CN111244201A - A flexible self-supporting ZnO ultraviolet detector and preparation method thereof - Google Patents
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Abstract
本发明提供了一种柔性自支撑ZnO紫外探测器,属于紫外探测技术领域,包括:四足状ZnO纳米结构层、设置于所述四足状ZnO纳米结构层表面的两个电极及柔性衬底;所述四足状ZnO纳米结构层独立存在实现自支撑,通过转移置于所述柔性衬底上。本发明还提供了一种柔性自支撑ZnO紫外探测器的制备方法。本发明的紫外探测器采用四足状ZnO纳米结构层,具有特殊的四足状结构,以四根纳米线为一个单元,堆叠成絮状自支撑结构,简单且高效地获得响应速度快的柔性紫外探测器;四足状ZnO纳米结构层结晶质量高、性能优异,光暗抑制比高,响应速度快,可应用于柔性紫外探测器的制造,有效解决现有ZnO微纳结构柔性紫外探测器中衬底不耐高温的问题。
The invention provides a flexible self-supporting ZnO ultraviolet detector, belonging to the technical field of ultraviolet detection, comprising: a tetrapod-shaped ZnO nanostructure layer, two electrodes arranged on the surface of the tetrapod-shaped ZnO nanostructure layer, and a flexible substrate ; The tetrapod-shaped ZnO nanostructure layer exists independently to realize self-support, and is placed on the flexible substrate by transferring. The invention also provides a preparation method of a flexible self-supporting ZnO ultraviolet detector. The ultraviolet detector of the present invention adopts a tetrapod-shaped ZnO nanostructure layer, which has a special tetrapod-shaped structure. Four nanowires are used as a unit to be stacked into a flocculent self-supporting structure, and a flexible and fast response speed can be obtained simply and efficiently. Ultraviolet detector; the tetrapod-like ZnO nanostructure layer has high crystal quality, excellent performance, high light-dark suppression ratio and fast response speed, which can be used in the manufacture of flexible ultraviolet detectors, effectively solving the existing ZnO micro-nanostructure flexible ultraviolet detectors The problem that the substrate is not resistant to high temperature.
Description
技术领域technical field
本发明涉及紫外探测技术领域,具体涉及一种柔性自支撑ZnO紫外探测器及其制备方法。The invention relates to the technical field of ultraviolet detection, in particular to a flexible self-supporting ZnO ultraviolet detector and a preparation method thereof.
背景技术Background technique
紫外探测技术是继激光和红外探测技术之后兴起的又一军民两用的探测技术,现代化的紫外探测技术是一个集紫外探测器、光学设计、微机械加工和集成电路等多学科为一体的精密探测系统。由于其具有虚警率低、隐蔽性好和抗电磁干扰能力强等优点,目前已广泛应用于污水净化紫外线检测、火灾监测、导弹预警、紫外通讯以及臭氧层空洞检测等诸多领域。近年来,宽禁带半导体紫外探测器因其体积小、重量轻、工作时不需滤光片、无需制冷等优点被认为是可以取代真空光电倍增管和Si光电倍增管的第三代紫外探测器。在众多宽禁带半导体材料中,ZnO基材料具有缺陷密度低,抗辐射能力强,环境友好等诸多优点,且可通过Mg的掺杂使其光学带隙在3.37-7.78eV范围连续可调,同时,ZnO具有典型的六方-纤锌矿晶体结构,可以非常容易地生长出不同的一维微纳结构,各种缺陷的存在进一步使ZnO纳米结构成为光电探测和先进光电子/发光技术的最理想的材料之一。Ultraviolet detection technology is another dual-use detection technology after laser and infrared detection technology. detection system. Due to its advantages of low false alarm rate, good concealment and strong anti-electromagnetic interference ability, it has been widely used in many fields such as sewage purification ultraviolet detection, fire monitoring, missile warning, ultraviolet communication and ozone hole detection. In recent years, wide-bandgap semiconductor UV detectors are considered to be the third-generation UV detectors that can replace vacuum photomultiplier tubes and Si photomultiplier tubes due to their small size, light weight, and no need for filters and refrigeration. device. Among many wide-bandgap semiconductor materials, ZnO-based materials have many advantages such as low defect density, strong radiation resistance, and environmental friendliness, and the optical band gap can be continuously adjusted in the range of 3.37-7.78 eV by doping with Mg. At the same time, ZnO has a typical hexagonal-wurtzite crystal structure, which can easily grow different one-dimensional micro-nano structures, and the existence of various defects further makes ZnO nanostructures the most ideal for photodetection and advanced optoelectronic/luminescence technologies one of the materials.
