WO2022126933A1 - 波长选择性响应的光电探测器的制备方法 - Google Patents

波长选择性响应的光电探测器的制备方法 Download PDF

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WO2022126933A1
WO2022126933A1 PCT/CN2021/084961 CN2021084961W WO2022126933A1 WO 2022126933 A1 WO2022126933 A1 WO 2022126933A1 CN 2021084961 W CN2021084961 W CN 2021084961W WO 2022126933 A1 WO2022126933 A1 WO 2022126933A1
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thin film
layer
film layer
metal thin
nanopore
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吴绍龙
詹纯
王冬唤
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苏州大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of optoelectronic devices, and relates to a preparation method of a photodetector with selective response to photons in the visible-near-infrared band, in particular to a spectrum regulation technology in a narrow band.
  • the transparent conductive layer is a thin film layer with high transmittance to photons in a certain wavelength range and good conductivity.
  • Transparent conductive layers are widely used as front electrodes for optoelectronic devices such as solar cells, photodetectors, light emitting diodes, and photocatalysis.
  • an ideal transparent conductive layer needs to exhibit high transparency (i.e. high light transmittance) and high conductivity (i.e. low sheet resistance) over the widest possible spectral range.
  • metal-doped wide-bandgap semiconductor films such as aluminum-doped zinc oxide and tin-doped indium oxide
  • metal mesh film with high duty cycle or ultra-thin metal films is used.
  • photodetectors used in optical communication, optical sensing, laser ranging, etc. often require pre-filtering devices to achieve selective response signal output for a single target wavelength or narrow-band spectrum.
  • a traditional oxide film system, a metal mesh with a high aperture ratio or an ultra-thin metal film is used as the transparent conductive electrode of the photodetector in the above fields, the photoelectric device will not only respond to the target wavelength, but also respond to interference or noise light waves. Also responsive.
  • an external filter system is essential. This operation not only increases the detection cost of the target optical signal, but also increases the volume of the detection system, which is not conducive to the miniaturization and integrated application of the photoelectric detection system.
  • the present invention solves the problem in the prior art that the photodetector cannot automatically selectively identify incident photons in the visible-near-infrared band and output response signals.
  • the technical solutions adopted are as follows.
  • the preparation method of the photodetector with wavelength selective response includes the following steps.
  • Quartz glass is used as the transparent substrate.
  • UV-ozone treatment is performed on the cleaned transparent substrate.
  • Reactive ion beam etching is performed on the micro/nanosphere self-assembled arrangement, so that the micro/nanosphere self-assembled arrangement becomes a sparse micro/nanosphere array.
  • the nanopore patterned metal thin film layer and the dense metal thin film layer form a Fabry-Perot resonant cavity.
  • the photosensitive semiconductor material layer includes: a single n-type doped semiconductor layer, a single p-type doped semiconductor layer, a p-n junction semiconductor layer, and one of the n-p junction semiconductor layers; the dense metal The thin film layer forms an ohmic contact with the photosensitive semiconductor material layer; when the photosensitive semiconductor material layer is a single n-type doped semiconductor layer or a single p-type doped semiconductor layer, the nanopore patterned metal thin film layer and the photosensitive semiconductor material The layer forms a Schottky contact; when the photosensitive semiconductor material layer is constructed as a p-n junction semiconductor layer or an n-p junction semiconductor layer, the nanopore patterned metal thin film layer forms an ohmic contact with the photosensitive semiconductor material layer.
  • the band range and the central wavelength of the nanopore patterned film can be adjusted.
  • the thickness of the nanopore By optimizing the thickness of the nanopore, the peak of the narrow-band light transmittance of the nanopore patterned film can be adjusted.
  • the nanopore patterned film can be used not only as a device electrode layer with excellent electrical conductivity, but also as a filtering device for incident photons.
  • the photosensitive material layer is a single p-type or n-type semiconductor material layer
  • the nano-hole patterned film also forms a Schottky junction with the photosensitive semiconductor material layer, thereby serving as a working junction of the photodetector.
  • the nanopore patterned metal thin film layer and the dense metal thin film layer form a Fabry-Perot resonant cavity, so that the target photons selectively transmitted through the nanopore patterned metal thin film layer can form an optical resonance in the photosensitive semiconductor material layer.
  • the absorption rate of the photosensitive semiconductor material layer to the target photons is greatly enhanced.
  • Figure 1 Schematic diagram of the structure of a wavelength-selective responsive photodetector.
