CN111710750B - Deep ultraviolet photoelectric detector based on hexagonal boron nitride thick film and preparation method - Google Patents
Deep ultraviolet photoelectric detector based on hexagonal boron nitride thick film and preparation method Download PDFInfo
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Abstract
一种基于六方氮化硼厚膜的深紫外光电探测器及制备方法，包括衬底、紫外光敏层和叉指电极，其中紫外光敏层为高质量六方氮化硼厚膜，对日盲波段有很好的响应。所述六方氮化硼厚膜本身具有的固有性能非常卓越，通过离子束溅射沉积方法制备六方氮化硼厚膜纯度非常高，具有良好的稳定性、厚度可控、无毒无污染等优点，通过掺杂目标杂质可以调整带隙宽度，从而提高了深紫外光电探测器的光电导增益和短波段光响应，实现紫外光电探测器对日盲波段的有效探测。
A deep ultraviolet photodetector based on a hexagonal boron nitride thick film and its preparation method, including a substrate, an ultraviolet photosensitive layer and an interdigital electrode, wherein the ultraviolet photosensitive layer is a high-quality hexagonal boron nitride thick film, which is effective for sun-blind bands Great response. The inherent performance of the hexagonal boron nitride thick film itself is very excellent, and the hexagonal boron nitride thick film prepared by ion beam sputtering deposition method has very high purity, good stability, controllable thickness, non-toxic and pollution-free, etc. , the bandgap width can be adjusted by doping target impurities, thereby improving the photoconductive gain and short-wavelength photoresponse of deep ultraviolet photodetectors, and realizing the effective detection of ultraviolet photodetectors in the sun-blind band.
Description
技术领域technical field
本发明属于半导体光电探测器技术领域，具体涉及一种基于六方氮化硼厚膜的深紫外光电探测器及制备方法。The invention belongs to the technical field of semiconductor photodetectors, and in particular relates to a deep ultraviolet photodetector based on a hexagonal boron nitride thick film and a preparation method.
背景技术Background technique
军事、航空、工业、环境、医药、生物等领域一直迫切需要性能优越的深紫外光电探测器。目前常见的紫外探测器主要以硅基探测器和光电倍增管为主。硅基探测器受限于材料Si的小禁带宽度(1.12eV)，使用时需要加上结构复杂、价格昂贵的滤光系统。虽然SiC、AlGaN、ZnMgO等一些宽禁带半导体具有抗辐射能力强、室温操作、固有的可见日盲、高导热率、耐高温、大功率、电子空穴迁移率低、高场强下电子速度大等优点，但其光电探测器的性能仍远低于预期。如，SiC的禁带宽度不可调节(3.26eV)，要想实现深紫外光电探测仍需加紫外滤光片。而ZnMgO的禁带宽度虽可以通过调节Mg组分来实现在3.3～7.8eV之间调节，但常常发生结构分凝。AlGaN则需要高Al组分来实现日盲深紫外探测，但是目前高晶体质量的材料很难实现。Military, aviation, industry, environment, medicine, biology and other fields have been in urgent need of deep ultraviolet photodetectors with superior performance. At present, the common ultraviolet detectors are mainly silicon-based detectors and photomultiplier tubes. Silicon-based detectors are limited by the small bandgap (1.12eV) of the material Si, and require a complex and expensive filter system when used. Although some wide-bandgap semiconductors such as SiC, AlGaN, and ZnMgO have strong radiation resistance, room temperature operation, inherent visible solar blindness, high thermal conductivity, high temperature resistance, high power, low electron-hole mobility, and electron velocity at high field strength However, the performance of its photodetectors is still far below expectations. For example, the band gap of SiC cannot be adjusted (3.26eV), and an ultraviolet filter is still required to realize deep ultraviolet photodetection. Although the band gap of ZnMgO can be adjusted between 3.3 and 7.8 eV by adjusting the Mg component, structural segregation often occurs. AlGaN requires a high Al composition to achieve solar-blind deep ultraviolet detection, but it is difficult to achieve high crystal quality materials at present.