传统ZnO紫外探测器主要以蓝宝石、硅片或石英为衬底,不可弯折不易转移。而ZnO微纳结构柔性紫外探测器所用衬底不耐高温,大多数所能承受的温度极限在150~200℃,材料无法直接制备在柔性衬底上,这限制了柔性器件的制备。鉴于此,急需研究一种柔性自支撑ZnO紫外探测器及其制备方法,解决现有ZnO微纳结构柔性紫外探测器柔性衬底不耐高温的技术问题。Traditional ZnO UV detectors mainly use sapphire, silicon wafer or quartz as the substrate, which cannot be bent or transferred easily. However, the substrates used in ZnO micro-nano structure flexible UV detectors are not resistant to high temperature, and most of them can withstand a temperature limit of 150-200 °C. Materials cannot be directly prepared on flexible substrates, which limits the preparation of flexible devices. In view of this, there is an urgent need to study a flexible self-supporting ZnO UV detector and its preparation method to solve the technical problem that the flexible substrate of the existing ZnO micro-nano structure flexible UV detector is not resistant to high temperature.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于针对现有技术的上述缺陷,提供一种柔性自支撑ZnO紫外探测器及其制备方法,采用四足状ZnO纳米结构层,具有特殊的四足状结构,以四根纳米线为一个单元,堆叠成絮状自支撑结构,四足状ZnO纳米结构层结晶质量高、性能优异,光暗抑制比高,响应速度快,可应用于柔性紫外探测器的制造,有效解决现有ZnO微纳结构柔性紫外探测器中衬底不耐高温的问题。The object of the present invention is to provide a flexible self-supporting ZnO ultraviolet detector and a preparation method thereof in view of the above-mentioned defects of the prior art, using a tetrapod-shaped ZnO nanostructure layer, which has a special tetrapod-shaped structure, and is composed of four nanowires. As a unit, stacked into a flocculent self-supporting structure, the tetrapod-like ZnO nanostructure layer has high crystal quality, excellent performance, high light-dark suppression ratio, and fast response speed. It can be used in the manufacture of flexible UV detectors, effectively solving existing problems. The substrate is not resistant to high temperature in the ZnO micro-nano structure flexible UV detector.
本发明的目的可通过以下的技术措施来实现:The purpose of the present invention can be achieved through the following technical measures:
本发明提供了一种柔性自支撑ZnO紫外探测器,包括:The present invention provides a flexible self-supporting ZnO ultraviolet detector, comprising:
四足状ZnO纳米结构层、设置于所述四足状ZnO纳米结构层表面的两个电极及柔性衬底;A tetrapod-shaped ZnO nanostructure layer, two electrodes disposed on the surface of the tetrapod-shaped ZnO nanostructure layer, and a flexible substrate;
所述四足状ZnO纳米结构层独立存在实现自支撑,通过转移置于所述柔性衬底上。The tetrapod-shaped ZnO nanostructure layer exists independently to realize self-support, and is placed on the flexible substrate by transferring.
进一步地,所述四足状ZnO纳米结构层的厚度为50~1000μm;其中,四足状ZnO纳米结构的四足直径为50~100nm,四足长度为2~5μm。Further, the thickness of the tetrapod-shaped ZnO nanostructure layer is 50-1000 μm; wherein, the tetrapod diameter of the tetrapod-shaped ZnO nanostructure is 50-100 nm, and the tetrapod length is 2-5 μm.
进一步地,所述两个电极独立设计,独立地选自In电极、Au电极、Ag电极或Al电极中的任意一种,电极厚度为30~50nm。Further, the two electrodes are independently designed and independently selected from any one of In electrodes, Au electrodes, Ag electrodes or Al electrodes, and the thickness of the electrodes is 30-50 nm.
