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CN113437164B - Photoconductive all-silicon solar blind ultraviolet detector and manufacturing method thereof - Google Patents

Photoconductive all-silicon solar blind ultraviolet detector and manufacturing method thereof Download PDF

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CN113437164B
CN113437164B CN202110661496.7A CN202110661496A CN113437164B CN 113437164 B CN113437164 B CN 113437164B CN 202110661496 A CN202110661496 A CN 202110661496A CN 113437164 B CN113437164 B CN 113437164B
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silicon
nitride film
silicon nitride
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董恒平
陈坤基
杨华烽
窦如凤
井娥林
李伟
徐骏
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Taizhou Institute Of Sci&tech Nust
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Abstract

The invention provides a photoconductive full-silicon-based solar blind ultraviolet detector and a manufacturing method thereof, belonging to the field of photoelectric detection, and the photoconductive full-silicon-based solar blind ultraviolet detector comprises: the silicon substrate is P-type crystalline silicon or intrinsic crystalline silicon and is configured to be a carrier transmission layer; the amorphous oxygen-doped silicon nitride film is formed on the surface of the silicon substrate and is configured to be an ultraviolet light absorption layer to generate carriers; and the interdigital electrode is formed on the surface of the amorphous oxygen-doped silicon nitride film. The solar blind ultraviolet detector adopts luminous wide-bandgap amorphous oxygen-doped silicon nitride (a-SiN) x O) film is used as an ultraviolet light absorption layer, P-type crystalline silicon (P-Si) or intrinsic crystalline silicon (i-Si) is used as a carrier transmission layer, and the constructed photoconductive full-silicon-based solar blind ultraviolet detector has low cost and can be compatible with a mature CMOS manufacturing process, thereby realizing large-area production.

Description

光导型全硅基日盲紫外探测器及其制作方法Photoconductive all-silicon-based solar-blind ultraviolet detector and manufacturing method thereof

技术领域technical field

本发明属于光电探测领域，具体涉及一种光导型全硅基日盲紫外线探测器，另外，本发明还涉及上述光导型全硅基日盲紫外探测器的制作方法。The invention belongs to the field of photoelectric detection, and specifically relates to a photoconductive all-silicon-based solar-blind ultraviolet detector. In addition, the invention also relates to a manufacturing method of the above-mentioned photoconductive-type all-silicon-based solar-blind ultraviolet detector.

背景技术Background technique

在自然界中，太阳是主要的紫外线光源，来自于太阳辐射的200-280nm波段的紫外光几乎被地球大气层中臭氧层吸收，不能到达地面，因此，在UV光谱中常将240-280nm的波长范围称为“日盲”窗口。工作在这一波段的日盲紫外探测器可以不受太阳背景辐射的影响，而具有较高的灵敏度和信噪比，使其成为光电探测研究领域的新宠。In nature, the sun is the main ultraviolet light source. The ultraviolet light from the solar radiation in the 200-280nm band is almost absorbed by the ozone layer in the earth's atmosphere and cannot reach the ground. Therefore, in the UV spectrum, the wavelength range of 240-280nm is often referred to as "Sunblind" window. The solar-blind ultraviolet detector working in this band can not be affected by the solar background radiation, but has high sensitivity and signal-to-noise ratio, making it a new favorite in the field of photoelectric detection research.

作为微电子工业的主流材料，半导体硅虽然具备一定的日盲紫外敏感特性，但由于禁带宽度很窄，会产生较高的可见和红外响应，对日盲紫外探测形成干扰，需要在探测器上加装特殊设计、价格昂贵的滤波片才能工作在紫外波段，这会导致探测器量子效率的损失和成本的增加。As a mainstream material in the microelectronics industry, although semiconductor silicon has certain solar-blind ultraviolet sensitivity characteristics, due to the narrow band gap, it will produce high visible and infrared responses, which will interfere with solar-blind ultraviolet detection. It can only work in the ultraviolet band by adding a specially designed and expensive filter on it, which will lead to the loss of the quantum efficiency of the detector and the increase of the cost.

近年来，为克服硅在日盲紫外探测器应用中的缺点，宽禁带半导体材料，如AlGaN合金材料、MgZnO、金刚石、和Ga2O3为制造更高性能的日盲紫外探测器提供了新的选择。In recent years, in order to overcome the shortcomings of silicon in the application of solar-blind ultraviolet detectors, wide-bandgap semiconductor materials, such as AlGaN alloy materials, MgZnO, diamond, and Ga2O3 , provide a great opportunity for the manufacture of higher-performance solar-blind ultraviolet detectors . new options.

在实现本发明的过程中，发明人发现现有技术至少存在以下缺陷：In the process of realizing the present invention, the inventor finds that the prior art has at least the following defects:

宽禁带半导体材料一般是基于蓝宝石衬底进行制备，而宽禁带晶态半导体的制备技术还不够成熟，不易于大规模生产，且不能与当前成熟的硅CMOS工艺相兼容，导致器件的制作成本较高；另外，宽禁带半导体日盲紫外探测器不能克服高响应度和高响应速度之间的固有矛盾，即不能同时达到高响应度和高响应速度。Wide bandgap semiconductor materials are generally prepared based on sapphire substrates, but the preparation technology of wide bandgap crystalline semiconductors is not mature enough, it is not easy to mass-produce, and it is not compatible with the current mature silicon CMOS process, resulting in the production of devices The cost is high; in addition, the wide-bandgap semiconductor solar-blind ultraviolet detector cannot overcome the inherent contradiction between high responsivity and high response speed, that is, it cannot achieve high responsivity and high response speed at the same time.

