CN105655419B - A kind of method for preparing black silicon material - Google Patents
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 69
- 239000010703 silicon Substances 0.000 claims abstract description 69
- 238000010521 absorption reaction Methods 0.000 claims abstract description 22
- 239000011669 selenium Substances 0.000 claims abstract description 22
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 20
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 16
- 238000005530 etching Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000010329 laser etching Methods 0.000 claims abstract description 11
- 239000011241 protective layer Substances 0.000 claims abstract description 11
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052798 chalcogen Inorganic materials 0.000 abstract description 6
- 150000001787 chalcogens Chemical class 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- OHKMFOAYJDGMHW-UHFFFAOYSA-N [Si].[Se] Chemical compound [Si].[Se] OHKMFOAYJDGMHW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 10
- 229910021419 crystalline silicon Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
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- H10F77/703—Surface textures, e.g. pyramid structures of the semiconductor bodies, e.g. textured active layers
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- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/10—Semiconductor bodies
- H10F77/12—Active materials
- H10F77/122—Active materials comprising only Group IV materials
- H10F77/1223—Active materials comprising only Group IV materials characterised by the dopants
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Abstract
本发明属于黑硅材料制备领域，具体涉及一种采用热蒸发和磁控溅射的方式制备硒硅复合膜，并利用飞秒激光刻蚀制备黑硅的方法。本发明通过在现有工艺中硒膜上溅射的一层硅膜作为保护层，减少了飞秒刻蚀过程中硫族元素的挥发，提高了掺杂含量，且可以阻止激光脉冲照射引入的杂质Se向晶粒边界扩散，从而保持其在表面的掺杂浓度，以提高黑硅的吸收率。使用该方法制备的黑硅在400～1100nm波段的吸收率高于95％，在1100～2200nm波段的吸收率高于90％。相比于未覆盖硅保护层，仅热蒸发一层硒膜制备的黑硅材料，本方法制备的黑硅在近红外波段的吸收率有明显提高。
The invention belongs to the field of black silicon material preparation, and in particular relates to a method for preparing a selenium-silicon composite film by means of thermal evaporation and magnetron sputtering, and using femtosecond laser etching to prepare black silicon. The invention uses a layer of silicon film sputtered on the selenium film as a protective layer in the existing process, which reduces the volatilization of chalcogen elements in the femtosecond etching process, increases the doping content, and can prevent the introduction of laser pulse irradiation. The impurity Se diffuses to the grain boundary, so as to maintain its doping concentration on the surface, so as to improve the absorption rate of black silicon. The absorption rate of the black silicon prepared by using the method is higher than 95% in the 400-1100nm wave band, and the absorption rate in the 1100-2200nm wave band is higher than 90%. Compared with the black silicon material prepared by thermally evaporating a layer of selenium film without covering the silicon protective layer, the absorption rate of the black silicon prepared by the method in the near-infrared band is significantly improved.
Description
技术领域technical field
本发明属于黑硅材料制备领域，具体涉及一种采用热蒸发和磁控溅射的方式制备硒硅复合膜，并利用飞秒激光刻蚀制备黑硅的方法。The invention belongs to the field of black silicon material preparation, and in particular relates to a method for preparing a selenium-silicon composite film by means of thermal evaporation and magnetron sputtering, and using femtosecond laser etching to prepare black silicon.
背景技术Background technique
晶体硅材料资源丰富，具有易获取、易提纯、耐高温、易掺杂的等优点，在半导体行业中扮演着重要的角色，在探测器、传感器、太阳能电池制备领域具有广泛的应用。但是，晶体硅的本身固有缺陷而限制其在光电器件的应用。晶体硅为间接带隙材料，室温下禁带宽度为1.124eV，晶体硅吸收的截止波长为1100nm。当入射光波长大于1100nm时，晶体硅的吸收率和响应率会大大降低。因此，在探测这些波段时常采用锗或三五族化合物材料制备探测器。Crystalline silicon is rich in resources and has the advantages of easy acquisition, easy purification, high temperature resistance, and easy doping. It plays an important role in the semiconductor industry and has a wide range of applications in the fields of detectors, sensors, and solar cell preparation. However, the inherent defects of crystalline silicon limit its application in optoelectronic devices. Crystalline silicon is an indirect bandgap material with a forbidden band width of 1.124eV at room temperature and a cut-off wavelength of crystalline silicon absorption of 1100nm. When the incident light wavelength is greater than 1100nm, the absorption rate and responsivity of crystalline silicon will be greatly reduced. Therefore, when detecting these wave bands, germanium or III-V compound materials are often used to prepare detectors.
