技术领域technical field
本发明属于光电检测技术领域，具体涉及一种基于黑硅和量子点的Si-APD光电探测器及其制备方法，其属于硅基雪崩光电探测器技术领域中光电探测器结构和半导体纳米材料。The invention belongs to the technical field of photoelectric detection, and specifically relates to a Si-APD photodetector based on black silicon and quantum dots and a preparation method thereof, which belongs to the photodetector structure and semiconductor nanomaterials in the technical field of silicon-based avalanche photodetectors.
背景技术Background technique
光电探测器是一种能把光信号转变为电信号的光电器件，其特点是封装体积小，光电响应快，探测灵敏度高，工艺成熟且价格低廉。光电探测器被广泛应用于信号传输处理，红外热成像遥感，射线探测，工业自动控制等军事和民用领域。A photodetector is a photoelectric device that can convert light signals into electrical signals. It is characterized by small package size, fast photoelectric response, high detection sensitivity, mature technology and low price. Photoelectric detectors are widely used in signal transmission processing, infrared thermal imaging remote sensing, ray detection, industrial automatic control and other military and civilian fields.
雪崩光电二极管(APD)是一种具有内部增益的光电探测器，工作在能使器件发生雪崩倍增效应的高反向偏压下，雪崩倍增效应造成了内部电流增益，使得APD器件比其他器件具有更高的响应度。因其具有灵敏度高、体积小、增益大灯一系列优点，实现对微弱信号的高校探测，被广泛的应用于光纤通讯、激光测距、激光引信、光谱测量、遥感测量、医学影像诊断、环境监测和军事侦察等方面。An avalanche photodiode (APD) is a photodetector with internal gain. It works at a high reverse bias voltage that can cause the device to undergo avalanche multiplication. The avalanche multiplication effect causes internal current gain, making the APD device more efficient than other devices. Higher responsiveness. Because of its advantages of high sensitivity, small size, and gain headlights, it can realize the detection of weak signals, and is widely used in optical fiber communication, laser ranging, laser fuze, spectral measurement, remote sensing measurement, medical imaging diagnosis, environmental surveillance and military reconnaissance.
目前商用的APD红外探测器主要包括HgCdTe材料APD和InGaAs-InP APD。HgCdTe材料根据Cd在HgCdTe材料中所占的比重调节材料禁带宽度(0eV-1.6eV)，但是HgCdTe材料APD需要工作低温条件下，InGaAs单晶半导体材料存在价格昂贵、热机械性能差、晶体质量较差、且不易与现有硅微电子工艺兼容等缺陷。Currently commercial APD infrared detectors mainly include HgCdTe material APD and InGaAs-InP APD. The HgCdTe material adjusts the material gap (0eV-1.6eV) according to the proportion of Cd in the HgCdTe material, but the HgCdTe material APD needs to work under low temperature conditions, and the InGaAs single crystal semiconductor material is expensive, has poor thermomechanical properties, and crystal quality. Poor, and not easy to be compatible with existing silicon microelectronics processes and other defects.
Si材料具有易于提纯、易于掺杂、资源丰富、成本低、易于大规模集成和相关技术成熟等优点，是半导体行业应用最为广泛的一类材料。Si材料具有高得碰撞电离系数比，用于光探测时可使器件的信噪比得到提高。然而，由于其禁带宽度较大(1.1eV)，即使在光敏区沉淀了增透膜，也无法探测波长大于1.1μm的光波信号，现有的Si-APD光电探测器存在红外响应低或者无法探测红外信号等问题。并且，传统的Si-APD光电探测器为了提高现有Si-APD的光电效率和量子效率，通常具有较厚的本征吸收层，进一步造成其响应时间长，响应速度慢，探测度低等问题。Si material has the advantages of easy purification, easy doping, rich resources, low cost, easy large-scale integration and mature related technologies, etc., and is the most widely used type of material in the semiconductor industry. Si material has a high impact ionization coefficient ratio, which can improve the signal-to-noise ratio of the device when used for photodetection. However, due to its large forbidden band width (1.1eV), even if an anti-reflection coating is deposited on the photosensitive area, it is impossible to detect light wave signals with a wavelength greater than 1.1 μm. The existing Si-APD photodetectors have low infrared response or cannot Detect issues such as infrared signals. Moreover, in order to improve the photoelectric efficiency and quantum efficiency of the existing Si-APD, the traditional Si-APD photodetector usually has a thicker intrinsic absorption layer, which further causes problems such as long response time, slow response speed, and low detection degree. .
发明内容Contents of the invention
基于现有技术存在的问题，本发明提供一种基于黑硅和量子点的Si-APD光电探测器及其制备方法，本发明以覆盖了量子点的黑硅层作为光敏层，利用其高的红外吸收特性，解决了传统Si-APD光电探测器无法响应近红外波段或者近红外响应度低等问题；本发明能够吸收近红外波段光波，具有光谱响应宽，响应度高，过噪声小，成本低，易于加工等优点。Based on the problems existing in the prior art, the present invention provides a Si-APD photodetector based on black silicon and quantum dots and a preparation method thereof. The present invention uses the black silicon layer covered with quantum dots as the photosensitive layer, and utilizes its high Infrared absorption characteristics solve the problem that the traditional Si-APD photodetector cannot respond to the near-infrared band or the near-infrared responsivity is low; Low, easy processing and other advantages.
依据本发明技术方案的第一方面，提供一种基于黑硅和量子点的Si-APD光电探测器，其包括本征Si衬底1、位于本征Si衬底1中心上方的P区2、位于本征Si衬底1两侧上方保护环区即N区3、位于P区2上方的N+区4、位于N+区4上方的N+黑硅层5、位于N+黑硅层5上表面的量子点区9、位于本征Si衬底1下方的P+区7、位于量子点区和环形保护区N区上表面的上电极6以及位于P+区7下表面的下电极8。According to the first aspect of the technical solution of the present invention, there is provided a Si-APD photodetector based on black silicon and quantum dots, which includes an intrinsic Si substrate 1, a P region 2 located above the center of the intrinsic Si substrate 1, N region 3, N+ region 4 above P region 2, N+ black silicon layer 5 above N+ region 4, N+ black silicon layer 5 on the upper surface of N+ black silicon layer 5. The dot area 9, the P+ area 7 located under the intrinsic Si substrate 1, the upper electrode 6 located on the upper surface of the quantum dot area and the ring-shaped protection area N area, and the lower electrode 8 located on the lower surface of the P+ area 7.