发明内容Contents of the invention

基于上述背景问题，本发明旨在提供一种光导型全硅基日盲紫外探测器，采用发光的宽禁带非晶掺氧氮化硅(a-SiNx:O)薄膜作为紫外光吸收层，以P型晶硅(p-Si)或本征晶硅(i-Si)作为载流子传输层，构建的光导型全硅基日盲紫外探测器不仅成本低廉，且能与成熟的CMOS制造工艺相兼容，并且能够同时获得高响应度和高响应速度；本发明的另一目的是提供上述光导型全硅基日盲紫外探测器的制作方法。Based on the above-mentioned background problem, the present invention aims to provide a photoconductive all-silicon-based solar-blind ultraviolet detector, which adopts a luminescent wide-bandgap amorphous silicon nitride (a-SiN x :O) thin film as the ultraviolet light absorbing layer , using P-type crystalline silicon (p-Si) or intrinsic crystalline silicon (i-Si) as the carrier transport layer, the photoconductive type all-silicon-based solar-blind ultraviolet detector is not only low in cost, but also compatible with mature CMOS The manufacturing process is compatible, and can obtain high responsivity and high response speed at the same time; another object of the present invention is to provide a manufacturing method of the above-mentioned photoconductive all-silicon-based solar-blind ultraviolet detector.

为达到上述目的，一方面，本发明实施例提供的技术方案是：In order to achieve the above object, on the one hand, the technical solutions provided by the embodiments of the present invention are:

光导型全硅基日盲紫外探测器，包括：Photoconductive all-silicon-based solar-blind UV detectors, including:

硅基底，所述硅基底为P型晶硅或本征晶硅，被配置为载流子传输层；a silicon substrate, the silicon substrate is p-type crystalline silicon or intrinsic crystalline silicon, and is configured as a carrier transport layer;

非晶掺氧氮化硅薄膜，形成于所述硅基底表面，被配置为紫外光吸收层以产生载流子；An amorphous oxygen-doped silicon nitride film is formed on the surface of the silicon substrate and configured as an ultraviolet light absorbing layer to generate carriers;

叉指状电极，形成于所述非晶掺氧氮化硅薄膜表面。Interdigitated electrodes are formed on the surface of the amorphous oxygen-doped silicon nitride film.

进一步地，所述非晶掺氧氮化硅薄膜的厚度为100-200nm。Further, the thickness of the amorphous oxy-doped silicon nitride film is 100-200 nm.

进一步地，所述叉指状电极为Ti/Au叉指状电极或Al叉指状电极，所述叉指状电极的受光面积为0.07-0.1mm2。Further, the interdigitated electrodes are Ti/Au interdigitated electrodes or Al interdigitated electrodes, and the light receiving area of the interdigitated electrodes is 0.07-0.1mm 2 .

本发明的日盲紫外探测器以非晶掺氧氮化硅(a-SiNx:O)薄膜为紫外光吸收层，a-SiNx:O薄膜在紫外光辐照下产生载流子，这些光生载流子可以通过a-SiNx:O薄膜中的复合中心进行复合；以硅基底为载流子传输层，a-SiNx:O薄膜与硅基底之间由于带隙差异会形成异质结，a-SiNx:O薄膜中产生的载流子会在异质结内建电场驱动下，从a-SiNx:O薄膜层转移至硅基底中，并在载流子迁移率高的p-Si或i-Si基底中进行传输直至到达叉指状电极；叉指状电极的使用，可以在增大紫外辐照受光面积的同时，缩短指状电极间的距离，使得载流子能够在短时间内通过p-Si或i-Si传输层，从而实现较大的光导增益。The solar-blind ultraviolet detector of the present invention uses amorphous oxygen-doped silicon nitride (a-SiN x : O) thin film as the ultraviolet light absorbing layer, and the a-SiN x : O thin film generates carriers under ultraviolet light irradiation, and these Photogenerated carriers can recombine through the recombination centers in the a-SiN x :O thin film; with the silicon substrate as the carrier transport layer, a heterogeneous structure will be formed between the a-SiN x :O thin film and the silicon substrate due to the difference in band gap junction, the carriers generated in the a-SiN x :O film will be transferred from the a-SiN x :O film layer to the silicon substrate under the drive of the built-in electric field of the heterojunction, and in the high carrier mobility Transport in the p-Si or i-Si substrate until it reaches the interdigitated electrodes; the use of interdigitated electrodes can increase the light-receiving area of ultraviolet radiation while shortening the distance between the interdigitated electrodes, so that the carriers can Through the p-Si or i-Si transport layer in a short time, so as to achieve a large light guide gain.

即本发明将载流子的产生/复合过程与载流子的运输过程相分离，克服了载流子的复合与运输在同一层中所导致的高响应度和高响应速度不能同时达到的固有矛盾。并且，载流子在a-SiNx:O薄膜中的复合寿命远大于在p-Si或i-Si传输层中的输运时间，从而形成较大的光导增益。That is, the present invention separates the generation/recombination process of carriers from the transport process of carriers, and overcomes the inherent problem that high responsivity and high response speed cannot be achieved simultaneously due to the recombination and transport of carriers in the same layer. contradiction. Moreover, the recombination lifetime of carriers in the a-SiN x :O thin film is much longer than the transport time in the p-Si or i-Si transport layer, thus forming a larger photoconductive gain.

另外，本发明的a-SiNx:O薄膜还会对p-Si或i-Si基底表面产生钝化作用，使得a-SiNx:O薄膜与硅基底界面处的缺陷态密度降低，可以使光生载流子几乎无损耗地从a-SiNx:O薄膜穿过a-SiNx:O/Si之间的界面，到达p-Si或i-Si传输层。In addition, the a-SiN x : O thin film of the present invention can also passivate the surface of the p-Si or i-Si substrate, so that the defect state density at the interface between the a-SiN x : O thin film and the silicon substrate can be reduced, which can make The photogenerated carriers pass through the interface between a-SiN x :O/Si from the a-SiN x :O film almost without loss, and reach the p-Si or i-Si transport layer.

本发明控制非晶掺氧氮化硅薄膜的厚度为100-200nm，薄膜厚度太薄(<100nm)，器件漏电流比较大；薄膜厚度太厚(>200nm)，薄膜中的光生载流子不能注入到p-Si或i-Si传输层，进而导致器件不能工作。The present invention controls the thickness of the amorphous oxygen-doped silicon nitride film to be 100-200nm, if the film thickness is too thin (<100nm), the device leakage current is relatively large; if the film thickness is too thick (>200nm), the photogenerated carriers in the film cannot Implanted into the p-Si or i-Si transport layer, which will cause the device to fail to work.

