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CN112054086B - A method for preparing a silicon-based photodetector with a lateral junction - Google Patents

A method for preparing a silicon-based photodetector with a lateral junction Download PDF

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CN112054086B
CN112054086B CN202010945696.0A CN202010945696A CN112054086B CN 112054086 B CN112054086 B CN 112054086B CN 202010945696 A CN202010945696 A CN 202010945696A CN 112054086 B CN112054086 B CN 112054086B
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silicon
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lateral junction
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annealing
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CN112054086A (en
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吴强
黄松
进晓荣
刘瑶瑶
宋冠廷
周旭
张春玲
姚江宏
许京军
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Nankai University
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10FINORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H10F30/21Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10FINORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00Constructional details of devices covered by this subclass
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Abstract

The invention relates to a preparation method of a lateral junction silicon-based photoelectric detector, which is characterized in that a lateral pn junction or a heterojunction is formed by the carrier conductivity type or concentration difference between the surface of black silicon prepared by pulse laser and an unprocessed silicon region, and the black silicon photoelectric detector with the lateral junction can be formed through subsequent processes of annealing, passivation, photoetching, electrode preparation and the like. The lateral junction silicon-based photoelectric detector can efficiently absorb photons to generate electron-hole pairs under the reverse bias voltage, and can transversely migrate under the action of an external electric field to finally form a lateral photocurrent, so that optical signal detection is realized. The invention has the advantages of simple process, easily obtained raw materials, easy operation and control, compatibility with the existing semiconductor device process and the like, and compared with the traditional vertical structure detector, the horizontal junction silicon-based photoelectric detector prepared by the invention has the advantages of effectively inhibiting dark current, improving the detection rate of the device, simplifying the preparation flow of the device and being more beneficial to the preparation and integration of the device.

Description

一种具有横向结硅基光电探测器的制备方法A method for preparing a silicon-based photodetector with a lateral junction

技术领域Technical Field

本发明涉及硅基光电器件领域,具体涉及一种光电探测器的制备方法,其为一种具有较低暗电流的横向结硅基光电探测器。The invention relates to the field of silicon-based photoelectric devices, and in particular to a method for preparing a photoelectric detector, which is a lateral junction silicon-based photoelectric detector with lower dark current.

背景技术Background technique

近几十年来,随着半导体工艺的快速发展,具有各种功能的半导体器件不断改善着人们的生活,并对于下一代产业革命(如人工智能,万物互联,无人驾驶等)具有巨大潜力。作为最常见且最重要的半导体材料,硅材料具有含量丰富、价格低廉、纯度高和缺陷少等优点。迄今为止,硅在微电子领域已经发挥出巨大潜能,不断突破摩尔定律的极限,推进着半导体技术的革新与发展。然而,在光电子领域,由于受到1.12eV的能带宽度的限制,以及单晶硅表面较高的反射率,抑制了硅的吸收率,尤其是红外波段的吸收,这极大地限制了硅光子学的发展。In recent decades, with the rapid development of semiconductor technology, semiconductor devices with various functions have continuously improved people's lives and have great potential for the next generation of industrial revolution (such as artificial intelligence, the Internet of Everything, unmanned driving, etc.). As the most common and important semiconductor material, silicon material has the advantages of abundant content, low price, high purity and few defects. So far, silicon has exerted great potential in the field of microelectronics, constantly breaking the limits of Moore's Law, and promoting the innovation and development of semiconductor technology. However, in the field of optoelectronics, due to the limitation of the energy band width of 1.12eV and the high reflectivity of the single crystal silicon surface, the absorption rate of silicon is suppressed, especially the absorption in the infrared band, which greatly limits the development of silicon photonics.

不同元素的掺杂是提高半导体材料光电特性的重要方法,是光电探测器、太阳能电池等领域常见的改性手段。然而由于固体固溶度的限制,传统的热扩散工艺很难实现掺杂元素的过饱和掺杂,随着半导体工艺的发展,离子注入和超快脉冲激光过饱和掺杂可以实现超越固溶度的过饱和掺杂。特别的,通过超快脉冲激光改性后,在晶体硅表面能同时形成微锥结构和过饱和掺杂层,可以实现光电探测器广谱高响应的特性,然而这一改性过程又将不可避免地引入大量的杂质和晶格缺陷,对器件的暗电流、信噪比造成不利影响,这极大的降低了半导体器件的性能,限制了器件的应用范围。Doping with different elements is an important method to improve the photoelectric properties of semiconductor materials, and is a common modification method in the fields of photodetectors, solar cells, etc. However, due to the limitation of solid solubility, it is difficult to achieve supersaturated doping of doping elements by traditional thermal diffusion process. With the development of semiconductor technology, ion implantation and ultrafast pulse laser supersaturated doping can achieve supersaturated doping beyond solid solubility. In particular, after ultrafast pulse laser modification, micro-cone structure and supersaturated doping layer can be formed on the surface of crystalline silicon at the same time, which can realize the characteristics of broad spectrum and high response of photodetectors. However, this modification process will inevitably introduce a large number of impurities and lattice defects, which will have an adverse effect on the dark current and signal-to-noise ratio of the device, which greatly reduces the performance of semiconductor devices and limits the application range of the devices.