其中，在基于黑硅和量子点的Si-APD光电探测器中，量子点区覆盖在N+黑硅层的上表面；表面涂覆有量子点区的N+黑硅层的复合结构作为光电探测器的光敏层；量子点区采用具有优良红外吸收特性的Ⅳ-Ⅵ族化合物，如PbS量子点。Among them, in the Si-APD photodetector based on black silicon and quantum dots, the quantum dot region covers the upper surface of the N+ black silicon layer; the composite structure of the N+ black silicon layer coated with the quantum dot region is used as a photodetector The photosensitive layer; the quantum dot area uses IV-VI compounds with excellent infrared absorption characteristics, such as PbS quantum dots.
进一步地，PbS量子点采用热注入法制备，量子点颗粒直径大小在1-4nm之间，量子点区厚度在10-30nm之间，制备的量子点保存在正辛烷溶液中；N+黑硅层采用在SF6气体和N2混合气体氛围中，飞秒激光扫描本征硅表面获得，黑硅层上表面为具有陷光作用的致密针状尖峰结构，尖峰高度在20μm-40μm之间。Further, PbS quantum dots are prepared by hot injection method, the diameter of quantum dot particles is between 1-4nm, the thickness of quantum dot area is between 10-30nm, and the prepared quantum dots are stored in n-octane solution; N+ black silicon The layer is obtained by scanning the intrinsic silicon surface with a femtosecond laser in an atmosphere of SF6 gas and N2 mixed gas. The upper surface of the black silicon layer is a dense needle-shaped peak structure with light trapping effect, and the peak height is between 20 μm and 40 μm.
依据本发明技术方案的第二方面，提供一种基于黑硅和量子点的Si-APD光电探测器的制备方法，其包括如下步骤：According to the second aspect of the technical solution of the present invention, a method for preparing a Si-APD photodetector based on black silicon and quantum dots is provided, comprising the steps of:
1)在本征硅衬底上1上氧化生长SiO2膜层，本征硅衬底厚度为300μm，SiO2膜层厚度为300-400nm；1) Oxidative growth of aSiO2 film layer on the intrinsic silicon substrate 1, the thickness of the intrinsic silicon substrate is 300 μm, and the thickness of theSiO2 film layer is 300-400nm;
2)在SiO2膜层表面四周光刻出环形N区3的图形，然后进行磷扩散掺杂形成环形N区3，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3，结深为1.5μm～3.5μm；2) Photoetching the pattern of the ring-shaped N region 3 around the surface of the SiO2 film layer, and then performing phosphorus diffusion doping to form the ring-shaped N region 3, the doping concentration is 4ⅹ1015 ion/cm-3 ~ 1ⅹ1017 ion/cm-3 , the junction depth is 1.5μm～3.5μm;
3)在SiO2膜层表面四周光刻出环形P区2的图形，然后进行硼扩散掺杂形成P区2，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3，结深为1.5μm～3.5μm；3) Photoetching the pattern of the ring-shaped P region 2 around the surface of the SiO2 film layer, and then performing boron diffusion doping to form the P region 2, the doping concentration is 4ⅹ1015 ion/cm-3 ~ 1ⅹ1017 ion/cm-3 , The junction depth is 1.5μm～3.5μm;
4)在SiO2膜层表面四周光刻出环形N+区4的图形，然后进行磷扩散掺杂形成N+区4，N+掺杂区3掺杂浓度≥1ⅹ1020ion/cm-3，结深为0.5μm～2μm；4) Photoetching the pattern of the ring-shaped N+ region 4 around the surface of the SiO2 film layer, and then performing phosphorus diffusion doping to form the N+ region 4, the doping concentration of the N+ doped region 3 is ≥ 1ⅹ1020 ion/cm-3 , and the junction depth is 0.5μm～2μm;
5)对本征硅衬底1的下表面进行硼扩散掺杂形成P+区7，掺杂浓度≥1ⅹ1020ion/cm-3，结深为0.5μm～2μm；5) Boron diffusion doping is performed on the lower surface of the intrinsic silicon substrate 1 to form a P+ region 7 with a doping concentration ≥ 1ⅹ1020 ion/cm-3 and a junction depth of 0.5 μm to 2 μm;
6)在SF6和N2的混合气体中，采用飞秒激光扫描本征硅衬底1的上表面制备黑硅层5，针状尖峰高度在20-40μm；6) In a mixed gas of SF6 and N2 , use a femtosecond laser to scan the upper surface of the intrinsic silicon substrate 1 to prepare a black silicon layer 5 with a needle-like peak height of 20-40 μm;
7)在黑硅层5的上表面旋涂PbS量子点的正辛烷溶液，旋涂速度为2500rpm/min，时间为15秒；7) Spin-coat the n-octane solution of PbS quantum dots on the upper surface of the black silicon layer 5, the spin-coating speed is 2500rpm/min, and the time is 15 seconds;
8)制备电极。8) Preparation of electrodes.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
一、黑硅是一种表面微结构化的硅材料，在SF6、Se、Te等氧族元素参与的环境下制备得到的黑硅，对可见光及近红外光的吸收率可达到90％以上，具有极宽的吸收光谱范围(0.25μm～2.5μm)。基于黑硅材料的光电探测器，其灵敏度与普通硅探测器相比有明显提高。黑硅材料的高吸收率原因主要有两个：表面微结构的陷光效应和硅材料能带结构的改变。光入射到尖锥结构里面要经过多次反射与折射，总的吸收光强为：n为反射次数，Rn为第n次的反射系数(<1)。氧族元素引入的杂质能级与制作黑硅时产生的缺陷能级改变了硅材料的能级结构，使得黑硅材料在近红外波段有良好的响应。1. Black silicon is a silicon material with a microstructured surface. The black silicon prepared in the environment of SF6 , Se, Te and other oxygen group elements can absorb more than 90% of visible light and near-infrared light. , with a very wide absorption spectrum range (0.25μm ~ 2.5μm). The sensitivity of photodetectors based on black silicon materials is significantly improved compared with ordinary silicon detectors. There are two main reasons for the high absorption rate of black silicon materials: the light trapping effect of the surface microstructure and the change of the energy band structure of silicon materials. The light incident into the cone structure has to go through multiple reflections and refractions, and the total absorbed light intensity is: n is the number of reflections, and Rn is the reflection coefficient of the nth time (<1). The impurity energy levels introduced by the oxygen group elements and the defect energy levels generated during the production of black silicon change the energy level structure of the silicon material, making the black silicon material have a good response in the near-infrared band.