另一方面，本发明实施例提供一种光导型全硅基日盲紫外探测器的制作方法，其特征在于，包括以下步骤：On the other hand, an embodiment of the present invention provides a method for manufacturing a photoconductive all-silicon-based solar-blind ultraviolet detector, which is characterized in that it includes the following steps:

提供一硅基底；providing a silicon substrate;

在所述硅基底上沉积一层非晶掺氧氮化硅薄膜；Depositing a layer of amorphous oxygen-doped silicon nitride film on the silicon substrate;

在所述非晶掺氧氮化硅薄膜表面形成叉指状电极。Interdigitated electrodes are formed on the surface of the amorphous oxygen-doped silicon nitride film.

进一步地，还包括硅基底预处理步骤，所述硅基底预处理步骤具体包括：Further, a silicon substrate pretreatment step is also included, and the silicon substrate pretreatment step specifically includes:

依次对硅基底进行酸洗、碱洗、水漂洗，烘干后再用酸液除去硅基底表面的氧化层，之后氮气吹干备用。Carry out pickling, alkali washing, and water rinsing on the silicon substrate in sequence, and then use acid solution to remove the oxide layer on the surface of the silicon substrate after drying, and then dry it with nitrogen gas for later use.

进一步地，硅基底上沉积非晶掺氧氮化硅薄膜步骤具体包括：Further, the step of depositing an amorphous oxygen-doped silicon nitride film on the silicon substrate specifically includes:

将硅烷、氨气和氮气的混合气体通过等离子气相沉积工艺在硅基底表面沉积一层非晶氮化硅薄膜，再对所述非晶氮化硅薄膜进行原位氧化得到非晶掺氧氮化硅薄膜。A mixed gas of silane, ammonia and nitrogen is deposited on the surface of a silicon substrate by a plasma vapor deposition process to form an amorphous silicon nitride film, and then the amorphous silicon nitride film is oxidized in situ to obtain an amorphous oxygen-doped nitride film. silicon thin film.

更进一步地，混合气体中硅烷、氨气、氮气的气体流量比为1:8:35-45。Furthermore, the gas flow ratio of silane, ammonia, and nitrogen in the mixed gas is 1:8:35-45.

更进一步地，等离子气相沉积工艺的参数为：射频功率18-22W、气压550-600mTorr、温度240-260℃。Furthermore, the parameters of the plasma vapor deposition process are: RF power 18-22W, air pressure 550-600mTorr, temperature 240-260°C.

进一步地，还包括退火步骤，所述退火步骤发生在非晶掺氧氮化硅薄膜沉积完成之后、叉指状电极形成之前；将形成有非晶掺氧氮化硅薄膜的硅基底在950-1050℃下，氮气氛围中退火0.5-1.5h。Further, an annealing step is also included, and the annealing step occurs after the deposition of the amorphous oxygen-doped silicon nitride film is completed and before the formation of the interdigitated electrodes; Anneal in nitrogen atmosphere at 1050°C for 0.5-1.5h.

进一步地，非晶掺氧氮化硅薄膜表面形成叉指状电极步骤具体包括：Further, the step of forming interdigitated electrodes on the surface of the amorphous oxy-doped silicon nitride film specifically includes:

在非晶掺氧氮化硅薄膜表面涂覆光刻胶，并在光刻胶上形成叉指状电极图形，然后在光刻胶表面蒸镀金属，最后在水浴加热下利用lift-off剥离工艺形成叉指状电极。Coating photoresist on the surface of amorphous oxygen-doped silicon nitride film, forming interdigitated electrode patterns on the photoresist, then evaporating metal on the surface of the photoresist, and finally using lift-off stripping process under water bath heating Interdigitated electrodes are formed.

本发明的制备方法中，混合气体中各气体的流量比对形成的非晶掺氧氮化硅薄膜的光学带隙有影响，当硅烷和氨气流量比为1:8时形成的非晶掺氧氮化硅薄膜的带隙(约为4.8eV)恰好落在日盲紫外波段范围内。In the preparation method of the present invention, the flow ratio of each gas in the mixed gas has an influence on the optical bandgap of the formed amorphous oxy-doped silicon nitride film, and the amorphous doped silicon nitride film formed when the flow ratio of silane and ammonia is 1:8 The bandgap (about 4.8eV) of the silicon oxynitride film just falls within the solar-blind ultraviolet range.

本发明对沉积形成的非晶掺氧氮化硅薄膜进行退火处理，退火处理可以降低薄膜中的缺陷态密度，提高薄膜质量，进而使得探测器的性能得到提升。The invention performs annealing treatment on the deposited amorphous oxygen-doped silicon nitride film, and the annealing treatment can reduce the defect state density in the film, improve the quality of the film, and further improve the performance of the detector.

与现有技术相比，本发明具有以下效果：Compared with the prior art, the present invention has the following effects:

1、本发明的日盲紫外探测器采用发光的宽禁带非晶掺氧氮化硅(a-SiNx:O)薄膜作为紫外光吸收层，以p-Si或i-Si作为载流子传输层，构建的光导型全硅基日盲紫外探测器不仅成本低廉，而且能与成熟的CMOS制造工艺相兼容，从而实现大面积生产。1. The solar-blind ultraviolet detector of the present invention adopts a luminous wide-bandgap amorphous silicon nitride (a-SiN x :O) thin film as the ultraviolet light absorbing layer, and uses p-Si or i-Si as the carrier The photoconductive all-silicon-based solar-blind ultraviolet detector constructed by the transmission layer is not only low in cost, but also compatible with mature CMOS manufacturing processes, thereby realizing large-area production.