发明内容Summary of the invention

为了解决上述问题,本发明人经过长期试验和研究,提出一种横向结硅基光电探测器制备方法。一方面改进了传统硅基光电探测器高暗电流、低信噪比的不足,另一方面也弥补了过饱和掺杂后硅基材料难以与现有CMOS兼容的缺点。In order to solve the above problems, the inventors have proposed a method for preparing a lateral junction silicon-based photodetector after long-term experiments and research. On the one hand, it improves the shortcomings of high dark current and low signal-to-noise ratio of traditional silicon-based photodetectors, and on the other hand, it makes up for the disadvantage that silicon-based materials are difficult to be compatible with existing CMOS after supersaturated doping.

依据本发明的技术方案,提供一种横向结硅基光电探测器的制备方法,包括如下步骤:According to the technical solution of the present invention, a method for preparing a lateral junction silicon-based photodetector is provided, comprising the following steps:

步骤1:,选取半导体单晶硅片,进行预处理,包括但不限于切片、RCA清洗、在硅表面预涂含有掺杂元素的薄膜;Step 1: Select a semiconductor single crystal silicon wafer and perform pretreatment, including but not limited to slicing, RCA cleaning, and pre-coating a film containing doping elements on the silicon surface;

步骤2:选取处理后单晶硅材料,通过超快脉冲激光在特定气氛中辐照其表面特定区域,制备过饱和掺杂层,即获得黑硅表面;Step 2: Select the processed single crystal silicon material, irradiate a specific area of its surface with an ultrafast pulse laser in a specific atmosphere to prepare a supersaturated doping layer, that is, obtain a black silicon surface;

步骤3:对制备好的黑硅材料进行退火处理,激活过饱和掺杂黑硅层中的杂质原子,并修复晶格,去除结构缺陷;Step 3: Annealing the prepared black silicon material to activate the impurity atoms in the supersaturated doped black silicon layer, repair the lattice, and remove structural defects;

步骤4:在黑硅和硅表面不需要电极接触的区域镀上钝化层,以保护探测器表面,以及隔绝空气污染和氧化;Step 4: A passivation layer is plated on the black silicon and the silicon surface areas where electrode contact is not required to protect the detector surface and isolate it from air pollution and oxidation;

步骤5:在硅和黑硅区域分别镀上接触电极;至此完成横向结硅基光电探测器的制备;Step 5: Contact electrodes are plated on the silicon and black silicon regions respectively; thus, the preparation of the lateral junction silicon-based photodetector is completed;

其中所述的横向结硅基光电探测器在-5V偏压下的的暗电流可降至783nA,远小于传统垂直结构的黑硅光电探测器;同时,器件的响应波段为500nm-1400nm,在-5V偏压下的峰值响应度为3.23A/W,其中峰值波长出现在1080nm附近。其中各数学符号的具体含义为:nm:纳米,V:伏特,A/W:安培/瓦特,nA:纳安培。The dark current of the lateral junction silicon-based photodetector under -5V bias can be reduced to 783nA, which is much smaller than the traditional vertical structure black silicon photodetector; at the same time, the device has a response band of 500nm-1400nm, and a peak responsivity of 3.23A/W under -5V bias, with the peak wavelength appearing around 1080nm. The specific meanings of the mathematical symbols are: nm: nanometer, V: volt, A/W: ampere/watt, nA: nanoampere.

进一步地,步骤1中所述单晶硅衬底既可以是n型也可以是p型,厚度为5μm-500μm(微米),半导体晶片的晶向、电阻率和大小不限;单晶硅衬底表面平整,表面平整度即材料表面最高点和最低点的差值小于或等于10μm。Furthermore, the single crystal silicon substrate described in step 1 can be either n-type or p-type, with a thickness of 5μm-500μm (micrometers), and the crystal orientation, resistivity and size of the semiconductor wafer are not limited; the surface of the single crystal silicon substrate is flat, and the surface flatness, that is, the difference between the highest point and the lowest point on the material surface is less than or equal to 10μm.

进一步地,步骤1中的预处理可以选择但不限于以下流程:(a)将单晶硅片切割成一定尺寸的小块;(b)通过RCA清洗法对单晶硅进行清洗;(c)通过镀膜工艺或薄膜生长工艺在硅表面沉积一层一定厚度的含有掺杂物质的薄膜。Furthermore, the pretreatment in step 1 may be selected from but not limited to the following processes: (a) cutting the single crystal silicon wafer into small pieces of a certain size; (b) cleaning the single crystal silicon by RCA cleaning method; (c) depositing a thin film containing doped substances of a certain thickness on the silicon surface by coating process or thin film growth process.

进一步地,步骤2中所述的超快脉冲激光辐照制备过饱和掺杂黑硅层的具体步骤如下:Furthermore, the specific steps of preparing the supersaturated doped black silicon layer by ultrafast pulse laser irradiation described in step 2 are as follows:

(1)将清洗过的单晶硅固定在真空腔内的三维平移台上,在平移台的驱动下,样品在垂直于入射激光的平面上作二维运动。通过三维平移台的参数设置选择合适的移动范围和移动速度,配合快门的开关实现不同图案和结构的制备;(1) The cleaned single crystal silicon is fixed on a three-dimensional translation stage in a vacuum chamber. Driven by the translation stage, the sample moves two-dimensionally on a plane perpendicular to the incident laser. The appropriate moving range and moving speed are selected by setting the parameters of the three-dimensional translation stage, and the shutter is switched on and off to achieve the preparation of different patterns and structures;