二、PbS是直接带隙半导体材料，具有很高的吸收系数，块状体材料禁带宽度为0.45eV，能够吸收红外波段的光信号。PbS量子点层不仅对入射光有良好的吸收效果，更能够在吸收入射光后能高效的产生光生载流子，对其能量进行有效的利用，使之转换为电能以提高器件的探测性能。PbS量子点的禁带宽度随着量子点半径的降低而增大。在制作过程中可通过控制反应温度、反应时间、反应物浓度制备具有不同禁带宽度的PbS量子点，以满足不同波段红外光电探测器的需求。PbS量子点表面原子占有相当大的比例，比表面积大，表面原子具有很高的活性，易于其他原子结合。PbS量子点层能有与Si表面完美配合，降低了传统Si基APD因表面配合不佳而产生的暗电流，提高了PbS量子点APD的探测性能。2. PbS is a direct bandgap semiconductor material with a high absorption coefficient. The bandgap width of the bulk material is 0.45eV, which can absorb optical signals in the infrared band. The PbS quantum dot layer not only has a good absorption effect on incident light, but also can efficiently generate photogenerated carriers after absorbing incident light, effectively utilize its energy, and convert it into electrical energy to improve the detection performance of the device. The forbidden band width of PbS quantum dots increases with the decrease of quantum dot radius. In the production process, PbS quantum dots with different band gaps can be prepared by controlling the reaction temperature, reaction time, and reactant concentration, so as to meet the needs of infrared photodetectors in different wavelength bands. The surface atoms of PbS quantum dots occupy a considerable proportion and have a large specific surface area. The surface atoms have high activity and are easy to combine with other atoms. The PbS quantum dot layer can perfectly cooperate with the Si surface, which reduces the dark current generated by the traditional Si-based APD due to poor surface coordination, and improves the detection performance of the PbS quantum dot APD.
三、本发明是将新型的黑硅材料和量子点纳米材料与传统的Si-APD光电探3. The present invention combines novel black silicon materials and quantum dot nanomaterials with traditional Si-APD photodetectors
测器相结合的一种新型高效宽谱的Si-APD光电探测器。本发明以覆盖有量子点的黑硅层作为APD光电探测器的光敏层，利用黑硅材料的陷光结构与PbS量子点材料对红外光信号的高吸收性，大大提高了Si-APD的红外响应度，解决了传统硅APD光电探测器无法响应红外信号或者红外信号响应低等不足。A new type of high-efficiency wide-spectrum Si-APD photodetector combined with a detector. In the present invention, the black silicon layer covered with quantum dots is used as the photosensitive layer of the APD photodetector, and the light-trapping structure of the black silicon material and the high absorption of the infrared light signal by the PbS quantum dot material are used to greatly improve the infrared light of the Si-APD. Responsivity solves the shortcomings of traditional silicon APD photodetectors that cannot respond to infrared signals or have low response to infrared signals.
四、本发明结合了新型黑硅材料与量子点材料的优点，其红外响应度远远大于现有单纯以黑硅材料或者量子点材料为光敏层的新型光电探测器。黑硅材料表面的森林状尖峰结构，使光在表面多次反射。同时，覆盖在黑硅材料表面的PbS量子点材料对红外光具有很高的吸收。光在黑硅表面的多次反射，也使得PbS材料对光信号可以多次吸收，从而使得本发明红外响应度远远大于现有黑硅材料或者量子点材料光电探测器。4. The present invention combines the advantages of novel black silicon materials and quantum dot materials, and its infrared responsivity is far greater than that of existing new photodetectors that simply use black silicon materials or quantum dot materials as photosensitive layers. The forest-like spike structure on the surface of the black silicon material makes light reflect on the surface multiple times. At the same time, the PbS quantum dot material covered on the surface of the black silicon material has a high absorption of infrared light. The multiple reflections of light on the black silicon surface also allow the PbS material to absorb light signals multiple times, so that the infrared responsivity of the present invention is much greater than that of the existing black silicon material or quantum dot material photodetectors.
五、黑硅材料在制备时，会在黑硅材料内部引入大量的错位、间隙等缺陷，使得黑硅材料的APD光电探测器在使用时具有暗电流大，响应速度低，并且黑硅材料与金属电极通常形成肖特基接触或者无法形成良好的欧姆接触。黑硅材料的光电探测器在使用时，往往需要进行高温退火处理，消除黑硅材料内部的缺陷以及与金属电极形成良好的欧姆接触，但是退火后，由于氧族元素的热扩散作用，黑硅材料的红外吸收特性会明显下降，本发明将PbS量子点覆盖在黑硅材料表面，PbS量子点层能够与金属电极的完美匹配，并且PbS量子点本身对红外光信号就有很高的响应度，解决了黑硅材料使用时以及在退火后红外吸收下降等问题。5. During the preparation of black silicon materials, a large number of defects such as dislocations and gaps will be introduced into the black silicon materials, so that the APD photodetectors of black silicon materials have large dark currents and low response speeds when used, and black silicon materials are compatible with Metal electrodes often form Schottky contacts or do not form good ohmic contacts. When the photodetector of black silicon material is used, high temperature annealing treatment is often required to eliminate the defects inside the black silicon material and form a good ohmic contact with the metal electrode, but after annealing, due to the thermal diffusion of oxygen group elements, the black silicon The infrared absorption characteristics of the material will be significantly reduced. In the present invention, PbS quantum dots are covered on the surface of the black silicon material. The PbS quantum dot layer can perfectly match the metal electrode, and the PbS quantum dot itself has a high response to infrared light signals. , to solve the problem of infrared absorption drop when black silicon material is used and after annealing.
