幅为0.05V，扫描频率为100Hz，取对应位置坐标-0.8V下SWV电流大小，得到电流-位置I-x曲线如图9a图所示，对I-x曲线进行微分处理后的曲线如图9b所示。由图9a可知，由于SU8会增加其覆盖区域的原位阻抗，当激光从SU8覆盖区域向无SU8区域移动时，光电流绝对值会急剧增加。通过微分处理后求半峰宽大小可知光寻址SWV的空间分辨率约为5.2μm。Through the linear movement of the displacement device in the x direction (step size: 2μm, dead time: 2.5s, scanning range: 90μm), perform optical addressing SWV scanning -0.78～-0.8V on the edge of the impedance-sensitive semiconductor chip SU8 pattern, with an amplitude of 0.05V, the scanning frequency is 100Hz, take the SWV current at the corresponding position coordinate -0.8V, and obtain the current-position I-x curve as shown in Figure 9a, and the curve after differential processing on the I-x curve is shown in Figure 9b. It can be seen from Figure 9a that since SU8 will increase the in-situ impedance of its coverage area, when the laser moves from the SU8 coverage area to the SU8-free area, the absolute value of the photocurrent will increase sharply. After calculating the half-peak width after differential processing, it can be known that the spatial resolution of the light-addressing SWV is about 5.2 μm.
本发明提出一种可寻址光电化学检测方法，使用一束恒定激光照射半导体场效应结构产生局部光生载流子，同时，利用电化学工作站的SWV或ACV功能调制半导体芯片外加电压，检测得到光电流。结果表明，当使用氮化硅作为敏感层时，可实现对溶液pH值的检测。此外，基于SAMs绝缘的半导体芯片可用于芯片表面阻抗的原位检测与成像。相较于传统的电化学分析方法，本发明提出的光寻址SWV/ACV具有一定的空间分辨能力，为高通量、多位点的电化学检测提供了一种解决方案。The present invention proposes an addressable photoelectrochemical detection method, which uses a beam of constant laser light to irradiate the semiconductor field effect structure to generate local photogenerated carriers. current. The results show that when silicon nitride is used as the sensitive layer, the detection of the pH value of the solution can be realized. In addition, semiconductor chips based on SAMs insulation can be used for in situ detection and imaging of chip surface impedance. Compared with traditional electrochemical analysis methods, the optical addressing SWV/ACV proposed by the present invention has a certain spatial resolution capability, and provides a solution for high-throughput, multi-site electrochemical detection.
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