  • 11 is a transparent substrate
  • 12 is a nano-hole patterned metal film layer
  • 13 is a photosensitive semiconductor material layer
  • 14 is a dense metal film layer
  • 15 is an insulating protective layer
  • 16 is a lead terminal.
  • Figure 2 Schematic diagram of the structure of the triangularly-arranged nanopore patterned metal thin film layer.
  • D is the diameter of the nanopore
  • P is the period of the nanopore
  • t is the thickness of the nanopore
  • Figure 3 Transmission spectrum of the nanopore patterned metal thin film layer deposited on the quartz glass substrate when the diameter of the nanopore changes.
  • 31 corresponds to a nanopore diameter of 280 nm
  • 32 corresponds to a nanopore diameter of 240 nm
  • 33 corresponds to a nanopore diameter of 200 nm
  • 34 corresponds to a nanopore diameter of 120 nm.
  • Figure 4 Transmission spectrum of the nanopore patterned metal thin film layer deposited on the quartz glass substrate when the nanopore period changes.
  • Figure 5 Transmission spectrum of a nanopore patterned metal thin film layer deposited on a silica glass substrate with varying nanopore thickness.
  • 51 corresponds to a nanopore thickness of 140 nm
  • 52 corresponds to a nanopore thickness of 100 nm
  • 53 corresponds to a nanopore thickness of 60 nm.
  • Figure 6 The corresponding transmission spectrum of the nanopore patterned metal thin film layer deposited on the quartz glass substrate with or without the introduction of the semiconductor absorber layer.
  • Embodiment 1 a method for preparing a photodetector with a wavelength selective response, including the following steps.
  • UV-ozone treatment is performed on the cleaned substrate.
  • Reactive ion beam etching is performed on the densely packed polystyrene micro/nanosphere array to reduce the diameter to 30% ⁇ 70% of the original value.
  • the titanium/gold thin films were deposited by electron beam evaporation with thicknesses of 0 ⁇ 5 nm and 50 ⁇ 150 nm, respectively.
  • the n-type semiconductor film and gold form Schottky contact; when the p and n-type semiconductor films are deposited successively, the nanopore patterned gold film and the p type semiconductor thin films to form ohmic contacts.
  • the photodetector with wavelength selective response prepared by the above method is a composite layer structure , and includes a transparent substrate 11, a nano-hole patterned metal film layer 12, and a photosensitive semiconductor material in sequence along the light incident direction.
  • Layer 13 , dense metal thin film layer 14 , insulating protection layer 15 , and two lead terminals 16 respectively drawn from the nanopore patterned metal thin film layer and the dense metal thin film layer.
  • the thickness of the nanopore patterned metal thin film layer is 50-100 nm.
  • the nano-hole pattern is triangularly arranged, the diameter is 100-1000 nm, and the nano-hole area duty ratio is 8%-30%.
  • the nanopore area duty cycle is defined as ⁇ (radius/period) 2 .
  • the material of the nanopore patterned metal thin film layer is any one of gold, silver and aluminum.
  • titanium or chromium with a thickness of 2-5 nm is introduced between the nanopore patterned metal thin film layer and the transparent substrate as an adhesion layer between the nanopore patterned metal thin film layer and the transparent substrate.
  • the insulating protective layer is any one of organic silica gel, polyvinyl fluoride, polyvinyl butyral, and ethylene polyvinyl acetate.
  • the transparent substrate has ultra-high light transmittance (>98%) in the entire visible-near-infrared band, and the periodic nanopore patterned film deposited on the transparent substrate has narrow-band selective transmission characteristics for incident photons.
  • Embodiment 2 Compared with Embodiment 1, a method for preparing a photodetector with wavelength selective response.
  • Replace step 5 with: take the quartz glass covered by the reduced size polystyrene micro/nanosphere array as the substrate, and use electron beam evaporation to deposit a chromium/silver (or chromium/aluminum) thin film with a thickness of 0 ⁇ 5 nm, respectively and 50 ⁇ 150 nm.
  • Replace step 7) with: using the quartz glass covered by the nanopore patterned metal film layer as the base, deposit p-type (or sequentially deposit n-type and p-type) amorphous, microcrystalline silicon, Cu(In,Ga)Se 2 , CuInSe 2 , CuInTe 2 , AgInSe 2 or AgAlTe 2 thin films.