1998年，哈佛大学Mazur等人在六氟化硫(SF6)气氛下利用飞秒激光照射硅片，在硅片表面形成了微米量级的有序排列的尖锥状森林结构，这种结构大大降低了表面反射率。由于外观呈黑色，这种材料被命名为“黑硅”。黑硅在近紫外—近红外(200-2500nm)波段均有高于90％的吸收率，具有超高的光电导增益，产生的光电流是传统硅材料的几百倍，且与现有硅工艺兼容性良好。因此，黑硅是目前很热门的一种材料，吸引众多国内外研究人员进行研究。In 1998, Mazur et al. of Harvard University irradiated silicon wafers with a femtosecond laser in an atmosphere of sulfur hexafluoride (SF 6 ), and formed a micron-scale orderly arrangement of pointed cone-like forest structures on the surface of silicon wafers. This structure Significantly reduces surface reflectivity. Due to its black appearance, this material is named "black silicon". Black silicon has an absorption rate higher than 90% in the near-ultraviolet-near-infrared (200-2500nm) band, has ultra-high photoconductive gain, and the photocurrent generated is hundreds of times that of traditional silicon materials, and it is different from existing silicon materials Good process compatibility. Therefore, black silicon is a very popular material at present, attracting many domestic and foreign researchers to conduct research.
传统的湿法刻蚀工艺制备的黑硅由于没有进行掺杂，尽管在可见光波段有高于90％的吸收率，在红外波段的吸收率的提高并不明显。利用飞秒激光在SF6背景气体下制备的黑硅在近红外波段的吸收率也可达到90％以上。研究表明，在飞秒激光扫描硅基片过程中能形成硫元素超饱和掺杂硅材料，在硅禁带中形成杂质能带并与硅带尾交叠，使硅禁带宽度降低至0.4eV，延展吸收频段，实现红外波段的高吸收。The black silicon prepared by the traditional wet etching process has no doping, although the absorption rate in the visible light band is higher than 90%, the improvement of the absorption rate in the infrared band is not obvious. The absorption rate of black silicon prepared by using femtosecond laser under SF 6 background gas in the near-infrared band can also reach more than 90%. Studies have shown that during the process of femtosecond laser scanning silicon substrates, supersaturated doped silicon materials with sulfur elements can be formed, and impurity energy bands can be formed in the silicon forbidden band and overlap with the silicon band tail, reducing the silicon forbidden band width to 0.4eV , Extend the absorption frequency band to achieve high absorption in the infrared band.
这种掺杂方式需要在气体环境下进行，而且限制了掺杂元素成分。2006年，Michael A.Sheehy利用粉末旋涂的方式在硅基片上旋涂一层硫族元素粉末作为掺杂源，利用飞秒刻蚀的方式，实现其他硫族元素(硒、碲)的掺杂。研究表明，硒、碲也可在黑硅表面禁带中引入杂质能级，提高红外波段吸收率。2009年，Brain R.Tull改进了硫族元素膜层的制备方法，采用热蒸发的方式在硅基片上蒸镀硫族元素膜层作为掺杂源。相对于粉末旋涂的方式来说，热蒸法制备的薄膜与硅基片接触更好且具有更好的均匀性。但是，在飞秒激光刻蚀的过程中，大量杂质吸收脉冲能量而挥发，影响黑硅的掺杂含量。This doping method needs to be carried out in a gas environment, and the composition of doping elements is limited. In 2006, Michael A. Sheehy spin-coated a layer of chalcogen powder on a silicon substrate as a doping source by means of powder spin coating, and used femtosecond etching to realize the doping of other chalcogen elements (selenium, tellurium). miscellaneous. Studies have shown that selenium and tellurium can also introduce impurity levels in the black silicon surface forbidden band to increase the absorption rate in the infrared band. In 2009, Brain R.Tull improved the preparation method of the chalcogen film layer, and used thermal evaporation to evaporate the chalcogen film layer on the silicon substrate as a doping source. Compared with the method of powder spin coating, the film prepared by thermal evaporation method has better contact with the silicon substrate and has better uniformity. However, during the femtosecond laser etching process, a large number of impurities absorb pulse energy and volatilize, which affects the doping content of black silicon.