六、传统Si-APD为了提高吸收效率和量子效率往往具有较厚的吸收层，即便倍增载流子在吸收层以饱和漂移速度运动，但现有Si-APD的响应时间依然在百毫秒量级，响应时间长，并且过厚的吸收层也引入了较大的暗电流，降低了Si-APD红外探测器的探测度。本发明采用覆盖了量子点层的黑硅层做为光敏层，大大提高了Si-APD的红外吸收能力，大大降低了本征吸收层的厚度，提高了Si-APD红外探测器的响应速度。6. In order to improve the absorption efficiency and quantum efficiency, the traditional Si-APD often has a thicker absorption layer. Even if the multiplied carriers move at the saturation drift speed in the absorption layer, the response time of the existing Si-APD is still on the order of hundreds of milliseconds. , the response time is long, and the too thick absorbing layer also introduces a large dark current, which reduces the detectability of the Si-APD infrared detector. The invention adopts the black silicon layer covered with the quantum dot layer as the photosensitive layer, greatly improves the infrared absorption ability of Si-APD, greatly reduces the thickness of intrinsic absorption layer, and improves the response speed of Si-APD infrared detector.
七、本发明是以Si-APD结构为基础制备的。硅材料成本低，而且易于与现有的半导体加工工艺兼容，被广泛应用于半导体器件和集成电路的制造。硅基雪崩光电探因其与现代硅集成电路工艺兼容、体积小、工作电压低和功耗低、对磁场不敏感等特点，在光电探测领域具有十分重要的意义。结合本发明所述制备工艺可知本发明具有成本低、制作简单、易集成等优点。7. The present invention is based on the Si-APD structure. Silicon material is low in cost and easily compatible with existing semiconductor processing technology, and is widely used in the manufacture of semiconductor devices and integrated circuits. Silicon-based avalanche photodetector is of great significance in the field of photoelectric detection because of its compatibility with modern silicon integrated circuit technology, small size, low operating voltage and power consumption, and insensitivity to magnetic fields. Combining with the preparation process described in the present invention, it can be seen that the present invention has the advantages of low cost, simple manufacture, easy integration and the like.
附图说明Description of drawings
图1是本发明提供的基于黑硅和量子点的Si-APD光电探测器剖面结构示意图；Fig. 1 is the Si-APD photodetector sectional structure schematic diagram based on black silicon and quantum dot provided by the present invention;
图2是是本发明提供的基于黑硅和量子点的Si-APD光电探测器的俯视平面结构示意图；Fig. 2 is the top view plane structure schematic diagram of the Si-APD photodetector based on black silicon and quantum dot provided by the present invention;
图3是本发明提供的基于黑硅和量子点的Si-APD光电探测器的量子点黑硅复合层结构示意图；Fig. 3 is the quantum dot black silicon composite layer structural representation of the Si-APD photodetector based on black silicon and quantum dot that the present invention provides;
图4是本发明提供的基于黑硅和量子点的Si-APD光电探测器的黑硅层表面微结构光学模型；Fig. 4 is the microstructure optical model of the black silicon layer surface of the Si-APD photodetector based on black silicon and quantum dot provided by the present invention;
其中附图标记：1是本征Si衬底、2是P区、3是环形N区、4是N+区、5是黑硅层、6是上电极、7是P+区，8是下电极，9是量子点层。Wherein reference numerals: 1 is the intrinsic Si substrate, 2 is the P region, 3 is the annular N region, 4 is the N+ region, 5 is the black silicon layer, 6 is the upper electrode, 7 is the P+ region, 8 is the lower electrode, 9 is a quantum dot layer.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。另外地，不应当将本发明的保护范围仅仅限制至下述具体实验方法或具体参数。The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention. Additionally, the protection scope of the present invention should not be limited only to the specific experimental methods or specific parameters described below.
本申请人致力于扩展Si的探测光谱的研究，基于黑硅和量子点进行长期开发及探索，本发明提供一种基于黑硅和量子点的Si-APD光电探测器及其制备方法。本发明基于的量子点，又可称为纳米晶，一般由Ⅱ-Ⅵ族或Ⅳ-Ⅵ族元素组成的纳米颗粒，粒径一般介于1～10nm之间。当量子点的尺寸与材料的激子波尔半径相当时，受到量子效应的影响，禁带展宽，电子态密度出现分立量化能级结构，主要表现为量子尺寸效应，表面效应和多激子效应等。量子点的合成方法主要包括外延生长、光刻、热注入等，其中热注入法对设备的要求相对较低，操作简单，各种形貌的量子点可控，已成为量子点合成的主要方法。PbS量子点因为其较窄的块体带隙(0.41eV)及较大的激子波尔半径，所以很容易覆盖太阳光谱的近红外吸收，且具有独特的电学性能，很高的载流子收集效率，在纳米半导体红外光伏器件中得到广泛的运用。The applicant is committed to the research of expanding the detection spectrum of Si, and has carried out long-term development and exploration based on black silicon and quantum dots. The present invention provides a Si-APD photodetector based on black silicon and quantum dots and its preparation method. The quantum dots based on the present invention can also be called nanocrystals, which are generally nanoparticles composed of II-VI or IV-VI elements, and the particle size is generally between 1 and 10 nm. When the size of quantum dots is equivalent to the exciton Bohr radius of the material, affected by quantum effects, the band gap is broadened, and the electronic density of states appears a discrete quantized energy level structure, mainly manifested in quantum size effects, surface effects and multi-exciton effects Wait. The synthesis methods of quantum dots mainly include epitaxial growth, photolithography, thermal injection, etc. Among them, the thermal injection method has relatively low requirements for equipment, simple operation, and controllable quantum dots of various shapes, which has become the main method of quantum dot synthesis. . Because of its narrow bulk bandgap (0.41eV) and large excitonic Bohr radius, PbS quantum dots can easily cover the near-infrared absorption of the solar spectrum, and have unique electrical properties and high carrier density. Collection efficiency is widely used in nano-semiconductor infrared photovoltaic devices.