2、本发明将载流子的产生/复合过程与载流子的运输过程相分离，克服了载流子的复合与输运在同一层中所导致的高响应度和高响应速度不能同时达到的固有矛盾，使得探测器同时达到高响应度(4×103A/W)和高响应速度(4μs)，探测率量级可达1014cm·Hz1 /2·W-1。2. The present invention separates the generation/recombination process of carriers from the transport process of carriers, which overcomes the fact that the high responsivity and high response speed caused by the recombination and transport of carriers in the same layer cannot be achieved at the same time. The inherent contradiction of the detector makes the detector achieve high responsivity (4×10 3 A/W) and high response speed (4μs) at the same time, and the detection rate can reach 10 14 cm·Hz 1 /2 ·W -1 .

3、本发明的a-SiNx:O薄膜还会对p-Si或i-Si基底表面产生钝化作用，使得a-SiNx:O薄膜与硅基底界面处缺陷态密度降低，可以使光生载流子几乎无损耗地从a-SiNx:O薄膜穿过a-SiNx:O/Si之间的界面，到达p-Si或i-Si传输层。3. The a-SiN x : O thin film of the present invention can also passivate the surface of the p-Si or i-Si substrate, so that the density of defect states at the interface between the a-SiN x : O thin film and the silicon substrate can be reduced, enabling photogenerated Carriers pass through the interface between a-SiN x :O/Si from the a-SiN x :O film almost without loss, and reach the p-Si or i-Si transport layer.

4、本发明的制作方法中将硅烷、氨气和氮气的混合气体通过等离子气相沉积工艺在硅基底表面沉积一层非晶氮化硅薄膜，再对所述非晶氮化硅薄膜进行原位氧化得到非晶掺氧氮化硅薄膜，通过这种方法制得的非晶掺氧氮化硅薄膜内部能够形成与氧有关的载流子复合中心，光生载流子从而可以通过复合中心进行复合，光生载流子的复合时间在纳秒量级，由此可以确保本发明的全硅基日盲紫外探测器微秒量级的高响应速度。4. In the production method of the present invention, a mixed gas of silane, ammonia and nitrogen is deposited on the surface of a silicon substrate by a plasma vapor deposition process, and then the amorphous silicon nitride film is in situ Amorphous oxygen-doped silicon nitride film is obtained by oxidation, and the carrier recombination center related to oxygen can be formed inside the amorphous oxygen-doped silicon nitride film prepared by this method, so that the photogenerated carriers can recombine through the recombination center , the recombination time of photogenerated carriers is on the order of nanoseconds, thereby ensuring the high response speed of the all-silicon-based solar-blind ultraviolet detector of the present invention on the order of microseconds.

附图说明Description of drawings

为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍。In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following will briefly introduce the drawings that need to be used in the description of the embodiments.

图1为本发明实施例1中光导型全硅基日盲紫外探测器的结构示意图。FIG. 1 is a schematic structural view of a photoconductive all-silicon-based solar-blind ultraviolet detector in Example 1 of the present invention.

具体实施方式Detailed ways

为使本发明实施例的目的、技术方案和优点更加清楚，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，所描述的实施例是本发明一部分实施例，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。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of embodiments of the present invention, but not all embodiments. 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.

在本发明的描述中，需要说明的是，术语“中心”、“顶”、“底”、“左”、“右”、“竖直”、“水平”、“内”、“外”、“前”、“后”等指示的方位或位置关系为基于具体使用状态所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。In the description of the present invention, it should be noted that the terms "center", "top", "bottom", "left", "right", "vertical", "horizontal", "inner", "outer", The orientation or positional relationship indicated by "front", "rear", etc. is based on the orientation or positional relationship shown in the specific use state, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the referred device or element must be Having a particular orientation, being constructed and operating in a particular orientation, and therefore not to be construed as limiting the invention.

为了解决现有宽禁带半导体材料制作日盲紫外探测器时存在的不易于大规模生产，且不能与当前成熟的硅CMOS工艺相兼容，导致器件的制作成本较高的缺陷，本发明采用发光的宽禁带非晶掺氧氮化硅(a-SiNx:O)薄膜作为紫外光吸收层，以p-Si或i-Si作为载流子传输层，构建的光导型全硅基日盲紫外探测器不仅成本低廉，而且能与成熟的CMOS制造工艺相兼容。In order to solve the defects that existing wide bandgap semiconductor materials are not easy to be mass-produced when making solar-blind ultraviolet detectors, and cannot be compatible with the current mature silicon CMOS process, resulting in high manufacturing costs of the device, the present invention adopts luminescent The wide-bandgap amorphous silicon nitride (a-SiN x :O) thin film is used as the ultraviolet light absorbing layer, and p-Si or i-Si is used as the carrier transport layer to construct a photoconductive all-silicon-based solar blind UV detectors are not only low cost, but also compatible with mature CMOS manufacturing processes.

接下来将通过具体实施例对本发明的技术方案进行详细描述。Next, the technical solutions of the present invention will be described in detail through specific examples.

需要说明的是，本发明实施例中使用的P型硅基底是(100)晶向，电阻率为1-5Ω·cm，厚度约为500μm；使用的本征晶硅基底是(100)晶向，电阻率为6000Ω·cm，厚度约为400μm。It should be noted that the P-type silicon substrate used in the embodiment of the present invention has a (100) crystal orientation, a resistivity of 1-5Ω·cm, and a thickness of about 500 μm; the intrinsic crystal silicon substrate used is a (100) crystal orientation , the resistivity is 6000Ω·cm, and the thickness is about 400μm.

实施例1Example 1

光导型全硅基日盲紫外探测器，如图1所示，包括：P型晶硅基底1、形成于所述P型晶硅基底1表面的非晶掺氧氮化硅薄膜2、以及形成于所述非晶掺氧氮化硅薄膜2表面的Ti/Au叉指状电极3。The photoconductive type all-silicon-based solar-blind ultraviolet detector, as shown in Figure 1, includes: a P-type crystalline silicon substrate 1, an amorphous oxygen-doped silicon nitride film 2 formed on the surface of the P-type crystalline silicon substrate 1, and a Ti/Au interdigitated electrodes 3 on the surface of the amorphous oxy-doped silicon nitride film 2 .

具体的，非晶掺氧氮化硅薄膜2的厚度为100nm，Ti/Au叉指状电极3的受光面积为0.07mm2。Specifically, the thickness of the amorphous oxy-doped silicon nitride film 2 is 100 nm, and the light-receiving area of the Ti/Au interdigitated electrode 3 is 0.07 mm 2 .