发明内容Contents of the invention
针对上述存在问题或不足，本发明在热蒸发镀膜的基础上，利用磁控溅射的方式沉积一层硅膜作为保护层，然后再进行飞秒激光刻蚀硅；保护层可以减少飞秒激光刻蚀过程中杂质元素中的挥发，提高掺杂浓度，进而实现提高红外吸收率的目的。In view of the above problems or deficiencies, on the basis of thermal evaporation coating, the present invention deposits a layer of silicon film as a protective layer by means of magnetron sputtering, and then performs femtosecond laser etching of silicon; the protective layer can reduce the amount of femtosecond laser The volatilization of impurity elements in the etching process increases the doping concentration, thereby achieving the purpose of increasing the infrared absorption rate.
发明公开的技术方案包括：The technical solutions disclosed by the invention include:
一种制备黑硅材料的方法，包括以下步骤：A method for preparing black silicon material, comprising the steps of:
步骤1、对硅衬底进行清洗，以获得清洁的硅衬底备用；Step 1, cleaning the silicon substrate to obtain a clean silicon substrate for use;
步骤2、采用热蒸发的方式在硅衬底表面沉积一层硒膜作为杂质源，硒膜厚度为50～300nm；Step 2. Deposit a layer of selenium film on the surface of the silicon substrate by thermal evaporation as an impurity source, and the thickness of the selenium film is 50-300nm;
步骤3、采用磁控溅射的方式在步骤2制备的硅衬底硒膜上再制备一层硅膜作为硅保护层，硅膜厚度为50～150nm；Step 3, using magnetron sputtering to prepare a layer of silicon film on the silicon substrate selenium film prepared in step 2 as a silicon protective layer, and the thickness of the silicon film is 50-150nm;
步骤4、将步骤3制备的硅衬底在0.2～0.8atm氮气气氛下进行飞秒激光刻蚀，飞秒激光刻蚀时入射光能量密度为1～10kJ/m2，扫描速度为0.5～10mm/s。Step 4. Perform femtosecond laser etching on the silicon substrate prepared in step 3 in a nitrogen atmosphere of 0.2-0.8 atm. During femtosecond laser etching, the incident light energy density is 1-10kJ/m 2 , and the scanning speed is 0.5-10mm /s.
步骤5、将扫描刻蚀后的硅衬底放入氢氟酸中，除去表面的氧化硅层；用去离子水洗净并用氮气吹干，得到黑硅。Step 5, putting the silicon substrate after scan etching into hydrofluoric acid to remove the silicon oxide layer on the surface; washing it with deionized water and blowing it dry with nitrogen to obtain black silicon.
所述硅衬底为N型衬底；The silicon substrate is an N-type substrate;
所述步骤1具体为采用RCA标准清洗法对硅衬底进行清洗；再将已清洗的硅衬底放入丙酮中超声除去表面残留的有机物；最后将硅衬底在去离子水中超声清洁，并在氮气气氛下吹干备用。The step 1 is specifically to clean the silicon substrate using the RCA standard cleaning method; then put the cleaned silicon substrate into acetone and ultrasonically remove the residual organic matter on the surface; finally, ultrasonically clean the silicon substrate in deionized water, and Blow dry under nitrogen atmosphere.
使用上述方法制备的黑硅在400～1100nm波段的吸收率高于95％，在1100～2200nm波段的吸收率高于90％。The absorption rate of the black silicon prepared by the above method is higher than 95% in the 400-1100nm wave band, and the absorption rate in the 1100-2200nm wave band is higher than 90%.