进一步地,所述两个电极均为圆形电极,直径为1~2mm;所述两个电极之间的距离≤1mm。Further, the two electrodes are circular electrodes with a diameter of 1-2 mm; the distance between the two electrodes is less than or equal to 1 mm.
进一步地,所述柔性衬底为聚对苯二甲酸乙二酯衬底或织布衬底。Further, the flexible substrate is a polyethylene terephthalate substrate or a woven cloth substrate.
本发明还提供了一种上述的柔性自支撑ZnO紫外探测器的制备方法,包括以下步骤:The present invention also provides a preparation method of the above-mentioned flexible self-supporting ZnO UV detector, comprising the following steps:
S1:制备所述四足状ZnO纳米结构层;S1: preparing the tetrapod-shaped ZnO nanostructure layer;
S2:采用粘接的方式将所述两个电极固定于所述四足状ZnO纳米结构层上;S2: fixing the two electrodes on the tetrapod-shaped ZnO nanostructure layer by means of bonding;
S3:将粘接有所述两个电极的四足状ZnO纳米结构层转移到所述柔性衬底上,并压实固定,在压实前先铺上硫酸纸避免所述四足状ZnO纳米结构层在压实过程中受损伤、沾污,得到柔性自支撑ZnO紫外探测器。S3: Transfer the tetrapod-shaped ZnO nanostructure layer bonded with the two electrodes to the flexible substrate, and compact and fix it, and lay sulfuric acid paper before compaction to avoid the tetrapod-shaped ZnO nanostructure layer. The structural layer was damaged and stained during the compaction process, and a flexible self-supporting ZnO UV detector was obtained.
进一步地,所述步骤S1中制备所述四足状ZnO纳米结构层的方法为火焰传输法、化学气相沉积法、水热法中的任意一种。Further, the method for preparing the tetrapod-shaped ZnO nanostructure layer in the step S1 is any one of a flame transmission method, a chemical vapor deposition method, and a hydrothermal method.
进一步地,所述步骤S1中采用化学气相沉积法制备所述四足状ZnO纳米结构层,制备步骤如下:Further, in the step S1, chemical vapor deposition method is used to prepare the tetrapod-shaped ZnO nanostructure layer, and the preparation steps are as follows:
S10:将ZnO粉末与石墨粉末按照1:1的质量比研磨混合均匀,之后置于化学气相沉积设备中作为生长源;S10: The ZnO powder and the graphite powder are ground and mixed uniformly according to the mass ratio of 1:1, and then placed in a chemical vapor deposition device as a growth source;
S11:在惰性气体保护下对化学气相沉积设备进行升温,升温控制参数为:(50±1)min从室温升至1000℃,(30±1)min从1000℃升至1130℃~1150℃;当温度上升至1000℃通入氧气,控制氧气流量为15~20sccm;S11: Heat up the chemical vapor deposition equipment under the protection of inert gas. The temperature control parameters are: (50±1)min from room temperature to 1000℃, (30±1)min from 1000℃ to 1130℃~1150℃ ; When the temperature rises to 1000°C, oxygen is introduced, and the oxygen flow rate is controlled to be 15-20sccm;
S12:在1130℃~1150℃温度下保温(60±1)min,用于生长沉积四足状ZnO纳米结构;S12: keep the temperature at 1130℃~1150℃ for (60±1)min to grow and deposit tetrapod-like ZnO nanostructures;
S13:沉积完成后降温至室温,用镊子直接分离取出即得述四足状ZnO纳米结构层。S13: After the deposition is completed, the temperature is lowered to room temperature, and the tetrapod-shaped ZnO nanostructure layer is obtained by directly separating and taking out with tweezers.
进一步地,所述惰性气体为氩气或氮气。Further, the inert gas is argon or nitrogen.
进一步地,所述惰性气体为氩气,氩气流量为90~110sccm。Further, the inert gas is argon, and the flow rate of argon is 90-110 sccm.