(2)抽真空,真空度为100-10-5Pa,然后,充入小于1个标准大气压的某种气体,如六氟化硫、氮气等,或抽至真空状态;(2) Evacuate the chamber to a vacuum degree of 10 0 -10 -5 Pa, then fill it with a gas with a pressure less than 1 standard atmosphere, such as sulfur hexafluoride, nitrogen, etc., or evacuate it to a vacuum state;

(3)控制样品台的运动:通过控制移动速度和移动范围来控制超快脉冲激光过饱和掺杂和改性的面积和扫描速度,即在垂直于入射激光方向的平面上作二维运动;通过一个格兰-泰勒棱镜和一个半波片调节辐照到单晶硅表面激光的偏振方向和功率大小,使辐照在单晶硅表面接的激光通量为0.01kJ/m2-100kJ/m2,单位面积上接收到的脉冲数为1-5000个,超快脉冲激光的脉宽为5fs-100ns,由此来控制表面改性强度和掺杂浓度;既可以逐行扫描加工大面积的过饱和掺杂层,也可以设定不同扫描图案和路径以及与快门开关相配合来制备微区过饱和掺杂层和不同图案的过饱和掺杂层;(3) Control the movement of the sample stage: Control the area and scanning speed of the ultrafast pulse laser supersaturation doping and modification by controlling the moving speed and moving range, that is, make a two-dimensional movement on a plane perpendicular to the incident laser direction; adjust the polarization direction and power of the laser irradiated to the single crystal silicon surface through a Glan-Taylor prism and a half-wave plate, so that the laser flux irradiated to the single crystal silicon surface is 0.01kJ/ m2-100kJ / m2 , the number of pulses received per unit area is 1-5000, and the pulse width of the ultrafast pulse laser is 5fs-100ns, thereby controlling the surface modification intensity and doping concentration; it can not only scan and process a large area of supersaturated doped layer line by line, but also set different scanning patterns and paths and cooperate with the shutter switch to prepare micro-area supersaturated doped layers and supersaturated doped layers of different patterns;

(4)扫描结束后,抽出真空腔内的气体,再充入氮气至一个标准大气压,打开真空腔盖,取出样品硅片,检测加工过的区域(即黑硅层)呈黑色或深灰色;经过上述步骤处理的单晶硅材料表面形成了准周期排列的微纳结构,并掺入了大量的杂质元素。(4) After the scan is completed, the gas in the vacuum chamber is evacuated and then filled with nitrogen to a standard atmospheric pressure. The vacuum chamber cover is opened, and the sample silicon wafer is taken out. The processed area (i.e., the black silicon layer) is detected to be black or dark gray. The surface of the single crystal silicon material processed by the above steps forms a quasi-periodic micro-nano structure and is doped with a large amount of impurity elements.

优选地,步骤3所述的退火的方法可以选择但不限于:快速热退火,管式炉退火,超快脉冲激光退火,飞秒激光退火等方法中的其中一种。Preferably, the annealing method described in step 3 can be selected from but not limited to: rapid thermal annealing, tube furnace annealing, ultrafast pulse laser annealing, femtosecond laser annealing and the like.

进一步地,步骤4所述钝化层的制备方法包括电阻热蒸发法、磁控溅射法、电子束蒸发法、脉冲激光沉积法、化学气相沉积法、异质外延法生长法等;钝化材料是Al2O3、SiNx、Si2O3、a-Si:H、磷硅玻璃、聚酰亚胺等钝化材料中的一种或其组合。制备方式可以是通过光刻图案后制备钝化层,也可以通过金属掩模版掩模后制备钝化层。Furthermore, the preparation method of the passivation layer in step 4 includes resistance thermal evaporation, magnetron sputtering, electron beam evaporation , pulsed laser deposition, chemical vapor deposition, heteroepitaxial growth, etc.; the passivation material is one or a combination of passivation materials such as Al2O3 , SiNx , Si2O3 , a-Si:H, phosphosilicate glass, polyimide, etc. The preparation method can be to prepare the passivation layer after photolithography patterning, or to prepare the passivation layer after metal mask masking.

进一步地,步骤5所述黑硅和硅区域的接触电极的制备方法为电阻热蒸发法、磁控溅射法、电子束蒸发法或脉冲激光沉积法;电极材料是铝、金、银、铬、镍、钛或铂中的一种或其组合;电极形状可制备为矩形、环状、圆形、椭圆形、或其他不规则图形。Furthermore, the contact electrodes of the black silicon and silicon regions in step 5 are prepared by resistance thermal evaporation, magnetron sputtering, electron beam evaporation or pulsed laser deposition; the electrode material is one or a combination of aluminum, gold, silver, chromium, nickel, titanium or platinum; the electrode shape can be prepared into a rectangular, annular, circular, elliptical, or other irregular shapes.

有益效果Beneficial Effects

与现有技术相比,本发明具有如下优点:Compared with the prior art, the present invention has the following advantages:

1.本发明所制备的横向结硅基光电探测器具有更加稳定的横向pn结或异质结,与垂直结构硅基光电探测器相比,降低了其暗电流,提高了器件的稳定性。1. The lateral junction silicon-based photodetector prepared by the present invention has a more stable lateral pn junction or heterojunction, and compared with the vertical structure silicon-based photodetector, it reduces its dark current and improves the stability of the device.