在本发明中，通过在现有工艺基础上引入硅膜作为杂质源保护层，即硒膜上溅射的硅膜作为保护层，可以减少飞秒刻蚀过程中硫族元素的挥发，提高掺杂含量，且可以阻止激光脉冲照射引入的杂质Se向晶粒边界扩散，从而保持其在表面的掺杂浓度，以提高黑硅的吸收率。In the present invention, by introducing a silicon film as an impurity source protective layer on the basis of the existing technology, that is, the silicon film sputtered on the selenium film is used as a protective layer, which can reduce the volatilization of chalcogen elements in the femtosecond etching process and increase the doping rate. impurity content, and can prevent the impurity Se introduced by laser pulse irradiation from diffusing to the grain boundary, so as to maintain its doping concentration on the surface, so as to improve the absorption rate of black silicon.
综上所述，本发明的有益效果是：使用该方法制备的黑硅在400～1100nm波段的吸收率高于95％，在1100～2200nm波段的吸收率高于90％。相比于未覆盖硅保护层，仅热蒸发硒膜而制备的掺杂黑硅材料，本方法制备的掺杂黑硅在近红外波段吸收率有明显提高。In summary, the beneficial effect of the present invention is that the black silicon prepared by the method has an absorption rate higher than 95% in the 400-1100nm band, and an absorption rate higher than 90% in the 1100-2200nm band. Compared with the doped black silicon material prepared by thermally evaporating the selenium film without covering the silicon protective layer, the absorptivity of the doped black silicon prepared by the method in the near-infrared band is obviously improved.
附图说明Description of drawings
图1是实施例的制造黑硅材料方法的工艺流程图；Fig. 1 is the process flow diagram of the method for manufacturing black silicon material of embodiment;
图2是实施例的热蒸发硒膜和溅射硅膜后的示意图；Fig. 2 is the schematic diagram after the thermal evaporation selenium film of embodiment and sputtering silicon film;
图3是实施例经过飞秒激光刻蚀后硅衬底材料的截面示意图；3 is a schematic cross-sectional view of the silicon substrate material after femtosecond laser etching in the embodiment;
图4是实施例经过飞秒激光刻蚀后硅衬底材料的吸收光谱图；Fig. 4 is the absorption spectrogram of silicon substrate material after femtosecond laser etching of embodiment;
附图标记：1-硅衬底，2-硒膜，3-硅膜，4-激光扫描刻蚀后形成的掺杂黑硅结构。Reference signs: 1—silicon substrate, 2—selenium film, 3—silicon film, 4—doped black silicon structure formed after laser scanning etching.
具体实施方式detailed description
下面将结合附图对本发明做以详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings.
如图1所示为本实施例的流程示意图。FIG. 1 is a schematic flow diagram of this embodiment.
步骤1：获取清洁硅衬底。Step 1: Obtain a clean silicon substrate.
选用掺杂磷的N型硅片为衬底材料。然后采用RCA标准清洗法对硅衬底进行清洗，除去表面氧化物。再将已清洗的硅衬底放入丙酮中超声10分钟，除去表面残留的有机物。最后将硅衬底在去离子水中超声5分钟，并在氮气气氛下吹干。N-type silicon chip doped with phosphorus is selected as the substrate material. Then use the RCA standard cleaning method to clean the silicon substrate to remove the surface oxide. Then put the cleaned silicon substrate into acetone for 10 minutes to sonicate to remove the residual organic matter on the surface. Finally, the silicon substrate was sonicated in deionized water for 5 minutes and dried under nitrogen atmosphere.
步骤2：热蒸发硒膜Step 2: Thermally evaporated selenium film
将步骤1清洗好的硅衬底放入真空蒸发装置的工作台上，将真空腔的真空度抽至6×10-4Pa。启动蒸发单元，在硅衬底抛光面蒸发一层100nm的硒膜作为杂质源。Put the silicon substrate cleaned in step 1 on the workbench of the vacuum evaporation device, and evacuate the vacuum of the vacuum chamber to 6×10 -4 Pa. Start the evaporation unit, and evaporate a layer of 100nm selenium film on the polished surface of the silicon substrate as an impurity source.