  • the p-type semiconductor film and silver (or aluminum) form Schottky contact; when the n and p-type semiconductor films are deposited successively, the nanohole pattern
  • the silver (or aluminum) thin film forms an ohmic contact with the n-type semiconductor thin film.
  • Embodiment 3 Compared with Embodiment 1, the preparation method of the photodetector with wavelength selective response.
  • the photosensitive semiconductor material layer does not use the quartz glass covered by the nano-hole patterned metal film layer as the base for film deposition, but directly uses the already grown n-type or p-n junction silicon, germanium, gallium arsenide, indium gallium arsenide or phosphorus
  • the indium oxide single wafer is the photosensitive layer.
  • the main process of preparation includes.
  • Step 1) Directly use the front surface of the n-type or p-n junction semiconductor single wafer that has been grown and the nano-hole patterned gold film based on quartz glass [preparation steps refer to Step 1) to Step 6) in Example 1] Tight fit.
  • the transmission spectrum of the quartz glass covered by the nanopore patterned metal thin film layer is shown in Figure 6 (the corresponding nanopore period is 550 nm and the diameter is 280 nm). nm, with a thickness of 100 nm, with light incident perpendicular to the exposed glass surface).
  • Embodiment 4 Compared with Embodiment 3, the main steps of the preparation process of a wavelength selective response photodetector have the following two changes.
  • the second is to replace “directly use the grown n-type (or p-n junction) silicon, germanium, gallium arsenide, indium gallium arsenide or indium phosphide single wafer as the photosensitive layer" with "directly use the already grown p-type (or n-p junction) silicon, germanium, gallium arsenide, indium gallium arsenide or indium phosphide monolithic wafer is the photosensitive layer".