2.本发明通过在超快脉冲激光辐照后同时在正面的黑硅与硅材料区域镀正负电极,与传统黑硅光电探测器在正反面镀正负电极或刻蚀台面后镀电极的方法相比,本发明既保证了器件的稳定性,降低了器件的漏电噪声,同时能简化制备流程;2. The present invention simultaneously plates positive and negative electrodes on the black silicon and silicon material areas on the front side after ultrafast pulse laser irradiation. Compared with the conventional method of plating positive and negative electrodes on the front and back sides of black silicon photodetectors or etching the table top before plating electrodes, the present invention not only ensures the stability of the device, reduces the leakage noise of the device, but also simplifies the preparation process;

3.本发明所制备的横向结硅基光电探测器在-5V偏压下,在640--1170nm波段范围内均的外量子效率均超过了100%,实现低偏压下宽光谱高增益的特性;此外,本发明所制备的横向结硅基光电探测器在-5V偏压下的暗电流为783nA,克服了飞秒激光过饱和掺杂及改性后光电探测器暗电流难以抑制的缺点。3. The external quantum efficiency of the lateral junction silicon-based photodetector prepared by the present invention exceeds 100% in the 640-1170nm band under a bias of -5V, achieving the characteristics of wide spectrum and high gain under low bias; in addition, the dark current of the lateral junction silicon-based photodetector prepared by the present invention is 783nA under a bias of -5V, overcoming the shortcomings of femtosecond laser oversaturation doping and the difficulty in suppressing the dark current of the modified photodetector.

4.本发明采用的制备流程均为CMOS兼容工艺,具有与现有CMOS、CCD等半导体工艺相兼容的优势。4. The preparation processes adopted by the present invention are all CMOS compatible processes, which have the advantage of being compatible with existing semiconductor processes such as CMOS and CCD.

5.本发明具有结构简单,工艺简单,原材料易获取,易加工和易保存等优点。5. The present invention has the advantages of simple structure, simple process, easy acquisition of raw materials, easy processing and easy storage.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

附图1是本发明提供的横向结硅基光电探测的制备方法流程示意图。FIG1 is a schematic flow chart of a method for preparing a lateral junction silicon-based photoelectric detector provided by the present invention.

附图2是本发明提供的横向结硅基光电探测的剖面结构图。FIG2 is a cross-sectional structural diagram of the lateral junction silicon-based photoelectric detection provided by the present invention.

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结构或部件或具体参数。The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. In addition, the scope of protection of the present invention should not be limited to the following specific structures or components or specific parameters.

本发明利用超快脉冲激光改性后的在黑硅与未加工过的硅之间形成的横向界面,通过后继钝化、金属电极制备等工艺,利用黑硅与硅的横向界面处载流子种类以及浓度的不同,形成横向pn结或n+-i结异质结构,以此形成横向结硅基光电探测器。其中,黑硅层表面具有准周期排列的微锥结构,且表面具有过饱和掺杂的杂质元素,经过后续退火处理激活黑硅掺杂层中的杂质元素,使其在宽谱段范围内(0.25μm-2.5μm)均有大于80%的光吸收率,这极大提高了半导体硅材料的吸收率并拓展了其光谱吸收范围。该横向结硅基光电探测器工作在反偏电压下,吸收光子产生光生电子-空穴对,并在电场的作用下横向迁移向两边的电极,被电极收集后形成横向光电流,从而实现了光响应和探测。The present invention utilizes the lateral interface formed between black silicon and unprocessed silicon after ultrafast pulse laser modification, and through subsequent passivation, metal electrode preparation and other processes, utilizes the difference in carrier types and concentrations at the lateral interface between black silicon and silicon to form a lateral pn junction or n + -i junction heterostructure, thereby forming a lateral junction silicon-based photodetector. Among them, the surface of the black silicon layer has a quasi-periodic arrangement of micro-cone structures, and the surface has supersaturated doped impurity elements. After subsequent annealing treatment, the impurity elements in the black silicon doping layer are activated, so that it has a light absorption rate greater than 80% in a wide spectrum range (0.25μm-2.5μm), which greatly improves the absorption rate of semiconductor silicon materials and expands its spectral absorption range. The lateral junction silicon-based photodetector works under reverse bias voltage, absorbs photons to generate photogenerated electron-hole pairs, and migrates laterally to the electrodes on both sides under the action of the electric field, and is collected by the electrodes to form a lateral photocurrent, thereby realizing light response and detection.

为使本发明的目的、技术方案和优点更加清楚明白,下面结合附图,对本发明的横向结硅基光电探测器的制备方法进一步说明,包括如下具体步骤:In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the preparation method of the lateral junction silicon-based photodetector of the present invention is further described below in conjunction with the accompanying drawings, including the following specific steps:

附图1是本发明提供的一种横向结硅基光电探测器的剖面结构图,其中,1-1是单晶硅基底,1-2是飞秒激光过饱和掺杂后的黑硅层,1-3是表面钝化层,1-4分别为黑硅和硅的接触电极。Figure 1 is a cross-sectional structural diagram of a lateral junction silicon-based photodetector provided by the present invention, wherein 1-1 is a single crystal silicon substrate, 1-2 is a black silicon layer after femtosecond laser supersaturation doping, 1-3 is a surface passivation layer, and 1-4 are contact electrodes of black silicon and silicon, respectively.

附图2是本发明提供的横向结硅基光电探测器的制备方法流程示意图。FIG2 is a schematic flow chart of a method for preparing a lateral junction silicon-based photodetector provided by the present invention.