本实施例的光导型全硅基日盲紫外探测器的制作方法包括如下步骤：The fabrication method of the photoconductive all-silicon-based solar-blind ultraviolet detector of the present embodiment comprises the following steps:

(1)利用氯化氢(HCl)溶液对p-Si基底酸洗，再通过NH4OH溶液对p-Si基底碱洗，然后利用去离子水对p-Si基底漂洗10次后烘干，最后用10％的氢氟酸(HF)溶液漂洗去除p-Si基底表面的氧化层，再利用氮气将p-Si基底表面吹干；(1) Pickling the p-Si substrate with hydrogen chloride (HCl) solution, then alkali-washing the p-Si substrate with NH 4 OH solution, then rinsing the p-Si substrate with deionized water for 10 times, drying it, and finally using Rinse with 10% hydrofluoric acid (HF) solution to remove the oxide layer on the surface of the p-Si substrate, and then use nitrogen to dry the surface of the p-Si substrate;

(2)将步骤(1)中清洗好的p-Si基底置于等离子体气相沉积(PECVD)设备中，然后通入气体流量比为1:8:35的硅烷(SiH4)、氨气(NH3)和氮气(N2)，在18W的射频功率、550mTorr的气压和240℃温度下，在p-Si衬底上淀积一层100nm的非晶氮化硅(a-SiNx)薄膜，最后通入氧气(O2)，利用氧等离子体对a-SiNx薄膜进行原位氧化，获得非晶掺氧氮化硅(a-SiNx:O)薄膜；(2) Place the p-Si substrate cleaned in step (1) in the plasma vapor deposition (PECVD) equipment, and then feed silane (SiH 4 ), ammonia ( NH 3 ) and nitrogen (N 2 ), at 18W RF power, 550mTorr pressure and 240°C temperature, a 100nm amorphous silicon nitride (a- SiNx ) film was deposited on the p-Si substrate , and finally introduce oxygen (O 2 ), and use oxygen plasma to oxidize the a-SiN x film in situ to obtain an amorphous oxygen-doped silicon nitride (a-SiN x :O) film;

(3)在950℃下，N2气氛中对a-SiNx:O薄膜退火1.5h；(3) Anneal the a-SiN x :O thin film at 950°C for 1.5h in N 2 atmosphere;

(4)在a-SiNx:O薄膜表面涂覆光刻胶，通过光刻方法在光刻胶上形成叉指状电极图形，然后利用电子束蒸发在其表面蒸镀20nm Ti和80nmAu电极，再在65℃水浴加热下，利用lift-off剥离工艺，最终在a-SiNx:O薄膜表面形成Ti/Au叉指状电极。(4) Coating photoresist on the surface of the a- SiNx :O film, forming interdigitated electrode patterns on the photoresist by photolithography, and then using electron beam evaporation to evaporate 20nm Ti and 80nmAu electrodes on the surface, Then, under heating in a water bath at 65°C, Ti/Au interdigitated electrodes were finally formed on the surface of the a-SiN x :O film by using the lift-off stripping process.

至此，光导型全硅基日盲紫外探测器制作完成。So far, the photoconductive all-silicon-based solar-blind ultraviolet detector has been fabricated.

实施例2Example 2

光导型全硅基日盲紫外探测器，本实施例中的非晶掺氧氮化硅薄膜的厚度为120nm，Ti/Au叉指状电极3的受光面积为0.08mm2。In the photoconductive all-silicon-based solar-blind ultraviolet detector, the thickness of the amorphous oxygen-doped silicon nitride film in this embodiment is 120 nm, and the light-receiving area of the Ti/Au interdigitated electrodes 3 is 0.08 mm 2 .

本实施例的光导型全硅基日盲紫外探测器的制作方法包括如下步骤：The fabrication method of the photoconductive all-silicon-based solar-blind ultraviolet detector of the present embodiment comprises the following steps:

(1)利用氯化氢(HCl)溶液对p-Si基底酸洗，再通过NH4OH溶液对p-Si基底碱洗，然后利用去离子水对p-Si基底漂洗10次后烘干，最后用10％的氢氟酸(HF)溶液漂洗去除p-Si基底表面的氧化层，再利用氮气将p-Si基底表面吹干；(1) Pickling the p-Si substrate with hydrogen chloride (HCl) solution, then alkali-washing the p-Si substrate with NH 4 OH solution, then rinsing the p-Si substrate with deionized water for 10 times, drying it, and finally using Rinse with 10% hydrofluoric acid (HF) solution to remove the oxide layer on the surface of the p-Si substrate, and then use nitrogen to dry the surface of the p-Si substrate;

(2)将步骤(1)中清洗好的p-Si基底置于等离子体气相沉积(PECVD)设备中，然后通入气体流量比为1:8:40的硅烷(SiH4)、氨气(NH3)和氮气(N2)，在20W的射频功率、580mTorr的气压和250℃温度下，在p-Si衬底上淀积一层120nm的非晶氮化硅(a-SiNx)薄膜，最后通入氧气(O2)，利用氧等离子体对a-SiNx薄膜进行原位氧化，获得非晶掺氧氮化硅(a-SiNx:O)薄膜；(2) Place the p-Si substrate cleaned in step (1) in the plasma vapor deposition (PECVD) equipment, and then feed silane (SiH 4 ), ammonia ( NH 3 ) and nitrogen (N 2 ), at 20W RF power, 580mTorr pressure and 250°C temperature, deposit a layer of 120nm amorphous silicon nitride (a- SiNx ) film on p-Si substrate , and finally introduce oxygen (O 2 ), and use oxygen plasma to oxidize the a-SiN x film in situ to obtain an amorphous oxygen-doped silicon nitride (a-SiN x :O) film;

(3)在1000℃下，N2气氛中对a-SiNx:O薄膜退火1h；(3) Anneal the a-SiN x :O thin film at 1000°C for 1h in N 2 atmosphere;

(4)在a-SiNx:O薄膜表面涂覆光刻胶，通过光刻方法在光刻胶上形成叉指状电极图形，然后利用电子束蒸发在其表面蒸镀20nm Ti和80nmAu电极，再在65℃水浴加热下，利用lift-off剥离工艺，最终在a-SiNx:O薄膜表面形成Ti/Au叉指状电极。(4) Coating photoresist on the surface of the a- SiNx :O film, forming interdigitated electrode patterns on the photoresist by photolithography, and then using electron beam evaporation to evaporate 20nm Ti and 80nmAu electrodes on the surface, Then, under heating in a water bath at 65°C, Ti/Au interdigitated electrodes were finally formed on the surface of the a-SiN x :O film by using the lift-off stripping process.