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Abstract

波长选择性响应光电探测器的制备方法，在透明基底（11）上依次设置纳米孔图案化金属薄膜层（12）、光敏半导体材料层（13）、致密金属薄膜层（14）、绝缘保护层（15）、以及分别在纳米孔图案化金属薄膜层（12）和致密金属薄膜层（14）引出两个引线端（16）；纳米孔图案化金属薄膜层（12）与致密金属薄膜层（14）形成法布里-珀罗谐振腔。由于纳米孔为对称的阵列结构，使其对入射光子的偏振角度具有不显著的依赖特性，进而使得光电探测器可实现偏振不敏感的波长选择性响应，法布里-珀罗谐振腔使得目标光子在光敏半导体材料层（13）中光学共振，增强了光敏半导体材料层（13）对目标光子的吸收率。

Description

波长选择性响应的光电探测器的制备方法 技术领域
本发明属于光电器件领域，涉及一种对可见-近红外波段范围内的光子具有选择性响应的光电探测器的制备方法，尤其涉及窄带波段范围内的光谱调控技术。
 背景技术
透明导电层是一种对一定波段范围内的光子具有较高透光率，同时具有良好导电性的薄膜层。透明导电层被广泛用作太阳能电池、光电探测器、发光二极管、光催化等光电子器件的正面电极。通常，理想的透明导电层需要在尽可能宽的光谱范围内呈现高透明性（即透光率高）和高导电率（即方块电阻很小）。目前，被广泛使用的透明导电材料主要有两类，一是金属掺杂的宽禁带半导体薄膜，如掺铝的氧化锌、掺锡的氧化铟；二是高占空比的金属网状薄膜或超薄的金属薄膜。
 技术问题
然而，用于光通信、光传感、激光测距等领域的光电探测器往往需要前置滤光装置，以实现器件针对单个目标波长或窄波段的光谱具有选择性的响应信号输出。若采用传统的氧化物膜系、高占孔比的金属网或超薄的金属薄膜作为上述领域光电探测器的透明导电电极，则光电器件不仅对目标波长会有响应，对干扰或噪声光波也同样具有响应。为了避免噪声光子的干扰，提高信噪比，外置滤光系统是必不可少的。如此操作，既增加了目标光信号的探测成本，还会增加探测系统的体积，不利于光电探测系统的小型化与集成化应用。
 技术解决方案
本发明为解决现有技术中光电探测器不能自动对可见-近红外波段范围内的入射光子进行选择性识别和输出响应信号的问题。采用的技术方案如下。
波长选择性响应的光电探测器的制备方法，包括以下步骤。
1）采用石英玻璃为透明基底。
2）对清洗后的透明基底进行紫外-臭氧处理。
3）在透明基底上进行微/纳米球自组装排列。
4）对微/纳米球自组装排列进行反应离子束刻蚀，使微/纳米球自组装排列变成稀疏微/纳米球阵列。
5）采用电子束蒸镀技术在稀疏微/纳米球阵列表面镀金属薄膜。
6）去除稀疏微/纳米球阵列，得到纳米孔图案化金属薄膜层。
7）在纳米孔图案化金属薄膜层上沉积光敏半导体材料层。
8）在光敏半导体材料层表面蒸镀、溅射或涂覆致密金属薄膜层。
9）分别在纳米孔图案化金属薄膜层和致密金属薄膜层上引出导线，作为器件的两个引线端。
10）涂覆绝缘保护层，将致密金属薄膜层及器件的侧壁完全包覆好，露出两个引线端与未被纳米孔图案化金薄膜覆盖的透明基底的表面。
       优选地，纳米孔图案化金属薄膜层与致密金属薄膜层形成法布里-珀罗谐振腔。
所述的光敏半导体材料层包括：单一的n型掺杂半导体层、单一的p型掺杂半导体层、构筑成p-n结型半导体层、构筑成n-p结型半导体层之一；所述的致密金属薄膜层与光敏半导体材料层形成欧姆接触；当光敏半导体材料层为单一的n型掺杂半导体层或单一的p型掺杂半导体层时，所述的纳米孔图案化金属薄膜层与光敏半导体材料层形成肖特基接触；当光敏半导体材料层为构筑成p-n结型半导体层或构筑成n-p结型半导体层，所述的纳米孔图案化金属薄膜层与光敏半导体材料层形成欧姆接触。
 有益效果
通过调控纳米孔的周期和半径，可以调控透过纳米孔图案化薄膜的波段范围及其中心波长，通过优化纳米孔的厚度，可以调控纳米孔图案化薄膜的窄带光透过率的峰值。纳米孔图案化薄膜既可作为导电性能优异的器件电极层，还可以作为入射光子的滤波装置。当光敏材料层为单一的p型或n型半导体材料层时，纳米孔图案化薄膜还与光敏半导体材料层构成肖特基结，进而作为光电探测器的工作结。由于纳米孔阵列为高对称性的结构，使其对入射光子的偏振角度具有不显著的依赖特性，进而使得光电探测器可实现偏振不敏感的波长选择性响应。此外，纳米孔图案化金属薄膜层与致密金属薄膜层形成法布里-珀罗谐振腔，使得选择性透过纳米孔图案化金属薄膜层的目标光子可在光敏半导体材料层中形成光学共振，从而极大增强了光敏半导体材料层对目标光子的吸收率。