结合并参阅附图2,说明本发明提供的更详细的横向结硅基光电探测器的制备方法,其包括如下步骤:In conjunction with and referring to FIG. 2 , a more detailed method for preparing a lateral junction silicon-based photodetector provided by the present invention is described, which comprises the following steps:

步骤1:选取一表面洁净平整的单晶硅衬底;Step 1: Select a single crystal silicon substrate with a clean and flat surface;

步骤2:对所选取的单晶硅片进行预处理,包括但不限于切片、RCA清洗、在硅表面镀含有待掺杂元素的薄膜;Step 2: pre-processing the selected single crystal silicon wafer, including but not limited to slicing, RCA cleaning, and coating a thin film containing the element to be doped on the silicon surface;

步骤3:将处理过的单晶硅放入真空腔中并将其固定在样品架上,使入射激光垂直照到样品表面;Step 3: Place the processed single crystal silicon into a vacuum chamber and fix it on a sample holder so that the incident laser is vertically irradiated onto the sample surface;

步骤4:抽真空至100-10-5Pa,根据掺杂元素充入低于1个大气压的特定气体或保持真空;Step 4: Evacuate to 10 0 -10 -5 Pa, fill with specific gas below 1 atmosphere pressure or maintain vacuum according to the doping elements;

步骤5:通过脉冲激光在特定压强和气氛中辐照单晶硅表面特定区域制备表面微纳结构和过饱和掺杂层,样品在三维平移台的驱动下作二维平面扫描运动,通过控制扫描速度逐行扫描,可以加工大面积的黑硅层。Step 5: Surface micro-nano structures and supersaturated doping layers are prepared by irradiating specific areas of the single crystal silicon surface with pulsed laser in a specific pressure and atmosphere. The sample is driven by a three-dimensional translation stage to perform two-dimensional plane scanning motion. By controlling the scanning speed and scanning line by line, a large area of black silicon layer can be processed.

步骤6:加工完成后,抽走加工腔内的气体,再充入氮气至一个标准大气压,打开腔盖,取出样品,肉眼观察可见加工过的区域颜色为黑色或深灰色,经过上述步骤处理过的硅材料表面形成了准周期排列的微纳结构,并掺入了大量的杂质元素,由此获得了黑硅表面;Step 6: After the processing is completed, the gas in the processing chamber is evacuated, and nitrogen is then filled to a standard atmospheric pressure. The chamber cover is opened, and the sample is taken out. The processed area is black or dark gray when observed with the naked eye. The surface of the silicon material treated by the above steps forms a quasi-periodic arrangement of micro-nano structures and is doped with a large amount of impurity elements, thereby obtaining a black silicon surface;

步骤7:选用合适的退火方法对制备好的黑硅材料做进一步处理,如快速热退火,管式炉退火,纳秒激光熔融退火或飞秒激光退火等,调节好退火温度与退火时间等参数,以激活黑硅层中的掺杂元素,同时去除缺陷,修复受损晶格;Step 7: Select a suitable annealing method to further process the prepared black silicon material, such as rapid thermal annealing, tube furnace annealing, nanosecond laser melting annealing or femtosecond laser annealing, etc., and adjust the annealing temperature and annealing time and other parameters to activate the doping elements in the black silicon layer, remove defects, and repair damaged lattices;

步骤8:在黑硅和硅与电极接触以外的区域制备钝化层,并通过光刻掩模工艺或物理掩模工艺,保留出需要与电极接触的区域,钝化层的制备方法可以为电阻热蒸发、磁控溅射、电子束蒸发、化学气相沉积、脉冲激光沉积、异质外延法生长法等;钝化材料可以是Al2O3、SiNx、Si2O3、a-Si:H、磷硅玻璃、聚酰亚胺等中的一种或其组合。Step 8: Prepare a passivation layer in the area other than the black silicon and silicon contacting the electrode, and reserve the area that needs to contact the electrode through a photolithography mask process or a physical mask process. The preparation method of the passivation layer can be resistance thermal evaporation, magnetron sputtering, electron beam evaporation, chemical vapor deposition, pulsed laser deposition, heteroepitaxial growth method, etc.; the passivation material can be one of Al2O3 , SiNx , Si2O3 , a-Si:H, phosphosilicate glass, polyimide, etc. , or a combination thereof.

步骤9:通过光刻掩模工艺或物理掩模工艺,在步骤8过程中保留出的电极接触区域,分别制备黑硅的接触电极和硅的接触电极,可以同时制备黑硅和硅的金属接触电极,也可以分别制备,金属电极的制备方法可以为电阻热蒸发、磁控溅射、电子束蒸发、脉冲激光沉积等;电极材料可以是铝、金、银、铬、镍、钛或铂中的一种或其组合;电极形状可以为矩形、环状、圆形、椭圆形、或其他不规则图形。Step 9: Through a photolithography mask process or a physical mask process, in the electrode contact area retained in step 8, a black silicon contact electrode and a silicon contact electrode are prepared respectively. The metal contact electrodes of black silicon and silicon can be prepared at the same time or separately. The preparation method of the metal electrode can be resistive thermal evaporation, magnetron sputtering, electron beam evaporation, pulsed laser deposition, etc.; the electrode material can be one of aluminum, gold, silver, chromium, nickel, titanium or platinum or a combination thereof; the electrode shape can be rectangular, annular, circular, elliptical, or other irregular shapes.