六方氮化硼，具有类似于石墨烯的结构单元，具有超宽的禁带宽度，且准直接带隙，具有制作深紫外光电探测器件的天然的材料性能。现有的基于六方氮化硼的深紫外光电探测器技术大多以二维氮化硼原子晶体或二维氮化硼原子晶体/石墨烯等其他二维材料作为紫外光敏层材(CN106505115A；CN108231945A；Gao,M.,Meng,J.,Chen,Y.,Ye,S.,Wang,Y.,Ding,C.,Li,Y.,Yin,Z.,Zeng,X.,You,J.,Jin,P.,Zhang,X.,Catalyst-free growthof two-dimensional hexagonal boron nitride few-layers on sapphire for deepultraviolet photodetectors,Journal of Materials Chemistry C,2019,7,14999-15006.；Lu,Y.,Wu,Z.,Xu,W.,Lin,S.,ZnO quantum dot-doped graphene/h-BN/GaN-heterostructure ultraviolet photodetector with extremely highresponsivity,Nanotechnology,2016,27,48LT03.)，制备出来原子层存在层数不可控、表面不平滑等问题，且通常需要沉积在催化金属/合金衬底上，后续的样品表征和器件制作会需要转移。因此在工艺和材料质量等方面都不能很好的得到保障。而少数以六方氮化硼膜为紫外光敏层材料的深紫外光电探测器的性能仍然不能满足需要(CN110649108A；Doan,T.C.,Majety,S.,Grenadier,S.,Li,J.,Lin,J.Y.,Jiang,H.X.,Fabrication and characterization ofsolid-state thermal neutron detectors based on hexagonal boron nitrideepilayers,Nuclear Instruments and Methods in Physics Research Section A:Accelerators,Spectrometers,Detectors and AssociatedEquipment,2014,748,84-90；Wang,Y.,Meng,J.,Tian,Y.,Chen,Y.,Wang,G.,Yin,Z.,Jin,P.,You,J.,Wu,J.,Zhang,X.,Deep ultraviolet photodetectors based on carbon-doped two-dimensionalhexagonal boron nitride,ACS Appl Mater Interfaces,2020,12,27361-27367)，主要是由于材料的晶体质量较差、厚度不均匀、掺杂效率不佳。因此，对六方氮化硼厚膜的晶体质量和厚度进行改进，通过适当的手段提高掺杂效率，有效的调控六方氮化硼的带隙宽度，减少甚至消除高错位密度，降低暗电流，提高载流子的传输速率，是提升深紫外光电探测性能的途径。Hexagonal boron nitride has a structural unit similar to graphene, has an ultra-wide band gap, and a quasi-direct band gap, and has natural material properties for making deep ultraviolet photodetection devices. Most of the existing deep ultraviolet photodetector technologies based on hexagonal boron nitride use two-dimensional boron nitride atomic crystals or two-dimensional boron nitride atomic crystals/graphene and other two-dimensional materials as ultraviolet photosensitive layers (CN106505115A; CN108231945A; Gao, M., Meng, J., Chen, Y., Ye, S., Wang, Y., Ding, C., Li, Y., Yin, Z., Zeng, X., You, J., Jin, P., Zhang, X., Catalyst-free growth of two-dimensional hexagonal boron nitride few-layers on sapphire for deep ultraviolet photodetectors, Journal of Materials Chemistry C, 2019, 7, 14999-15006.; Lu, Y., Wu , Z., Xu, W., Lin, S., ZnO quantum dot-doped graphene/h-BN/GaN-heterostructure ultraviolet photodetector with extremely high responsivity, Nanotechnology, 2016, 27, 48LT03.), prepared atomic layer existing layer The number is uncontrollable, the surface is not smooth, etc., and it usually needs to be deposited on the catalytic metal/alloy substrate, and the subsequent sample characterization and device fabrication will need to be transferred. Therefore, aspects such as process and material quality cannot be well guaranteed. However, the performance of a small number of deep ultraviolet photodetectors with hexagonal boron nitride film as the ultraviolet photosensitive layer material still cannot meet the needs (CN110649108A; Doan, T.C., Majety, S., Grenadier, S., Li, J., Lin, J.Y. ,Jiang,H.X.,Fabrication and characterization of solid-state thermal neutron detectors based on hexagonal boron nitrodeepilayers,Nuclear Instruments and Methods in Physics Research Section A:Accelerators,Spectrometers,Detectors and Associated Equipment,2014,748,84-90; ,Meng,J.,Tian,Y.,Chen,Y.,Wang,G.,Yin,Z.,Jin,P.,You,J.,Wu,J.,Zhang,X.,Deep ultraviolet photodetectors based on carbon-doped two-dimensional hexagonal boron nitride, ACS Appl Mater Interfaces, 2020, 12, 27361-27367), mainly due to poor crystal quality, uneven thickness, and poor doping efficiency of the material. Therefore, to improve the crystal quality and thickness of hexagonal boron nitride thick film, improve the doping efficiency by appropriate means, effectively regulate the bandgap width of hexagonal boron nitride, reduce or even eliminate high dislocation density, reduce dark current, and improve The carrier transport rate is the way to improve the performance of deep ultraviolet photodetection.