黑硅材料即重掺杂微纳结构硅，是一种基于晶体硅进行表面处理的新型硅材料。黑硅表面微纳结构的陷光作用及重掺杂引入的杂质能级和缺陷能级，使得黑硅对近紫外－近红外波段的光(0.25～2.5μm)几乎全部吸收。由于具有特殊的表面结构而显示出无比的吸光优越性，黑硅材料在可见-近红外光电探测和光伏器件领域都有非常光明的应用前景。然而，基于黑硅材料的光电探测器在使用时，为了消除材料内部的缺陷以及与金属电极形成良好的欧姆接触需要进行高温退火处理，退火处理后的黑硅红外吸收明显下降。Black silicon material is heavily doped micro-nano structure silicon, which is a new type of silicon material based on crystalline silicon for surface treatment. The light trapping effect of the micro-nano structure on the surface of black silicon and the impurity level and defect energy level introduced by heavy doping make black silicon absorb almost all the light in the near ultraviolet-near infrared band (0.25-2.5 μm). Due to its special surface structure, it shows incomparable light-absorbing advantages, and black silicon materials have very bright application prospects in the fields of visible-near-infrared photodetection and photovoltaic devices. However, when photodetectors based on black silicon materials are used, high-temperature annealing treatment is required in order to eliminate defects inside the material and form good ohmic contacts with metal electrodes, and the infrared absorption of black silicon after annealing treatment decreases significantly.
上述属于本发明的过程研究，其中尚存在以下问题：HgCdTe APD必须工作在低温环境下；InGaAs-InP APD价格昂贵、热机械性能差、晶体质量较差、且不易与现有硅微电子工艺兼容；Si半导体材料由于禁带宽度较大，无法探测红外波段光信号，响应度低，光谱探测范围有限等不足；Si-APD红外响应低或者无法响应红外信号，吸收层过厚，响应时间长，量子效率低等不足；黑硅材料退火后，红外吸收下降。基于这些问题，本申请对此进行了进一步改良。The above belongs to the process research of the present invention, and there are still the following problems: HgCdTe APD must work in a low temperature environment; InGaAs-InP APD is expensive, has poor thermomechanical properties, poor crystal quality, and is not easy to be compatible with existing silicon microelectronics processes ;Due to the large band gap, Si semiconductor materials cannot detect infrared light signals, low responsivity, and limited spectral detection range; Si-APD has low infrared response or cannot respond to infrared signals, the absorption layer is too thick, and the response time is long. Insufficiencies such as low quantum efficiency; after the black silicon material is annealed, the infrared absorption decreases. Based on these problems, the present application has carried out further improvement on this.
为了解决上述技术问题，本发明采用如下技术方案：In order to solve the above technical problems, the present invention adopts the following technical solutions:
一种基于黑硅和量子点的Si-APD光电探测器包括本征Si衬底1、位于本征Si衬底1中心上方的P区2、位于本征Si衬底1两侧上方保护环区即N区3、位于P区2上方的N+区4、位于N+区4上方的N+黑硅层5、位于N+黑硅层5上表面的量子点区9、位于本征Si衬底1下方的P+区7、位于量子点区和环形保护区N区上表面的上电极6以及位于P+区7下表面的下电极8。A Si-APD photodetector based on black silicon and quantum dots includes an intrinsic Si substrate 1, a P region 2 located above the center of the intrinsic Si substrate 1, and a guard ring region located above the two sides of the intrinsic Si substrate 1 That is, the N region 3, the N+ region 4 located above the P region 2, the N+ black silicon layer 5 located above the N+ region 4, the quantum dot region 9 located on the upper surface of the N+ black silicon layer 5, and the The P+ area 7, the upper electrode 6 located on the upper surface of the quantum dot area and the ring-shaped protection area N area, and the lower electrode 8 located on the lower surface of the P+ area 7 .
本发明中，所述P区2为硼扩散掺杂P型区，结深为1.5μm～3.5μm，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3。In the present invention, the P region 2 is a boron diffusion-doped P-type region with a junction depth of 1.5 μm-3.5 μm and a doping concentration of 4ⅹ1015 ion/cm−3 to 1ⅹ1017 ion/cm−3 .
本发明中，所述环形区N区3为磷扩散掺杂N型区，结深为1.5μm～3.5μm，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3。In the present invention, the ring-shaped N region 3 is an N-type region doped with phosphorus diffusion, with a junction depth of 1.5 μm to 3.5 μm, and a doping concentration of 4ⅹ1015 ion/cm−3 to 1ⅹ1017 ion/cm−3 .
本发明中，所述N+区4为磷重扩散掺杂N型区，结深为0.5μm～2μm，掺杂浓度≥1ⅹ1020ion/cm-3。In the present invention, the N+ region 4 is an N-type region heavily diffused and doped with phosphorus, the junction depth is 0.5 μm-2 μm, and the doping concentration is ≥1ⅹ1020 ion/cm−3 .
本发明中，所述P+区7为硼重扩散掺杂P型区，结深为0.5μm～2μm，掺杂浓度≥1ⅹ1020ion/cm-3。In the present invention, the P+ region 7 is a heavily diffused boron doped P-type region with a junction depth of 0.5 μm-2 μm and a doping concentration ≥ 1ⅹ1020 ion/cm−3 .
本发明中，量子点区采用具有优良红外吸收特性的Ⅳ-Ⅵ族化合物，如PbS量子点。PbS量子点采用热注入法制备，量子点颗粒直径大小在1-4nm之间，制备的量子点保存在正辛烷溶液中，量子点区厚度在10-30nm之间。In the present invention, the quantum dot area adopts group IV-VI compounds with excellent infrared absorption characteristics, such as PbS quantum dots. The PbS quantum dots are prepared by a thermal injection method, the particle diameter of the quantum dots is between 1-4nm, the prepared quantum dots are stored in n-octane solution, and the thickness of the quantum dot area is between 10-30nm.
本发明中，N+黑硅层采用在SF6气体和N2混合气体氛围中，飞秒激光扫描本征硅表面获得，黑硅层上表面为具有陷光作用的致密针状尖峰结构，尖峰高度在20-40μm之间。In the present invention, the N+ black silicon layer is obtained by scanning the intrinsic silicon surface with a femtosecond laser in an atmosphere of SF6 gas and N2 mixed gas. Between 20-40μm.
本发明中，量子点区覆盖在N+黑硅层的上表面，表面涂覆有量子点区的N+黑硅层的复合结构作为光电探测器的光敏层。In the present invention, the quantum dot area is covered on the upper surface of the N+ black silicon layer, and the composite structure of the N+ black silicon layer coated with the quantum dot area serves as the photosensitive layer of the photodetector.