其中,步骤1中所述单晶硅衬底既可以是n型也可以是p型,厚度为100μm-500μm(微米),半导体晶片的晶向、电阻率和大小不限;单晶硅衬底要求表面平整,表面平整度即材料表面最高点和最低点的差值小于或等于10μm。Among them, the single crystal silicon substrate described in step 1 can be either n-type or p-type, with a thickness of 100μm-500μm (micrometers), and the crystal orientation, resistivity and size of the semiconductor wafer are not limited; the single crystal silicon substrate requires a flat surface, and the surface flatness, that is, the difference between the highest point and the lowest point on the material surface is less than or equal to 10μm.

进一步的,上述步骤4中的气体可以是氮气、氢气、六氟化硫、氧气、氦气、氩气、四氟化碳等其中一种或其组合,也可以是真空环境,压强可以为10-5Pa至1个大气压。Furthermore, the gas in step 4 can be one of nitrogen, hydrogen, sulfur hexafluoride, oxygen, helium, argon, carbon tetrafluoride, etc. or a combination thereof, or can be a vacuum environment, and the pressure can be from 10 -5 Pa to 1 atmosphere.

进一步的,上述步骤5中的激光参数和辐照条件可以有多种选择,如纳秒激光、皮秒激光、飞秒激光、阿秒激光,本案例中使用的激光参数为中心波长为800nm,脉宽为120fs的飞秒激光;并可通过一个格兰-泰勒棱镜和一个半波片的组合连续调节辐照到单晶硅表面的激光偏振方向和功率大小,使飞秒激光通量为0.8kJ/m2-8kJ/m2,通过步进电机的调节可以使单位面积上接收到的脉冲数为1-500个;Furthermore, there are many options for the laser parameters and irradiation conditions in the above step 5, such as nanosecond laser, picosecond laser, femtosecond laser, attosecond laser. The laser parameters used in this case are femtosecond laser with a central wavelength of 800nm and a pulse width of 120fs. The polarization direction and power of the laser irradiated to the surface of the single crystal silicon can be continuously adjusted through a combination of a Glan-Taylor prism and a half-wave plate, so that the femtosecond laser flux is 0.8kJ/ m2-8kJ / m2 . The number of pulses received per unit area can be 1-500 by adjusting the stepper motor.

所制作的横向结硅基光电探测器在-5V偏压下的的暗电流可降至783nA,远小于传统垂直结构的黑硅光电探测器;同时,器件的响应波段为500nm-1400nm,在-5V偏压下的峰值响应度为3.23A/W,其中峰值波长出现在1080nm附近。其中各数学符号的具体含义为:nm:纳米,V:伏特,A/W:安培/瓦特,nA:纳安培。The dark current of the fabricated lateral junction silicon-based photodetector can be reduced to 783nA under a bias voltage of -5V, which is much smaller than the traditional vertical structure black silicon photodetector; at the same time, the device has a response band of 500nm-1400nm, and a peak responsivity of 3.23A/W under a bias voltage of -5V, with a peak wavelength of around 1080nm. The specific meanings of the mathematical symbols are: nm: nanometer, V: volt, A/W: ampere/watt, nA: nanoampere.

综上,使用上述制备方法制备的横向结硅基光电探测器包括-制备过饱和掺杂黑硅表面以及形成黑硅-硅的横向界面;-对制备好的黑硅材料做退火处理;-钝化以保护材料表面;-制作黑硅和硅与金属的接触电极。至此,横向结硅基光电探测器件制备完成。In summary, the lateral junction silicon-based photodetector prepared using the above preparation method includes: preparing a supersaturated doped black silicon surface and forming a black silicon-silicon lateral interface; annealing the prepared black silicon material; passivation to protect the material surface; and making contact electrodes between black silicon and silicon and metal. At this point, the lateral junction silicon-based photodetector device is completed.

实施示例1:Implementation Example 1:

横向结硅基光电探测器的制备方法,包括如下步骤:A method for preparing a lateral junction silicon-based photodetector comprises the following steps:

步骤1:选取2英寸n型(100)区熔单晶硅片,其电阻率为3000-5000Ω·cm,厚度为430±10μm;Step 1: Select a 2-inch n-type (100) zone-melting single crystal silicon wafer with a resistivity of 3000-5000Ω·cm and a thickness of 430±10μm;

步骤2:对所选取的单晶硅片进行预处理,具体步骤为:(a)通过标准RCA清洗法对单晶硅片进行清洗;(b)将单晶硅片切割成小块单元。Step 2: Pre-treat the selected single crystal silicon wafer, the specific steps are: (a) clean the single crystal silicon wafer by a standard RCA cleaning method; (b) cut the single crystal silicon wafer into small units.

步骤3:将清洗过的单晶硅放入真空腔中并将其固定在样品架上,使入射激光垂直照到样品表面,样品架与一个三维移动台相连,在平移台的驱动下,样品可以在垂直于入射激光的平面上作二维运动;Step 3: Place the cleaned single crystal silicon into a vacuum chamber and fix it on a sample holder so that the incident laser is perpendicular to the sample surface. The sample holder is connected to a three-dimensional moving stage. Driven by the translation stage, the sample can move two-dimensionally on a plane perpendicular to the incident laser.