本实施例构建的探测器的高响应度为4×103A/W，响应速度为4μs，探测率量级为1014cm·Hz1/2·W-1。The detector constructed in this embodiment has a high responsivity of 4×10 3 A/W, a response speed of 4 μs, and a detection rate of 10 14 cm·Hz 1/2 ·W -1 .

实施例3Example 3

光导型全硅基日盲紫外探测器，本实施例中的非晶掺氧氮化硅薄膜的厚度为150nm，Ti/Au叉指状电极3的受光面积为0.1mm2。In the photoconductive all-silicon-based solar-blind ultraviolet detector, the thickness of the amorphous oxygen-doped silicon nitride film in this embodiment is 150 nm, and the light-receiving area of the Ti/Au interdigitated electrodes 3 is 0.1 mm 2 .

本实施例的光导型全硅基日盲紫外探测器的制作方法包括如下步骤：The fabrication method of the photoconductive all-silicon-based solar-blind ultraviolet detector of the present embodiment comprises the following steps:

(1)利用氯化氢(HCl)溶液对p-Si基底酸洗，再通过NH4OH溶液对p-Si基底碱洗，然后利用去离子水对p-Si基底漂洗10次后烘干，最后用10％的氢氟酸(HF)溶液漂洗去除p-Si基底表面的氧化层，再利用氮气将p-Si基底表面吹干；(1) Pickling the p-Si substrate with hydrogen chloride (HCl) solution, then alkali-washing the p-Si substrate with NH 4 OH solution, then rinsing the p-Si substrate with deionized water for 10 times, drying it, and finally using Rinse with 10% hydrofluoric acid (HF) solution to remove the oxide layer on the surface of the p-Si substrate, and then use nitrogen to dry the surface of the p-Si substrate;

(2)将步骤(1)中清洗好的p-Si基底置于等离子体气相沉积(PECVD)设备中，然后通入气体流量比为1:8:45的硅烷(SiH4)、氨气(NH3)和氮气(N2)，在22W的射频功率、600mTorr的气压和260℃温度下，在p-Si衬底上淀积一层150nm的非晶氮化硅(a-SiNx)薄膜，最后通入氧气(O2)，利用氧等离子体对a-SiNx薄膜进行原位氧化，获得非晶掺氧氮化硅(a-SiNx:O)薄膜；(2) Place the p-Si substrate cleaned in step (1) in the plasma vapor deposition (PECVD) equipment, and then feed silane (SiH 4 ), ammonia ( NH 3 ) and nitrogen (N 2 ), at 22W RF power, 600mTorr pressure and 260°C temperature, deposit a 150nm amorphous silicon nitride (a- SiNx ) film on p-Si substrate , and finally introduce oxygen (O 2 ), and use oxygen plasma to oxidize the a-SiN x film in situ to obtain an amorphous oxygen-doped silicon nitride (a-SiN x :O) film;

(3)在1050℃下，N2气氛中对a-SiNx:O薄膜退火0.5h；(3) Anneal the a-SiN x :O thin film at 1050°C for 0.5h in N 2 atmosphere;

(4)在a-SiNx:O薄膜表面涂覆光刻胶，通过光刻方法在光刻胶上形成叉指状电极图形，然后利用电子束蒸发在其表面蒸镀20nm Ti和80nmAu电极，再在65℃水浴加热下，利用lift-off剥离工艺，最终在a-SiNx:O薄膜表面形成Ti/Au叉指状电极。(4) Coating photoresist on the surface of the a- SiNx :O film, forming interdigitated electrode patterns on the photoresist by photolithography, and then using electron beam evaporation to evaporate 20nm Ti and 80nmAu electrodes on the surface, Then, under heating in a water bath at 65°C, Ti/Au interdigitated electrodes were finally formed on the surface of the a-SiN x :O film by using the lift-off stripping process.

实施例4Example 4

光导型全硅基日盲紫外探测器，本实施例中的非晶掺氧氮化硅薄膜的厚度为200nm，Al叉指状电极的受光面积为0.08mm2。For the photoconductive all-silicon-based solar-blind ultraviolet detector, the thickness of the amorphous oxygen-doped silicon nitride film in this embodiment is 200 nm, and the light-receiving area of the Al interdigitated electrode is 0.08 mm 2 .

本实施例的光导型全硅基日盲紫外探测器的制作方法包括如下步骤：The fabrication method of the photoconductive all-silicon-based solar-blind ultraviolet detector of the present embodiment comprises the following steps:

(1)利用氯化氢(HCl)溶液对i-Si基底酸洗，再通过NH4OH溶液对i-Si基底碱洗，然后利用去离子水对i-Si基底漂洗10次后烘干，最后用10％的氢氟酸(HF)溶液漂洗去除i-Si基底表面的氧化层，再利用氮气将i-Si基底表面吹干；(1) Pickling the i-Si substrate with hydrogen chloride (HCl) solution, then alkali-washing the i-Si substrate with NH 4 OH solution, then rinsing the i-Si substrate with deionized water for 10 times, drying it, and finally using Rinse with 10% hydrofluoric acid (HF) solution to remove the oxide layer on the surface of the i-Si substrate, and then use nitrogen to dry the surface of the i-Si substrate;