本发明中，所述环形保护区N区3的厚度大于倍增区P区2、N+区4和黑硅层5的厚度之和。In the present invention, the thickness of the N-region 3 in the annular protection region is greater than the sum of the thicknesses of the multiplication region P-region 2 , the N+ region 4 and the black silicon layer 5 .
本发明中，所述上电极6和下电极8采用金属薄膜电极，电极材料为金(Au)、银(Ag)和镍铬合金。In the present invention, the upper electrode 6 and the lower electrode 8 are metal thin film electrodes, and the electrode materials are gold (Au), silver (Ag) and nickel-chromium alloy.
制备前文所述的基于黑硅和量子点的Si-APD光电探测器的制备方法，其特征在于，包括以下步骤：The method for preparing the Si-APD photodetector based on black silicon and quantum dots described above is characterized in that it comprises the following steps:
1)在本征硅衬底上1上氧化生长SiO2膜层，本征硅衬底厚度为300μm，SiO2膜层厚度为300nm-400nm；1) Oxidative growth of aSiO2 film layer on the intrinsic silicon substrate 1, the thickness of the intrinsic silicon substrate is 300 μm, and the thickness of theSiO2 film layer is 300nm-400nm;
2)在SiO2膜层表面四周光刻出环形N区3的图形，然后进行磷扩散掺杂形成环形N区3，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3，结深为1.5μm～3.5μm；2) Photoetching the pattern of the ring-shaped N region 3 around the surface of the SiO2 film layer, and then performing phosphorus diffusion doping to form the ring-shaped N region 3, the doping concentration is 4ⅹ1015 ion/cm-3 ~ 1ⅹ1017 ion/cm-3 , the junction depth is 1.5μm～3.5μm;
3)在SiO2膜层表面四周光刻出环形P区2的图形，然后进行硼扩散掺杂形成P区2，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3，结深为1.5μm～3.5μm；3) Photoetching the pattern of the ring-shaped P region 2 around the surface of the SiO2 film layer, and then performing boron diffusion doping to form the P region 2, the doping concentration is 4ⅹ1015 ion/cm-3 ~ 1ⅹ1017 ion/cm-3 , The junction depth is 1.5μm～3.5μm;
4)在SiO2膜层表面四周光刻出环形N+区4的图形，然后进行磷扩散掺杂形成N+区4，N+掺杂区(3)掺杂浓度≥1ⅹ1020ion/cm-3，结深为0.5μm～2μm；4) Photoetching the pattern of the annular N+ region 4 around the surface of the SiO2 film layer, and then performing phosphorus diffusion doping to form the N+ region 4, the doping concentration of the N+ doped region (3) ≥ 1ⅹ1020 ion/cm-3 , the junction The depth is 0.5μm～2μm;
5)对本征硅衬底1的下表面进行硼扩散掺杂形成P+区7，掺杂浓度≥1ⅹ1020ion/cm-3，结深为0.5μm～2μm；5) Boron diffusion doping is performed on the lower surface of the intrinsic silicon substrate 1 to form a P+ region 7 with a doping concentration ≥ 1ⅹ1020 ion/cm-3 and a junction depth of 0.5 μm to 2 μm;
6)在SF6和N2的混合气体中，采用飞秒激光扫描本征硅衬底1的上表面制备黑硅层5，针状尖峰高度在20μm-40μm；6) In a mixed gas of SF6 and N2 , use a femtosecond laser to scan the upper surface of the intrinsic silicon substrate 1 to prepare a black silicon layer 5 , and the height of the needle-like peaks is 20 μm-40 μm;
7)在黑硅层5的上表面旋涂PbS量子点的正辛烷溶液，旋涂速度为2500rpm/min，时间为15秒；7) Spin-coat the n-octane solution of PbS quantum dots on the upper surface of the black silicon layer 5, the spin-coating speed is 2500rpm/min, and the time is 15 seconds;
8)制备电极。8) Preparation of electrodes.
进一步地，步骤7中的PbS量子点溶液采用热注入法制备，步骤如下：Further, the PbS quantum dot solution in step 7 is prepared by hot injection method, the steps are as follows:
1)制备Pb前驱体。将446mg的PbO(2mmol)，1.6ml的油酸(5mmol)，25ml的十八烯(ODE)加入到一个50ml的三颈瓶中，N2保护下，加热到150℃，使PbO完全溶解，制得Pb前驱体。1) Preparation of Pb precursor. The PbO (2mmol) of 446mg, the oleic acid (5mmol) of 1.6ml, the octadecene (ODE) of 25ml are joined in a 50ml three-necked bottle, under N2 protection, be heated to 150 ℃, make PbO dissolve completely, prepare Get Pb precursor.
2)制备S前驱体。将210μl六甲基二硅硫烷(TMS)溶解在5ml ODE中，N2保护下，加热1h，制得S前驱体。2) Preparation of S precursor. Dissolve 210 μl of hexamethyldisilazane (TMS) in 5 ml of ODE, and heat for 1 h under N2 protection to prepare the S precursor.
3)将S前驱体迅速注入Pb前驱体中，溶液在几秒内完全转变为黑色。反应30秒，将三口瓶从油浴中移除，自然冷却至室温。3) The S precursor was quickly injected into the Pb precursor, and the solution completely turned black within a few seconds. After reacting for 30 seconds, the three-neck flask was removed from the oil bath, and cooled to room temperature naturally.
4)待冷却至室温，用无水甲醇洗涤，离心，反复多次。将洗涤后的黑色固体溶于正辛烷溶液中。4) After cooling to room temperature, wash with anhydrous methanol, centrifuge, and repeat several times. The washed black solid was dissolved in n-octane solution.
作为本发明的进一步说明，步骤6中的黑硅层采用飞秒激光制备，具体步骤如下：As a further illustration of the present invention, the black silicon layer in step 6 is prepared by femtosecond laser, and the specific steps are as follows:
1)采用RAC工艺对硅片进行清洗，并将清洗好的硅片固定在真空腔内。1) The silicon wafer is cleaned by the RAC process, and the cleaned silicon wafer is fixed in a vacuum chamber.
2)将真空腔抽真空后，通入SF6和N2混合气体(1:1)。2) After the vacuum chamber is evacuated, a mixed gas of SF6 and N2 (1:1) is introduced.