步骤3：磁控溅射硅膜Step 3: Magnetron sputtering silicon film
将步骤2制备完的硅衬底放入磁控溅射机真空腔内的行走单元上，先将真空腔的真空度抽至5×10-4Pa，再通入氩气，至真空腔真空度为5×10-1Pa。开启电源，调节功率至氩气启辉，开启行走单元，在硒膜上再溅射一层50nm的硅膜作为保护层。Put the silicon substrate prepared in step 2 on the walking unit in the vacuum chamber of the magnetron sputtering machine, first evacuate the vacuum degree of the vacuum chamber to 5×10 -4 Pa, and then pass in argon gas until the vacuum chamber is vacuumed. The degree is 5×10 -1 Pa. Turn on the power, adjust the power to argon ignition, turn on the walking unit, and sputter a layer of 50nm silicon film on the selenium film as a protective layer.
步骤3处理后的硅衬底材料结构如图2所示。硅衬底为1，硒膜为2，硅膜为3。The material structure of the silicon substrate processed in step 3 is shown in FIG. 2 . The silicon substrate is 1, the selenium film is 2, and the silicon film is 3.
步骤4：飞秒激光扫描刻蚀黑硅Step 4: Femtosecond laser scanning etching black silicon
将步骤3制备好的硅衬底放入真空腔内，抽去腔内空气后通入氮气作为保护气体，氮气压强为0.5atm。用飞秒激光以能量密度3kJ/m2，扫描速度0.5mm/s进行扫描刻蚀，从而在硅衬底上形成微结构并实现掺杂。经过飞秒激光扫描刻蚀的硅衬底可以在表面形成掺杂黑硅结构。本实施例中，激光刻蚀后的硅衬底材料截面示意图如图3所示，其中1为硅衬底，4为激光扫描刻蚀后形成的掺杂黑硅结构。Put the silicon substrate prepared in step 3 into a vacuum chamber, pump out the air in the chamber, and then inject nitrogen gas as a protective gas, and the nitrogen pressure is 0.5 atm. A femtosecond laser is used for scanning etching with an energy density of 3kJ/m 2 and a scanning speed of 0.5mm/s, so as to form a microstructure and achieve doping on the silicon substrate. The silicon substrate etched by femtosecond laser scanning can form a doped black silicon structure on the surface. In this embodiment, a schematic cross-sectional view of the silicon substrate material after laser etching is shown in FIG. 3 , wherein 1 is a silicon substrate, and 4 is a doped black silicon structure formed after laser scanning etching.
步骤5：去除表面氧化硅层Step 5: Remove the surface silicon oxide layer
将扫描刻蚀后的硅衬底放入浓度为5％的氢氟酸内浸泡5分钟，除去表面的氧化硅层。用去离子水洗净并用氮气吹干，制备得到黑硅。The silicon substrate after scanning etching is immersed in hydrofluoric acid with a concentration of 5% for 5 minutes to remove the silicon oxide layer on the surface. Wash with deionized water and dry with nitrogen to prepare black silicon.
本实施例中，激光刻蚀硅衬底材料吸收光谱图如图4所示，分别为硒硅复合膜制备掺杂黑硅、热蒸发硒膜制备掺杂黑硅的吸收光谱。相比于未覆盖硅保护层，仅热蒸发硒膜而制备的掺杂黑硅材料，本方法制备的掺杂黑硅在近红外波段吸收率有明显提高。In this embodiment, the absorption spectrum of the laser-etched silicon substrate material is shown in FIG. 4 , which are respectively the absorption spectra of doped black silicon prepared by selenium-silicon composite film and doped black silicon prepared by thermally evaporating selenium film. Compared with the doped black silicon material prepared by thermally evaporating the selenium film without covering the silicon protective layer, the absorptivity of the doped black silicon prepared by the method in the near-infrared band is obviously improved.
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