步骤4:抽真空至10-5Pa,再充入0.67bar六氟化硫气体,最后在0.67bar的六氟化硫气氛下加工;Step 4: Evacuate to 10 -5 Pa, then fill with 0.67 bar sulfur hexafluoride gas, and finally process in a 0.67 bar sulfur hexafluoride atmosphere;

步骤5:入射飞秒激光的中心波长为800nm,脉宽为120fs,辐照到硅片表面的激光通量为1.0kJ/m2,样品在二维平移台的驱动下作二维扫描运动,逐行扫描,扫描一片面积为1cm×1cm的方形区域,扫描行间距为50μm,扫描速度为1mm/s;Step 5: The central wavelength of the incident femtosecond laser is 800nm, the pulse width is 120fs, and the laser flux irradiated to the silicon wafer surface is 1.0kJ/ m2 . The sample is driven by a two-dimensional translation stage to perform a two-dimensional scanning motion, scanning line by line, scanning a square area of 1cm×1cm, with a scanning line spacing of 50μm and a scanning speed of 1mm/s;

步骤6:加工完成后,将腔内抽真空至10-5Pa,再充入氮气至大气压,打开腔盖,取出样品,肉眼观察加工过的区域颜色为黑色或深灰色,即硫元素过饱和掺杂的黑硅层,掺杂层的厚度约为100nm,而未加工的区域仍保持单晶硅的平滑抛光特性;Step 6: After the processing is completed, the chamber is evacuated to 10 -5 Pa, and then filled with nitrogen to atmospheric pressure. The chamber cover is opened and the sample is taken out. The processed area is observed by naked eyes to be black or dark gray, that is, a black silicon layer supersaturated with sulfur. The thickness of the doped layer is about 100nm, while the unprocessed area still maintains the smooth polishing characteristics of single crystal silicon;

步骤7:用快速热退火方法处理飞秒激光辐照过的样品,第一步升温,首先在10s内升温至240℃,再在5s内升温至600℃;第二步恒温,温度保持为600℃至600s;第三步自然降温至100℃以下,取出样品;Step 7: Treat the sample irradiated by femtosecond laser with a rapid thermal annealing method. The first step is to increase the temperature, first to 240°C within 10s, and then to 600°C within 5s; the second step is to maintain a constant temperature, and the temperature is maintained at 600°C for 600s; the third step is to naturally cool down to below 100°C and take out the sample;

步骤8:采用等离子体增强化学气相沉积(PECVD)法在黑硅表面制备SiO2钝化层,钝化层厚度约为1μm;随后通过紫外光刻技术,使用光刻胶保护材料表面,仅仅暴露出部分需要电极接触的黑硅和硅区域;随后将样品放入稀释的氢氟酸中清洗5秒,以去除未被光刻胶覆盖区域的SiO2钝化层;随后通过丙酮清洗去除光刻胶。Step 8: Use plasma enhanced chemical vapor deposition (PECVD) to prepare a SiO2 passivation layer on the black silicon surface, and the thickness of the passivation layer is about 1μm; then use ultraviolet photolithography technology to use photoresist to protect the material surface, exposing only some black silicon and silicon areas that need electrode contact; then place the sample in diluted hydrofluoric acid for cleaning for 5 seconds to remove the SiO2 passivation layer in the area not covered by the photoresist; then remove the photoresist by cleaning with acetone.

步骤9:采用电阻热蒸发的方法在黑硅和硅表面区域制备铝金属电极作为正负接触电极,具体方法如下:通过旋涂光刻胶和紫外光刻技术对材料表面进行掩模,掩膜后未被光刻胶覆盖的镂空区域与黑硅以及硅上需要镀电极的区域相对应,将光刻掩模后的样品固定在蒸发镀膜机的钼舟正上方,在钼舟中放入适量的铝颗粒,抽真空至3×10-3Pa后蒸发蒸镀铝电极;随后通过丙酮清洗去除光刻胶,至此完成器件制作。Step 9: Use the method of resistive thermal evaporation to prepare aluminum metal electrodes as positive and negative contact electrodes on the black silicon and silicon surface areas. The specific method is as follows: Mask the material surface by spin coating photoresist and ultraviolet photolithography technology. The hollow areas not covered by the photoresist after masking correspond to the black silicon and the areas on the silicon that need to be plated with electrodes. Fix the sample after photolithography masking directly above the molybdenum boat of the evaporation coating machine, put an appropriate amount of aluminum particles in the molybdenum boat, evacuate to 3× 10-3 Pa, and then evaporate and deposit aluminum electrodes; then remove the photoresist by acetone cleaning, and the device manufacturing is completed.

经过以上步骤制备的横向结硅基光电探测器在-5V偏压下的的暗电流可降至783nA,该横向异质结有效地解决了黑硅光电探测器暗电流难以抑制的缺陷;并在低偏压下实现了高增益和宽谱的特性,器件的响应波段为500nm-1400nm,在-5V偏压下的峰值响应度为3.23A/W,其中峰值波长出现在1080nm附近。有效地提高了器件的信噪比和动态范围。The dark current of the lateral junction silicon-based photodetector prepared through the above steps can be reduced to 783nA under -5V bias. The lateral heterojunction effectively solves the defect that the dark current of the black silicon photodetector is difficult to suppress; and achieves high gain and wide spectrum characteristics under low bias. The response band of the device is 500nm-1400nm, and the peak responsivity under -5V bias is 3.23A/W, where the peak wavelength appears near 1080nm. The signal-to-noise ratio and dynamic range of the device are effectively improved.

以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。本领域普通的技术人员可以理解,在不背离所附权利要求定义的本发明的精神和范围的情况下,可以在形式和细节中做出各种各样的修改。The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. It can be understood by a person of ordinary skill in the art that various modifications can be made in form and details without departing from the spirit and scope of the present invention defined in the appended claims.