利用计算机控制移动平台移动，将激光聚焦在硅片的右上角，然后控制三维移动平台使得飞秒激光以蛇形的轨迹对硅片进行刻蚀。我们实验所所需的激光能量为0.1mJ，扫描速度恒定为1mm/s，扫描间隔为50μm。Use the computer to control the movement of the mobile platform, focus the laser on the upper right corner of the silicon wafer, and then control the three-dimensional mobile platform to make the femtosecond laser etch the silicon wafer in a serpentine trajectory. The laser energy required for our experiment is 0.1mJ, the scanning speed is constant at 1mm/s, and the scanning interval is 50μm.
下面结合附图，对本发明进一步说明。如图1和图2所示，基于黑硅和量子点的Si-APD光电探测器包括本征Si衬底1、位于本征Si衬底1中心上方的P区2、位于本征Si衬底1两侧上方保护环区即N区3、位于P区2上方的N+区4、位于N+区4上方的N+黑硅层5、位于N+黑硅层5上表面的量子点区9、位于本征Si衬底1下方的P+区7、位于量子点区和环形保护区N区上表面的上电极6以及位于P+区7下表面的下电极8。Below in conjunction with accompanying drawing, the present invention is further described. As shown in Figures 1 and 2, the Si-APD photodetector based on black silicon and quantum dots includes an intrinsic Si substrate 1, a P region 2 located above the center of the intrinsic Si substrate 1, and a 1 The protective ring area on both sides is the N area 3, the N+ area 4 located above the P area 2, the N+ black silicon layer 5 located above the N+ area 4, the quantum dot area 9 located on the upper surface of the N+ black silicon layer 5, and the The P+ region 7 under the Si substrate 1, the upper electrode 6 located on the upper surface of the quantum dot area and the ring-shaped protection area N region, and the lower electrode 8 located on the lower surface of the P+ region 7.
上述技术方案中：所述P区2优选为硼扩散掺杂P型区，结深为1.5μm～3.5μm，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3。所述环形区N区3优选为磷扩散掺杂N型区，结深为1.5μm～3.5μm，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3。In the above technical solution: the P region 2 is preferably a boron diffusion-doped P-type region, the junction depth is 1.5 μm to 3.5 μm, and the doping concentration is 4ⅹ1015 ion/cm−3 to 1ⅹ1017 ion/cm−3 . The ring-shaped N region 3 is preferably a phosphorous doped N-type region, with a junction depth of 1.5 μm to 3.5 μm and a doping concentration of 4ⅹ1015 ion/cm −3 to 1ⅹ1017 ion/cm−3 .
所述N+区4优选为磷重扩散掺杂N型区，结深为0.5μm～2μm，掺杂浓度≥1ⅹ1020ion/cm-3。所述P+区7优选为硼重扩散掺杂P型区，结深为0.5μm～2μm，掺杂浓度≥1ⅹ1020ion/cm-3。The N+ region 4 is preferably an N-type region heavily diffused and doped with phosphorus, with a junction depth of 0.5 μm to 2 μm and a doping concentration ≥ 1ⅹ1020 ion/cm−3 . The P+ region 7 is preferably a boron heavily diffused doped P-type region with a junction depth of 0.5 μm-2 μm and a doping concentration ≥ 1ⅹ1020 ion/cm−3 .
量子点区可选择采用具有优良红外吸收特性的Ⅳ-Ⅵ族化合物，如PbS量子点。PbS量子点采用热注入法制备，量子点颗粒直径大小在1-4nm之间，制备的量子点保存在正辛烷溶液中，量子点区厚度在10-30nm之间。N+黑硅层采用在SF6气体和N2混合气体氛围中，飞秒激光扫描本征硅表面获得，黑硅层上表面为具有陷光作用的致密针状尖峰结构，尖峰高度在20-40μm之间。The quantum dot area can choose to use IV-VI compounds with excellent infrared absorption characteristics, such as PbS quantum dots. The PbS quantum dots are prepared by a thermal injection method, the particle diameter of the quantum dots is between 1-4nm, the prepared quantum dots are stored in n-octane solution, and the thickness of the quantum dot area is between 10-30nm. The N+ black silicon layer is obtained by scanning the intrinsic silicon surface with a femtosecond laser in an atmosphere of SF6 gas and N2 mixed gas. The upper surface of the black silicon layer is a dense needle-like peak structure with light trapping effect, and the peak height is 20-40 μm between.
此外，量子点区覆盖在N+黑硅层的上表面，表面涂覆有量子点区的N+黑硅层的复合结构作为光电探测器的光敏层。所述环形保护区N区3的厚度大于倍增区P区2、N+区4和黑硅层5的厚度之和。所述上电极6和下电极8采用金属薄膜电极，电极材料为金(Au)、银(Ag)和镍铬合金。In addition, the quantum dot area covers the upper surface of the N+ black silicon layer, and the composite structure of the N+ black silicon layer coated with the quantum dot area serves as the photosensitive layer of the photodetector. The thickness of the N-region 3 in the annular protection region is greater than the sum of the thicknesses of the multiplication region P-region 2 , the N+ region 4 and the black silicon layer 5 . The upper electrode 6 and the lower electrode 8 are metal film electrodes, and the electrode materials are gold (Au), silver (Ag) and nickel-chromium alloy.
制备前文所述的PbS量子点层，采用如下方法：To prepare the PbS quantum dot layer described above, the following method is adopted:
1)制备Pb前驱体。将446mg的PbO(2mmol)，1.6ml的油酸(5mmol)，25ml的十八烯(ODE)加入到一个50ml的三颈瓶中，N2保护下，加热到150℃，使PbO完全溶解，制得Pb前驱体。1) Preparation of Pb precursor. Add 446mg of PbO (2mmol), 1.6ml of oleic acid (5mmol), and 25ml of octadecene (ODE) into a 50ml three-necked flask, and underN2 protection, heat to 150°C to completely dissolve the PbO. Prepare the Pb precursor.
2)制备S前驱体。将210μl六甲基二硅硫烷(TMS)溶解在5ml ODE中，N2保护下，加热1h(一小时)，制得S前驱体。2) Preparation of S precursor. Dissolve 210 μl of hexamethyldisilathane (TMS) in 5 ml of ODE, and heat for 1 h (one hour) under the protection of N2 to prepare the S precursor.