(2)将步骤(1)中清洗好的i-Si基底置于等离子体气相沉积(PECVD)设备中，然后通入气体流量比为1:8:40的硅烷(SiH4)、氨气(NH3)和氮气(N2)，在20W的射频功率、580mTorr的气压和250℃温度下，在i-Si衬底上淀积一层200nm的非晶氮化硅(a-SiNx)薄膜，最后通入氧气(O2)，利用氧等离子体对a-SiNx薄膜进行原位氧化，获得非晶掺氧氮化硅(a-SiNx:O)薄膜；(2) Place the i-Si substrate cleaned in step (1) in the plasma vapor deposition (PECVD) equipment, and then feed silane (SiH 4 ), ammonia ( NH 3 ) and nitrogen (N 2 ), at 20W RF power, 580mTorr pressure and 250°C temperature, a 200nm amorphous silicon nitride (a- SiNx ) film was deposited on the i-Si substrate , and finally introduce oxygen (O 2 ), and use oxygen plasma to oxidize the a-SiN x film in situ to obtain an amorphous oxygen-doped silicon nitride (a-SiN x :O) film;

(3)在1000℃下，N2气氛中对a-SiNx:O薄膜退火1h；(3) Anneal the a-SiN x :O thin film at 1000°C for 1h in N 2 atmosphere;

(4)在a-SiNx:O薄膜表面涂覆光刻胶，通过光刻方法在光刻胶上形成叉指状电极图形，然后利用电子束蒸发在其表面蒸镀100nm的Al电极，再在65℃水浴加热下，利用lift-off剥离工艺，最终在a-SiNx:O薄膜表面形成Al叉指状电极。(4) Coating photoresist on the surface of a- SiNx :O thin film, forming interdigitated electrode patterns on the photoresist by photolithography, then utilizing electron beam evaporation to vapor-deposit 100nm Al electrodes on its surface, and then Al interdigitated electrodes were finally formed on the surface of the a-SiN x :O film by using the lift-off process under heating in a water bath at 65°C.

对比例1Comparative example 1

光导型全硅基日盲紫外探测器，包括：N型晶硅基底、形成于所述N型晶硅基底的非晶掺氧氮化硅薄膜、以及形成于所述非晶掺氧氮化硅薄膜表面的Ti/Au叉指状电极；其中，N型晶硅基底的厚度为500μm，非晶掺氧氮化硅薄膜的厚度为120nm，Ti/Au叉指状电极的受光面积为0.08mm2。A photoconductive all-silicon-based solar-blind ultraviolet detector, comprising: an N-type crystalline silicon substrate, an amorphous oxygen-doped silicon nitride film formed on the N-type crystalline silicon substrate, and an amorphous oxygen-doped silicon nitride film formed on the Ti/Au interdigitated electrodes on the surface of the film; among them, the thickness of the N-type crystalline silicon substrate is 500μm, the thickness of the amorphous oxygen-doped silicon nitride film is 120nm, and the light receiving area of the Ti/Au interdigitated electrodes is 0.08mm 2 .

对比例1中的光导型全硅基日盲紫外探测器的制作方法与实施例2中的制作方法相同。The fabrication method of the photoconductive all-silicon-based solar-blind ultraviolet detector in Comparative Example 1 is the same as that in Example 2.

经检测得出：对比例1中制备的以N型晶硅为基底的掺氧氮化硅薄膜，没有显现日盲探测器相关性能。It was found through testing that the oxygen-doped silicon nitride thin film based on N-type crystalline silicon prepared in Comparative Example 1 did not exhibit performance related to solar-blind detectors.

对比例2Comparative example 2

光导型全硅基日盲紫外探测器，包括：P型晶硅基底、形成于所述P型晶硅基底表面的非晶氮化硅薄膜、以及形成于所述非晶氮化硅薄膜表面的Ti/Au叉指状电极；其中，P型晶硅基底的厚度为500μm，非晶氮化硅薄膜的厚度为120nm，Ti/Au叉指状电极的受光面积为0.08mm2。A photoconductive all-silicon-based solar-blind ultraviolet detector, comprising: a P-type crystalline silicon substrate, an amorphous silicon nitride film formed on the surface of the P-type crystalline silicon substrate, and an amorphous silicon nitride film formed on the surface of the amorphous silicon nitride film. Ti/Au interdigitated electrodes; wherein, the thickness of the P-type crystalline silicon substrate is 500 μm, the thickness of the amorphous silicon nitride film is 120 nm, and the light receiving area of the Ti/Au interdigitated electrodes is 0.08 mm 2 .

对比例2的光导型全硅基日盲紫外探测器的制备方法包括以下步骤：The preparation method of the photoconductive type all-silicon-based solar-blind ultraviolet detector of comparative example 2 comprises the following steps:

(1)利用氯化氢(HCl)溶液对p-Si基底酸洗，再通过NH4OH溶液对p-Si基底碱洗，然后利用去离子水对p-Si基底漂洗10次后烘干，最后用10％的氢氟酸(HF)溶液漂洗去除p-Si基底表面的氧化层，再利用氮气将p-Si基底表面吹干；(1) Pickling the p-Si substrate with hydrogen chloride (HCl) solution, then alkali-washing the p-Si substrate with NH 4 OH solution, then rinsing the p-Si substrate with deionized water for 10 times, drying it, and finally using Rinse with 10% hydrofluoric acid (HF) solution to remove the oxide layer on the surface of the p-Si substrate, and then use nitrogen to dry the surface of the p-Si substrate;

(2)将步骤(1)中清洗好的p-Si基底置于等离子体气相沉积(PECVD)设备中，然后通入气体流量比为1:8:40的硅烷(SiH4)、氨气(NH3)和氮气(N2)，在20W的射频功率、580mTorr的气压和250℃温度下，在p-Si衬底上淀积一层100nm的非晶氮化硅(a-SiNx)薄膜；(2) Place the p-Si substrate cleaned in step (1) in the plasma vapor deposition (PECVD) equipment, and then feed silane (SiH 4 ), ammonia ( NH 3 ) and nitrogen (N 2 ), at 20W RF power, 580mTorr pressure and 250°C temperature, deposit a 100nm amorphous silicon nitride (a- SiNx ) film on p-Si substrate ;