 附图说明
图1：一种波长选择性响应光电探测器的结构示意图。
其中：11透明基底，12为纳米孔图案化金属薄膜层； 13为光敏半导体材料层；14为致密金属薄膜层；15为绝缘保护层；16为引线端。
图2：三角排列的纳米孔图案化金属薄膜层的结构示意图。
其中： D为纳米孔直径； P为纳米孔周期； t为纳米孔的厚度。
图3：纳米孔直径变化时，沉积于石英玻璃上基底的纳米孔图案化金属薄膜层的透射光谱图。
其中：31对应的纳米孔直径为280 nm；32对应的纳米孔直径为240 nm；33对应的纳米孔直径为200 nm；34对应的纳米孔直径为120 nm。
图4：纳米孔周期变化时，沉积于石英玻璃上基底的纳米孔图案化金属薄膜层的透射光谱图。
其中：41对应的纳米孔周期为2000 nm； 42对应的纳米孔周期为1800 nm；43对应的纳米孔周期为1600 nm；44对应的纳米孔周期为1400 nm；45为相同厚度的连续金薄膜。
图5：纳米孔厚度变化时，沉积于石英玻璃上基底的纳米孔图案化金属薄膜层的透射光谱图。
其中：51对应的纳米孔厚度为140 nm；52对应的纳米孔厚度为100 nm；53对应的纳米孔厚度为60 nm。
图6：沉积于石英玻璃上基底的纳米孔图案化金属薄膜层有无引入半导体吸收层时对应的透射光谱图。
其中：61对应为没有引入半导体材料层；62对应为引入了单晶硅薄膜层；63对应为将纳米孔图案化金属薄膜层替换为连续致密金属薄膜。
 本发明的实施方式
为了更清楚地说明本技术方案，下面结合附图及实施例作进一步描述。
实施例一：波长选择性响应的光电探测器的制备方法，包括以下步骤。
1）对透明基底进行RCA标准化学清洗。
2）对清洗后的基底进行紫外-臭氧处理。
3）在石英玻璃基底上对原始直径为200~4000 nm的聚苯乙烯微/纳米球进行自组装排列。
4）对密排好的聚苯乙烯微/纳米球阵列进行反应离子束刻蚀，使其直径减小为原始值的30%~70%。
5）以尺寸减小后的聚苯乙烯微/纳米球阵列覆盖的石英玻璃为基底，采用电子束蒸镀钛/金薄膜，厚度分别为0~5 nm和50~150 nm。
6）去除聚苯乙烯微/纳米球阵列，得到不同尺寸的纳米孔图案化金薄膜层。沉积于石英玻璃基底上的不同尺寸的纳米孔图案化金薄膜及对比样对应的计算所得的透射光谱图分别如图3~5所示，其中：图3中纳米孔的周期为550 nm，厚度为100 nm, 纳米孔直径是变化的；图4中纳米孔的直径为周期的一半，厚度为100 nm, 纳米孔周期是变化的；图5中纳米孔的周期为550 nm，厚度为100 nm, 纳米孔厚度是变化的。
7）以纳米孔图案化金属薄膜层覆盖的石英玻璃为基底，采用共蒸发法或等离子体反应法在纳米孔图案化金属薄膜层上沉积n型（或先后沉积p型和n型）非晶、微晶硅、Cu(In,Ga)Se 2、CuInSe 2、CuInTe 2、AgInSe 2或AgAlTe 2薄膜。通过调控与纳米孔图案化金薄膜直接接触的半导体材料的掺杂浓度，使得n型半导体薄膜与金形成肖特基接触；先后沉积p、n型半导体薄膜时，纳米孔图案化金薄膜与p型半导体薄膜形成欧姆接触。
8）在半导体薄膜层的另一面蒸镀、溅射或涂覆致密金属薄膜层，通过选择金属材质，使得致密金属薄膜层与最后沉积的半导体薄膜形成欧姆接触。
9）分别在纳米孔图案化金属薄膜层和连续致密金属薄膜层上引出导电电线，作为器件的两个引线端。
10）涂覆绝缘保护层，将致密金属薄膜层及器件的侧壁包覆好，只露出两个引线端与未被纳米孔图案化金薄膜覆盖的石英玻璃的表面。
通过上述方法制备得到的波长选择性响应的光电探测器，如图1所述，为复合层式结构 ，沿着光入射方向依次包括透明基底11、纳米孔图案化金属薄膜层12、光敏半导体材料层13、致密金属薄膜层14、绝缘保护层15、以及分别在纳米孔图案化金属薄膜层和致密金属薄膜层引出的两个引线端16。
优选地，所述纳米孔图案化金属薄膜层的厚度为50~100 nm。
优选地，所述纳米孔图案为三角排列，直径为100~1000 nm，纳米孔面积占空比为8%~30%。纳米孔面积占空比定义为π×(半径/周期) 2。
优选地，所述纳米孔图案化金属薄膜层的材质为金、银、铝中任意一种。
       优选地，在所述纳米孔图案化金属薄膜层和所述透明基底之间引入厚度为2~5 nm的钛或铬，作为纳米孔图案化金属薄膜层与透明基底的粘附层。
优选地，绝缘保护层为有机硅胶、聚氟乙烯、聚乙烯醇缩丁醛、乙烯聚醋酸乙烯酯中的任一种。