3)将S前驱体迅速注入Pb前驱体中，溶液在几秒内完全转变为黑色。反应30秒，将三口瓶从油浴中移除，自然冷却至室温。3) The S precursor was quickly injected into the Pb precursor, and the solution completely turned black within a few seconds. After reacting for 30 seconds, the three-neck flask was removed from the oil bath, and cooled to room temperature naturally.
4)待冷却至室温，用无水甲醇洗涤，离心，反复多次。将洗涤后的黑色固体溶于正辛烷溶液中。4) After cooling to room temperature, wash with anhydrous methanol, centrifuge, and repeat several times. The washed black solid was dissolved in n-octane solution.
制备前述的黑硅层，采用如下方法：To prepare the aforementioned black silicon layer, the following method is adopted:
1)采用RAC工艺对硅片进行清洗，并将清洗好的硅片固定在真空腔内。1) The silicon wafer is cleaned by the RAC process, and the cleaned silicon wafer is fixed in a vacuum chamber.
2)将真空腔抽真空后，通入SF6和N2混合气体(1:1)。2) After the vacuum chamber is evacuated, a mixed gas of SF6 and N2 (1:1) is introduced.
3)利用计算机控制移动平台移动，将激光聚焦在硅片的右上角，然后控制三维移动平台使得飞秒激光以蛇形的轨迹对硅片进行刻蚀。我们实验所所需的激光能量为0.1mJ，扫描速度恒定为1mm/s，扫描间隔为50μm。3) Use the computer to control the movement of the mobile platform, focus the laser on the upper right corner of the silicon wafer, and then control the three-dimensional mobile platform to make the femtosecond laser etch the silicon wafer in a serpentine trajectory. The laser energy required for our experiment is 0.1mJ, the scanning speed is constant at 1mm/s, and the scanning interval is 50μm.
基于黑硅和量子点的Si-APD光电探测器的制备方法包括以下步骤：The preparation method of the Si-APD photodetector based on black silicon and quantum dots comprises the following steps:
1)在本征硅衬底上1上氧化生长SiO2膜层，本征硅衬底厚度为300μm，SiO2膜层厚度为300nm-400nm；1) Oxidative growth of aSiO2 film layer on the intrinsic silicon substrate 1, the thickness of the intrinsic silicon substrate is 300 μm, and the thickness of theSiO2 film layer is 300nm-400nm;
2)在SiO2膜层表面四周光刻出环形N区3的图形，然后进行磷扩散掺杂形成环形N区3，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3，结深为1.5μm～3.5μm；2) Photoetching the pattern of the ring-shaped N region 3 around the surface of the SiO2 film layer, and then performing phosphorus diffusion doping to form the ring-shaped N region 3, the doping concentration is 4ⅹ1015 ion/cm-3 ~ 1ⅹ1017 ion/cm-3 , the junction depth is 1.5μm～3.5μm;
3)在SiO2膜层表面四周光刻出环形P区2的图形，然后进行硼扩散掺杂形成P区2，掺杂浓度为4ⅹ1015ion/cm-3～1ⅹ1017ion/cm-3，结深为1.5μm～3.5μm；3) Photoetching the pattern of the ring-shaped P region 2 around the surface of the SiO2 film layer, and then performing boron diffusion doping to form the P region 2, the doping concentration is 4ⅹ1015 ion/cm-3 ~ 1ⅹ1017 ion/cm-3 , The junction depth is 1.5μm～3.5μm;
4)在SiO2膜层表面四周光刻出环形N+区4的图形，然后进行磷扩散掺杂形成N+区4，N+掺杂区(3)掺杂浓度≥1ⅹ1020ion/cm-3，结深为0.5μm～2μm；4) Photoetching the pattern of the annular N+ region 4 around the surface of the SiO2 film layer, and then performing phosphorus diffusion doping to form the N+ region 4, the doping concentration of the N+ doped region (3) ≥ 1ⅹ1020 ion/cm-3 , the junction The depth is 0.5μm～2μm;
5)对本征硅衬底1的下表面进行硼扩散掺杂形成P+区7，掺杂浓度≥1ⅹ1020ion/cm-3，结深为0.5μm～2μm；5) Boron diffusion doping is performed on the lower surface of the intrinsic silicon substrate 1 to form a P+ region 7 with a doping concentration ≥ 1ⅹ1020 ion/cm-3 and a junction depth of 0.5 μm to 2 μm;
6)在SF6和N2的混合气体中，采用飞秒激光扫描本征硅衬底1的上表面制备黑硅层5，针状尖峰高度在20μm-40μm；6) In a mixed gas of SF6 and N2 , use a femtosecond laser to scan the upper surface of the intrinsic silicon substrate 1 to prepare a black silicon layer 5 , and the height of the needle-like peaks is 20 μm-40 μm;
7)在黑硅层5的上表面旋涂PbS量子点的正辛烷溶液，旋涂速度为2500rpm/min，时间为15秒；7) Spin-coat the n-octane solution of PbS quantum dots on the upper surface of the black silicon layer 5, the spin-coating speed is 2500rpm/min, and the time is 15 seconds;
8)制备电极。8) Preparation of electrodes.
至此，已经结合附图对本发明实施例进行了详细的描述。需要说明的是，在附图或说明书正文中，未绘示或描述的实现方式，均为所属技术领域中普通技术人员所知的形式，并未进行详细说明。So far, the embodiments of the present invention have been described in detail with reference to the accompanying drawings. It should be noted that, in the accompanying drawings or in the text of the specification, implementations that are not shown or described are forms known to those of ordinary skill in the art, and are not described in detail.
还需说明的是，图中各部件的形状和尺寸不反应真实大小和比例，而仅示意本发明实施例的内容。It should also be noted that the shapes and sizes of the components in the drawings do not reflect the actual sizes and proportions, but only illustrate the content of the embodiments of the present invention.
本发明未详细阐述部分属于本领域技术人员的公知技术。以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Parts not described in detail in the present invention belong to the known techniques of those skilled in the art. The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of the present invention. within the scope of protection.
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| CN201910669697.4ACN110416332B (en) | 2019-07-24 | 2019-07-24 | Si-APD photoelectric detector based on black silicon and quantum dots and preparation method thereof |
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