发明内容Contents of the invention
本发明的目的在于，提供一种基于六方氮化硼厚膜的深紫外光电探测器及制备方法，其可保证器件在深紫外区具有高的响应度和响应速度，同时采用在位掺杂，实现对紫外光敏层材料的带隙调控，提高其掺杂效率，既保证晶体质量，又提升器件性能。The object of the present invention is to provide a deep ultraviolet photodetector based on a hexagonal boron nitride thick film and a preparation method, which can ensure that the device has high responsivity and response speed in the deep ultraviolet region, and at the same time adopts in-situ doping, Realize the bandgap control of the ultraviolet photosensitive layer material, improve its doping efficiency, not only ensure the crystal quality, but also improve the device performance.
为实现以上目的，本发明提供一种基于六方氮化硼厚膜的深紫外光电探测器，包括：To achieve the above object, the present invention provides a deep ultraviolet photodetector based on hexagonal boron nitride thick film, including:
(1)衬底；(1) Substrate;
(2)紫外光敏层，其制作在衬底上，并完全覆盖所述衬底；(2) UV-sensitive layer, which is made on the substrate and completely covers the substrate;
(3)叉指电极，其制作在深紫外光敏层上，并覆盖部分紫外光敏层。(3) Interdigitated electrodes, which are fabricated on the deep ultraviolet photosensitive layer and cover part of the ultraviolet photosensitive layer.
所述步骤(1)衬底的材料为多晶或单晶金刚石、石英玻璃、硅或蓝宝石，优选为硅衬底。The material of the substrate in the step (1) is polycrystalline or single crystal diamond, quartz glass, silicon or sapphire, preferably a silicon substrate.
所述步骤(2)紫外光敏层的材料为六方氮化硼厚膜，膜厚为40nm以上，优选为500nm。The material of the ultraviolet photosensitive layer in the step (2) is a thick film of hexagonal boron nitride, and the film thickness is more than 40nm, preferably 500nm.
所述步骤(2)紫外光敏层为掺杂的六方氮化硼厚膜，其目标掺杂杂质为碳、铝、镁、硫或铁，优选为碳。The ultraviolet photosensitive layer in the step (2) is a doped hexagonal boron nitride thick film, and its target doping impurity is carbon, aluminum, magnesium, sulfur or iron, preferably carbon.
所述步骤(2)紫外光敏层的带隙宽度为1.8～6.0eV，优选为2.5～3.5eV。The bandgap width of the ultraviolet photosensitive layer in the step (2) is 1.8-6.0 eV, preferably 2.5-3.5 eV.
所述步骤(3)制作叉指电极的材料为钛、铬、钼、金和银，优选为金电极；电极的指宽为3.2～3.6μm，优选为3.6μm；指间距为5.6～6.4μm，优选为6.4μm；厚度为80～120nm，优选为100nm。The material for making interdigitated electrodes in the step (3) is titanium, chromium, molybdenum, gold and silver, preferably gold electrodes; the finger width of the electrodes is 3.2-3.6 μm, preferably 3.6 μm; the finger spacing is 5.6-6.4 μm , preferably 6.4 μm; the thickness is 80-120 nm, preferably 100 nm.