(3)在1000℃下，N2气氛中对a-SiNx薄膜退火1h；(3) Anneal the a-SiN x film for 1 h in N 2 atmosphere at 1000°C;

(4)在a-SiNx薄膜表面涂覆光刻胶，通过光刻方法在光刻胶上形成叉指状电极图形，然后利用电子束蒸发在其表面蒸镀20nm Ti和80nmAu电极，再在65℃水浴加热下，利用lift-off剥离工艺，最终在a-SiNx薄膜表面形成Ti/Au叉指状电极。(4) Coating photoresist on the surface of the a-SiN x film, forming interdigitated electrode patterns on the photoresist by photolithography, and then using electron beam evaporation to evaporate 20nm Ti and 80nmAu electrodes on the surface, and then Ti/Au interdigitated electrodes were finally formed on the surface of the a-SiN x film by using the lift-off process under heating in a water bath at 65°C.

经检测得出对比例2的探测器的响应度仅为30A/W，远小于实施例2中探测器的响应度，说明非晶掺氧氮化硅薄膜相较于氮化硅薄膜能显著提高探测器的响应度。After testing, the responsivity of the detector in Comparative Example 2 is only 30A/W, which is far less than that of the detector in Example 2, indicating that the amorphous oxygen-doped silicon nitride film can significantly improve the The responsivity of the detector.

需要说明的是，本发明实施例中响应度测量采用Keithley源表作为电压源，500W的氙灯作为光源，将氙灯的复色光通过单色仪变为单色光，经过光纤将单色光直接照射在探测器的表面，测量光照情况下的光电流，入射光的光功率通过标准Si探测器进行标定。It should be noted that in the embodiment of the present invention, the responsivity measurement uses a Keithley source meter as the voltage source, and a 500W xenon lamp as the light source. The polychromatic light of the xenon lamp is changed into monochromatic light by a monochromator, and the monochromatic light is directly irradiated through an optical fiber. On the surface of the detector, the photocurrent under illumination is measured, and the optical power of the incident light is calibrated by a standard Si detector.

响应速度通过拟合探测器的瞬态响应谱线可得，器件瞬态响应采用213nm脉冲激发作为光源，电流放大器对光电流放大后用数字示波器进行显示。The response speed can be obtained by fitting the transient response spectrum of the detector. The transient response of the device uses 213nm pulse excitation as the light source, and the current amplifier amplifies the photocurrent and displays it with a digital oscilloscope.

应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the inventive concept of the present invention, and these all belong to the protection scope of the present invention.

Claims (10)

1. Light guide type all silicon-based solar blind ultraviolet detector is characterized by comprising:
a silicon substrate, which is P-type crystalline silicon or intrinsic crystalline silicon, configured as a carrier transport layer;
the amorphous oxygen-doped silicon nitride film is formed on the surface of the silicon substrate and is configured to be an ultraviolet light absorption layer to generate carriers;
and the interdigital electrode is formed on the surface of the amorphous oxygen-doped silicon nitride film.
2. The light-guide type all-silicon solar-blind ultraviolet detector as claimed in claim 1, wherein the thickness of the amorphous oxygen-doped silicon nitride film is 100-200nm.
3. The photoconductive-type all-silicon-based solar blind ultraviolet detector according to claim 1, wherein the interdigital electrode is a Ti/Au interdigital electrode or an Al interdigital electrode, and the light receiving area of the interdigital electrode is 0.07-0.1mm 2 。
4. The manufacturing method of the light guide type all-silicon solar blind ultraviolet detector is characterized by comprising the following steps of:
providing a silicon substrate;
depositing an amorphous oxygen-doped silicon nitride film on the silicon substrate;
and forming interdigital electrodes on the surface of the amorphous oxygen-doped silicon nitride film.
5. The manufacturing method of the light guide type all-silicon solar blind ultraviolet detector according to claim 4, further comprising a silicon substrate pretreatment step, wherein the silicon substrate pretreatment step specifically comprises:
and sequentially carrying out acid washing, alkali washing and water rinsing on the silicon substrate, drying, removing an oxide layer on the surface of the silicon substrate by using acid liquor, and then blowing by using nitrogen for later use.
6. The method for manufacturing the light guide type all-silicon-based solar blind ultraviolet detector according to claim 4, wherein the step of depositing the amorphous oxygen-doped silicon nitride film on the silicon substrate comprises the following steps:
depositing a layer of amorphous silicon nitride film on the surface of a silicon substrate by using a mixed gas of silane, ammonia and nitrogen through a plasma vapor deposition process, and then carrying out in-situ oxidation on the amorphous silicon nitride film to obtain the amorphous oxygen-doped silicon nitride film.
7. The method for manufacturing the light guide type all-silicon solar blind ultraviolet detector according to claim 6, wherein the gas flow ratio of silane, ammonia and nitrogen in the mixed gas is 1.
8. The method for manufacturing the light guide type all-silicon solar blind ultraviolet detector according to claim 6, wherein the parameters of the plasma vapor deposition process are as follows: the radio frequency power is 18-22W, the air pressure is 550-600mTorr, and the temperature is 240-260 ℃.
9. The method for manufacturing the light guide type all-silicon-based solar blind ultraviolet detector according to claim 4, further comprising an annealing step, wherein the annealing step is carried out after the deposition of the amorphous oxygen-doped silicon nitride film is completed and before the formation of the interdigital electrodes; and annealing the silicon substrate with the amorphous oxygen-doped silicon nitride film for 0.5-1.5h at 950-1050 ℃ in a nitrogen atmosphere.
10. The method for manufacturing the photoconductive type all-silicon-based solar blind ultraviolet detector according to claim 4, wherein the step of forming interdigital electrodes on the surface of the amorphous oxygen-doped silicon nitride film comprises the following steps:
coating photoresist on the surface of the amorphous oxygen-doped silicon nitride film, forming an interdigital electrode pattern on the photoresist, then evaporating metal on the surface of the photoresist, and finally forming the interdigital electrode by using a lift-off stripping process under the heating of water bath.
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