上述方案中透明基底在整个可见-近红外波段具有超高的光透射率（>98%），沉积于透明基底的周期性纳米孔图案化薄膜对入射光子具有窄带选择性的透过特性。
实施例二：与实施例一相比，波长选择性响应的光电探测器的制备方法。
将步骤5）替换为：以尺寸减小后的聚苯乙烯微/纳米球阵列覆盖的石英玻璃为基底，采用电子束蒸镀铬/银（或铬/铝）薄膜，厚度分别为0~5 nm和50~150 nm。
将步骤7）替换为：以纳米孔图案化金属薄膜层覆盖的石英玻璃为基底，采用共蒸发法或等离子体反应法在纳米孔图案化金属薄膜层上沉积p型（或先后沉积n型和p型）非晶、微晶硅、Cu(In,Ga)Se 2、CuInSe 2、CuInTe 2、AgInSe 2或AgAlTe 2薄膜。通过调控与纳米孔图案化金属薄膜层直接接触的半导体材料的掺杂浓度，使得p型半导体薄膜与银（或铝）形成肖特基接触；先后沉积n、p型半导体薄膜时，纳米孔图案化银（或铝）薄膜与n型半导体薄膜形成欧姆接触。
实施例三：与实施例一相比，波长选择性响应的光电探测器的制备方法。
光敏半导体材料层不以纳米孔图案化金属薄膜层覆盖的石英玻璃为基底进行薄膜沉积，而是直接采用已经生长好的n型或p-n结型硅、锗、砷化镓、铟镓砷或磷化铟单晶片为光敏层。制备的主要过程包括。
1）直接采用已经生长好的n型或p-n结型半导体单晶片的正面与以石英玻璃为基底的纳米孔图案化金薄膜【制备步骤参见与实施例一中的步骤1）至步骤6）】紧密贴合。通过仿真计算得到，透过纳米孔图案化金属薄膜层覆盖的石英玻璃的透射谱如图6所示（此时对应的纳米孔周期为550 nm，直径为280 nm, 厚度为100 nm, 光垂直入射于裸露的玻璃面）。
2）在已经生长好的n型或p-n结型半导体单晶片的背面沉积致密的金属薄膜，通过选择金属材质和对半导体单晶片的背面进行掺杂，使得半导体单晶片的背面与致密的金属薄膜形成欧姆接触。
3）分别在纳米孔图案化金薄膜层和致密金属薄膜层上引出两个导电端，然后涂覆绝缘保护层，将致密金属薄膜层和器件的侧壁完全密封起来，只露出两个引线端与未被纳米孔图案化金薄膜覆盖的石英玻璃的表面。
实施例四：与实施例三相比，一种波长选择性响应光电探测器的制备过程的主要步骤有如下两处改变。
一是将“电子束蒸镀钛/金薄膜”替换为“电子束蒸镀铬/银（或铬/铝）薄膜”。
二是将“直接采用已经生长好的n型（或p-n结型）硅、锗、砷化镓、铟镓砷或磷化铟单晶片为光敏层”替换为“直接采用已经生长好的p型（或n-p结型）硅、锗、砷化镓、铟镓砷或磷化铟单晶片为光敏层”。

Claims (3)

  1. 波长选择性响应的光电探测器的制备方法，其特征在于包括以下步骤：
    1）采用石英玻璃为透明基底；
    2）对清洗后的透明基底进行紫外-臭氧处理；
    3）在透明基底上进行微/纳米球自组装排列；
    4）对微/纳米球自组装排列进行反应离子束刻蚀，使微/纳米球自组装排列变成稀疏微/纳米球阵列；
    5）采用电子束蒸镀技术在稀疏微/纳米球阵列表面镀金属薄膜；
    6）去除稀疏微/纳米球阵列，得到纳米孔图案化金属薄膜层；
    7）在纳米孔图案化金属薄膜层上沉积光敏半导体材料层；
    8）在光敏半导体材料层表面蒸镀、溅射或涂覆致密金属薄膜层；
    9）分别在纳米孔图案化金属薄膜层和致密金属薄膜层上引出导线，作为器件的两个引线端；
    10）涂覆绝缘保护层，将致密金属薄膜层及器件的侧壁完全包覆好，露出两个引线端与未被纳米孔图案化金薄膜覆盖的透明基底的表面。
  2. 根据权利要求1所述的波长选择性响应的光电探测器的制备方法，其特征在于：所述的纳米孔图案化金属薄膜层沉积于透明基底，并呈周期性排列分布；所述的光敏半导体材料层包括：单一的n型掺杂半导体层、单一的p型掺杂半导体层、构筑成p-n结型半导体层、构筑成n-p结型半导体层之一；所述的致密金属薄膜层与光敏半导体材料层形成欧姆接触；当光敏半导体材料层为单一的n型掺杂半导体层或单一的p型掺杂半导体层时，所述的纳米孔图案化金属薄膜层与光敏半导体材料层形成肖特基接触；当光敏半导体材料层为构筑成p-n结型半导体层或构筑成n-p结型半导体层，所述的纳米孔图案化金属薄膜层与光敏半导体材料层形成欧姆接触。
  3. 根据权利要求1所述的波长选择性响应的光电探测器的制备方法，其特征在于：纳米孔图案化金属薄膜层与致密金属薄膜层形成法布里-珀罗谐振腔。
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