一种基于六方氮化硼厚膜的深紫外光电探测器的制备方法，其特征在于，包括以下步骤：A method for preparing a deep ultraviolet photodetector based on a hexagonal boron nitride thick film, characterized in that it comprises the following steps:
1)提供衬底；1) Provide the substrate;
2)采用双离子束溅射沉积方法在衬底表面制备六方氮化硼厚膜或在位掺杂六方氮化硼厚膜；2) A thick film of hexagonal boron nitride or a thick film of in-situ doped hexagonal boron nitride is prepared on the surface of the substrate by a dual ion beam sputtering deposition method;
3)随后在所制备的六方氮化硼厚膜表面制备叉指电极。3) Subsequent preparation of interdigitated electrodes on the surface of the as-prepared hexagonal boron nitride thick film.
所述步骤1)一种基于六方氮化硼厚膜的深紫外光电探测器的制备方法，其特征在于，所述衬底的材料为多晶或单晶金刚石、石英玻璃、硅或蓝宝石，优选为硅衬底。Described step 1) a kind of preparation method based on the deep ultraviolet photodetector of hexagonal boron nitride thick film, it is characterized in that, the material of described substrate is polycrystalline or monocrystalline diamond, quartz glass, silicon or sapphire, preferably for the silicon substrate.
所述步骤2)采用双离子束溅射沉积方法对六方氮化硼厚膜进行在位掺杂时向辅助离子源通入含有目标掺杂杂质碳、铝、镁、硫或铁的气源，优选为碳。The step 2) adopting the double ion beam sputtering deposition method to conduct in-situ doping on the hexagonal boron nitride thick film, and supplying a gas source containing target doping impurities carbon, aluminum, magnesium, sulfur or iron to the auxiliary ion source, Carbon is preferred.
所述步骤3)叉指电极的材料为钛、铬、钼、金或银；电极的指宽为3.2～3.6μm，优选为3.6μm；指间距为5.6～6.4μm，优选为6.4μm；厚度为80～120nm，优选为100nm。Step 3) The material of the interdigitated electrodes is titanium, chromium, molybdenum, gold or silver; the finger width of the electrode is 3.2-3.6 μm, preferably 3.6 μm; the finger spacing is 5.6-6.4 μm, preferably 6.4 μm; the thickness 80 to 120 nm, preferably 100 nm.
本发明提供了基于六方氮化硼厚膜的深紫外光电探测器的六方氮化硼厚膜紫外光敏层具有高纯度和低错位密度，载流子的传输速率高，暗电流小的优点。The invention provides the hexagonal boron nitride thick film ultraviolet photosensitive layer of the deep ultraviolet photodetector based on the hexagonal boron nitride thick film, which has the advantages of high purity and low dislocation density, high carrier transmission rate and small dark current.
本发明提供了一种性能优越的基于六方氮化硼厚膜的深紫外光电探测器，具有较短的截止波长，电压增至15V时，就可以在215nm处有一个非常好的响应峰。在低电压时就可以得到很好的响应，为深紫外光电探测器扩宽了材料的选择。The invention provides a hexagonal boron nitride thick film-based deep ultraviolet photodetector with superior performance, which has a shorter cut-off wavelength and can have a very good response peak at 215nm when the voltage is increased to 15V. A good response can be obtained at low voltage, which broadens the choice of materials for deep ultraviolet photodetectors.
本发明的有益效果主要体现在：The beneficial effects of the present invention are mainly reflected in:
(1)本发明通过双离子束溅射沉积方法在多种衬底上直接生长高质量的六方氮化硼厚膜，可以通过调节生长参数来控制六方氮化硼厚膜的结构和生长质量，获得了高质量、大面积的厚膜，这种微观结构改善了六方氮化硼厚膜的位错密度和提高了六方氮化硼的纯度等重要深紫外光电探测器性能参数，并降低了引起产生紫外光电响应的电压，从20V降低到15V。(1) The present invention directly grows high-quality hexagonal boron nitride thick films on various substrates by a dual ion beam sputtering deposition method, and can control the structure and growth quality of hexagonal boron nitride thick films by adjusting growth parameters, A high-quality, large-area thick film is obtained. This microstructure improves the dislocation density of the hexagonal boron nitride thick film and the purity of the hexagonal boron nitride and other important deep ultraviolet photodetector performance parameters, and reduces the induced The voltage to generate the UV photoresponse was reduced from 20V to 15V.