Claims (7)

1. A preparation method of a lateral junction silicon-based photoelectric detector with low dark current is characterized by comprising the following steps:
step 1: selecting a monocrystalline silicon wafer, and preprocessing the selected silicon wafer;
step 2: selecting pretreated monocrystalline silicon, irradiating a specific area of the surface of the monocrystalline silicon in a specific atmosphere or vacuum by pulse laser, and preparing a supersaturated doped layer to obtain a black silicon surface;
Step 3: annealing the prepared black silicon material, activating impurity atoms in the supersaturated doped black silicon layer, repairing crystal lattices, and removing structural defects;
Step 4: plating a passivation layer on the black silicon surface except for the electrode contact area to protect the black silicon surface and isolate air pollution and oxidation;
Step 5: plating contact electrodes on the electrode contact areas of the silicon and the black silicon respectively; thus, the preparation of the transverse silicon-based photoelectric detector is completed;
The specific atmosphere is one or a combination of nitrogen, hydrogen, sulfur hexafluoride, oxygen, helium, argon and carbon tetrafluoride; the specific region is a region having a size of 1 μm (micrometer) -1cm (centimeter) and a shape that is one of square, rectangle, circle, ellipse, triangle, or a combination thereof.
2. The method of fabricating a lateral junction silicon-based photodetector device of claim 1, wherein the single crystal silicon selected in step 1 is either n-type or p-type and has a thickness of 5 μm to 500 μm (micrometers).
3. The method of fabricating a lateral junction silicon-based photodetector of claim 1, wherein the pretreatment process in step 1 comprises: (1) cutting a monocrystalline silicon piece into small pieces of a certain size; (2) cleaning the monocrystalline silicon by an RCA cleaning method; (3) And depositing a layer of film containing doping substances on the surface of the silicon by a film plating process or a film growing process.
4. The method for preparing the lateral junction silicon-based photoelectric detector according to claim 1, wherein the specific steps for preparing the supersaturated doped black silicon surface by pulse laser irradiation in the step 2 are as follows:
(1) Fixing the pretreated monocrystalline silicon material on a three-dimensional translation stage in a vacuum cavity, driving the translation stage to make a sample perform two-dimensional motion on a plane vertical to incident laser, and selecting a proper moving range and a proper moving speed through parameter setting of the three-dimensional translation stage so as to control the area and the scanning speed of a supersaturated doped and modified area of pulse laser and realize preparation of different patterns and structures by matching with a shutter;
(2) Vacuumizing, wherein the vacuum degree is 10 0-10-5 Pa, and then filling a specific atmosphere with the pressure less than 1 standard atmosphere or maintaining the vacuum state;
(3) Scanning pulse laser: the sample is subjected to two-dimensional motion on a plane perpendicular to the direction of incident laser by controlling the translation stage; the pulse width of the incident pulse laser is 5fs-100ns, the polarization direction and the power of the laser irradiated to the surface of the monocrystalline silicon are regulated through a gram-Taylor prism and a half-wave plate, so that the laser flux irradiated to the surface of the monocrystalline silicon is 0.01kJ/m 2-100kJ/m2, and the number of pulses received per unit area is 1-5000, thereby controlling the surface modification strength and the doping concentration; the method can scan and process a large-area supersaturated doped layer line by line, and can set different scanning patterns and paths or be matched with a shutter switch to prepare a micro-area supersaturated doped layer and supersaturated doped layers with different patterns;
(4) After the scanning is finished, the gas in the vacuum cavity is pumped out, then nitrogen is filled to a standard atmospheric pressure, the vacuum cavity cover can be opened, the sample silicon wafer is taken out, and the processed area, namely the black silicon layer, is detected to be black or dark gray; the surface of the silicon material treated by the steps forms a micro-nano structure with quasi-periodic arrangement, and a large amount of impurity elements are doped.
5. The method for manufacturing a lateral junction silicon-based photodetector according to claim 1, wherein the annealing method in step 3 is one of rapid thermal annealing, tube furnace annealing, ultra-rapid pulse laser annealing, femtosecond laser annealing, or a combination thereof.
6. The method for manufacturing a lateral junction silicon-based photodetector according to claim 1, wherein the method for manufacturing a passivation layer in step 4 comprises a resistive thermal evaporation method, a magnetron sputtering method, an electron beam evaporation method, a pulse laser deposition method, a chemical vapor deposition method, a heteroepitaxial growth method; the passivation material is Al 2O3、SiNx、Si2O3, a-Si: H. one or a combination of phosphosilicate glass and polyimide, the mask mode can be to prepare the passivation layer after photoetching patterns, remove the passivation layer of the electrode contact area after preparing the passivation layer by photoetching, and also can prepare the passivation layer after masking through a mask plate.
7. The method for manufacturing a lateral junction silicon-based photodetector according to claim 1, wherein the method for manufacturing a contact electrode of the electrode contact region of the black silicon and the silicon in step 5 is a resistive thermal evaporation method, a magnetron sputtering method, an electron beam evaporation method or a pulsed laser deposition method; the electrode material is one or a combination of aluminum, gold, silver, chromium, nickel, titanium or platinum; the electrode shape is prepared into rectangle, ring, round and oval; the mask mode can be to prepare the metal electrode after photoetching patterns, or to prepare the metal electrode after physical mask masking.
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