(2)本发明采用双离子束溅射沉积方法制备出的六方氮化硼厚膜做深紫外光电探测器的光敏层材料，扩宽了紫外光检测的范围，增强了在特定区域光谱的响应度。该方法成本低廉、技术工艺可控、便于操作，易于工业化推广。(2) The present invention uses the hexagonal boron nitride thick film prepared by the double ion beam sputtering deposition method as the photosensitive layer material of the deep ultraviolet photodetector, which broadens the range of ultraviolet light detection and enhances the response of the spectrum in a specific area Spend. The method has the advantages of low cost, controllable technical process, convenient operation and easy industrial promotion.
(3)本发明通过在位掺杂的手段，对六方氮化硼厚膜的带隙进行了有效调控，在提高掺杂效率的同时，又保证了材料的晶体质量，有利于器件性能的提升。(3) The present invention effectively regulates the band gap of the hexagonal boron nitride thick film by means of in-situ doping, while improving the doping efficiency, it also ensures the crystal quality of the material, which is beneficial to the improvement of device performance .
附图说明Description of drawings
构成本发明的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：The drawings constituting a part of the present invention are used to provide a further understanding of the present invention, and the schematic embodiments and descriptions of the present invention are used to explain the present invention, and do not constitute an improper limitation of the present invention. In the attached picture:
图1为本发明所述的深紫外光电探测器结构示意图；Fig. 1 is the structural representation of deep ultraviolet photodetector of the present invention;
图2为本发明所述的紫外光敏层的扫描电子显微镜(SEM)平面图；Fig. 2 is the scanning electron microscope (SEM) plane view of ultraviolet photosensitive layer of the present invention;
图3为本发明所述的叉指电极SEM平面图。Fig. 3 is a SEM plan view of the interdigitated electrode according to the present invention.
具体实施方式detailed description
为使本发明的上述目的、特征和优点能够更为明显易懂，下面结合附图对本发明的具体实施例做详细的说明。In order to make the above objects, features and advantages of the present invention more comprehensible, specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings.
参照图1，本实施例具体公开了一种基于六方氮化硼厚膜的深紫外光电探测器。Referring to FIG. 1 , this embodiment specifically discloses a deep ultraviolet photodetector based on a hexagonal boron nitride thick film.
该深紫外光电探测器包括叉指电极1、六方氮化硼厚膜紫外光敏层2、硅衬底3以及光电检测装置4。The deep ultraviolet photodetector includes an interdigital electrode 1 , a hexagonal boron nitride thick film ultraviolet
硅衬底3上生长六方氮化硼厚膜紫外光敏层2，叉指电极1部分覆盖六方氮化硼厚膜紫外光敏层2，叉指电极1通过导线与光电检测装置4连接。A hexagonal boron nitride thick-film ultraviolet-
衬底的制备及清洗：1)将所需尺寸的N型硅片(100)切好；2)将切好的硅片放到煮沸的石油醚中2min(石油醚沸点80～90℃)，然后用丙酮超声清洗，之后用去离子水冲洗干净；3)放入沸腾的氨水、双氧水和去离子水的混合物中2min(混合物的沸点：60℃)，氨水、双氧水和去离子水的比例为1:2:5，然后用去离子水冲洗干净；4)放入沸腾的盐酸、双氧水和去离子水的混合液中2min(混合物的沸点：90℃)，盐酸、双氧水和去离子水的比例为1:2:8。取出后用去离子水冲洗干净；5)放入10％的氢氟酸溶液中浸泡15s后取出并用去离子水冲洗。将较为干净的衬底送入离子束沉积室，在500℃下将离子束沉积室抽至9×10-5Pa以下；通入2sccm氩气；开启辅助离子源，能量为300eV。利用离子束溅射沉积产生的氩离子束对衬底刻蚀清洗十分钟。即可获得原子级的清洁表面。Preparation and cleaning of the substrate: 1) Cut the N-type silicon wafer (100) of the required size; 2) Put the cut silicon wafer in boiling petroleum ether for 2 minutes (petroleum ether boiling point 80-90°C), Then use acetone to ultrasonically clean it, and then rinse it with deionized water; 3) put it into a mixture of boiling ammonia, hydrogen peroxide and deionized water for 2 minutes (the boiling point of the mixture: 60 ° C), the ratio of ammonia, hydrogen peroxide and deionized water is 1:2:5, then rinse with deionized water; 4) Put it into a mixture of boiling hydrochloric acid, hydrogen peroxide and deionized water for 2 minutes (the boiling point of the mixture: 90°C), the ratio of hydrochloric acid, hydrogen peroxide and deionized water It is 1:2:8. After taking it out, rinse it with deionized water; 5) soak it in 10% hydrofluoric acid solution for 15 seconds, then take it out and rinse it with deionized water. Send the relatively clean substrate into the ion beam deposition chamber, and pump the ion beam deposition chamber below 9×10 -5 Pa at 500°C; inject 2 sccm of argon gas; turn on the auxiliary ion source with an energy of 300eV. The substrate was etched and cleaned for ten minutes with an argon ion beam generated by ion beam sputtering deposition. A clean surface at the atomic level can be obtained.
紫外光敏层的制备：利用双离子束溅射沉积方法通入主离子源氩气为6sccm；辅助离子源氩气为2sccm；辅助离子源氮气为3sccm，工作气压3.4～3.6×10-2Pa；开启双离子源，主离子源能量为1500eV；辅助离子源能量为280eV；加速电压为60eV；将基底移至工作区，溅射8h，制备六方氮化硼光敏层。图2为制备六方氮化硼光敏层的SEM平面图，厚膜表面致密、平整、均匀、无脱落现象。所制备六方氮化硼厚膜紫外光敏层与硅衬底紧密粘连，厚度为452nm。FTIR光谱图和XRD光谱图证明膜是高质量单晶六方氮化硼厚膜，且结晶度很好。The preparation of the ultraviolet photosensitive layer: using the double ion beam sputtering deposition method, the argon gas of the main ion source is 6 sccm; the argon gas of the auxiliary ion source is 2 sccm; the nitrogen gas of the auxiliary ion source is 3 sccm, and the working pressure is 3.4～3.6×10 -2 Pa; Turn on the dual ion source, the energy of the main ion source is 1500eV; the energy of the auxiliary ion source is 280eV; the acceleration voltage is 60eV; the substrate is moved to the working area, and the hexagonal boron nitride photosensitive layer is prepared by sputtering for 8 hours. Figure 2 is a SEM plan view of the prepared hexagonal boron nitride photosensitive layer, the surface of the thick film is dense, smooth, uniform and free of shedding. The prepared hexagonal boron nitride thick film ultraviolet photosensitive layer is tightly adhered to the silicon substrate, and the thickness is 452nm. The FTIR spectrum and XRD spectrum prove that the film is a high-quality single crystal hexagonal boron nitride thick film with good crystallinity.
叉指电极的制备：将生长了六方氮化硼紫外光敏层的衬底放入射频磁控溅射仪器中，并将有叉指电极图案掩膜版按照操作要求放置，之后在1×10-3Pa下溅射金原子，溅射时间为6min，厚度为100nm；特制的掩膜版上叉指电极图形的尺寸为1×1cm(图3)。Preparation of interdigitated electrodes: Put the substrate grown with the hexagonal boron nitride ultraviolet photosensitive layer into the radio frequency magnetron sputtering instrument, and place the mask plate with the interdigitated electrode pattern according to the operation requirements, and then place it at 1×10 - Gold atoms were sputtered at 3 Pa, the sputtering time was 6min, and the thickness was 100nm; the size of the interdigitated electrode pattern on the special mask was 1×1cm (Figure 3).
将制备好叉指电极的样品在其两端电极上连接光电检测装置，对探测器进行日盲波段性能的检测；当电压加之15V时，在215nm处出现明显属于六方氮化硼的光电响应信号。The sample prepared with interdigitated electrodes is connected to the photoelectric detection device on the electrodes at both ends, and the solar-blind band performance of the detector is tested; when the voltage is added to 15V, a photoelectric response signal obviously belonging to hexagonal boron nitride appears at 215nm .
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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