本发明的柔性自支撑ZnO紫外探测器,采用四足状ZnO纳米结构层,具有特殊的四足状结构,以四根纳米线为一个单元,每个结构单元紧密连接,结构相对牢固,当厚度足够大时可脱离衬底独立存在,堆叠成絮状自支撑结构,为柔性紫外探测器的衬底选择上提供更多可能,有效解决现有ZnO微纳结构柔性紫外探测器中衬底不耐高温的问题;四足状ZnO纳米结构层结晶质量高、性能优异,光暗抑制比高,响应速度快,可以转移到柔性衬底上,简单且高效地获得响应速度快的柔性紫外探测器。本发明的柔性自支撑ZnO紫外探测器的制备方法简单、高效,四足状ZnO纳米结构层的制备过程可控可设计,可以实现对四足状ZnO纳米结构层的厚度进行设计。The flexible self-supporting ZnO ultraviolet detector of the present invention adopts a tetrapod-shaped ZnO nanostructure layer and has a special tetrapod-shaped structure. Four nanowires are used as a unit, each structural unit is closely connected, and the structure is relatively firm. When it is large enough, it can exist independently from the substrate, and can be stacked into a floc-like self-supporting structure, which provides more possibilities for the substrate selection of flexible UV detectors, and effectively solves the problem of substrate intolerance in the existing ZnO micro-nano structure flexible UV detectors. The problem of high temperature; the tetrapod-like ZnO nanostructure layer has high crystal quality, excellent performance, high light-dark suppression ratio, and fast response speed, which can be transferred to flexible substrates, and a flexible UV detector with fast response speed can be obtained simply and efficiently. The preparation method of the flexible self-supporting ZnO ultraviolet detector of the present invention is simple and efficient, the preparation process of the tetrapod ZnO nanostructure layer is controllable and can be designed, and the thickness of the tetrapod ZnO nanostructure layer can be designed.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative effort.
图1是本发明的柔性自支撑ZnO紫外探测器的结构示意图;Fig. 1 is the structural representation of the flexible self-supporting ZnO ultraviolet detector of the present invention;
图2是本发明的柔性自支撑ZnO紫外探测器在弯曲状态下的结构示意图;2 is a schematic structural diagram of the flexible self-supporting ZnO ultraviolet detector of the present invention in a bent state;
图3是本发明一实施例中四足状ZnO纳米结构的扫描电子显微镜(SEM)照片;3 is a scanning electron microscope (SEM) photograph of a tetrapod-shaped ZnO nanostructure in an embodiment of the present invention;
图4是本发明一实施例的柔性自支撑ZnO紫外探测器在暗态下和365nm光照下的电压-电流(I-V)特性曲线;4 is a voltage-current (I-V) characteristic curve of a flexible self-supporting ZnO UV detector in a dark state and 365 nm illumination according to an embodiment of the present invention;
图5是本发明一实施例的柔性自支撑ZnO紫外探测器处于弯曲状态时在暗态下和365nm光照下的电压-电流(I-V)特性曲线;Fig. 5 is the voltage-current (I-V) characteristic curve of the flexible self-supporting ZnO ultraviolet detector in the dark state and 365nm illumination when the flexible self-supporting ZnO ultraviolet detector according to an embodiment of the present invention is in a bent state;
图6是图4和图5的对比图。FIG. 6 is a comparison diagram of FIGS. 4 and 5 .
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白,下面结合附图和具体实施例对本发明作进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to illustrate the present invention, but not to limit the present invention.
为了使本揭示内容的叙述更加详尽与完备,下文针对本发明的实施方式与具体实施例提出了说明性的描述;但这并非实施或运用本发明具体实施例的唯一形式。实施方式中涵盖了多个具体实施例的特征以及用以建构与操作这些具体实施例的方法步骤与其顺序。然而,亦可利用其它具体实施例来达成相同或均等的功能与步骤顺序。In order to make the description of the present disclosure more detailed and complete, the following provides an illustrative description of the embodiments and specific embodiments of the present invention; but this is not the only form of implementing or using the specific embodiments of the present invention. The features of various specific embodiments as well as method steps and sequences for constructing and operating these specific embodiments are encompassed in the detailed description. However, other embodiments may also be utilized to achieve the same or equivalent function and sequence of steps.
本发明提供了一种柔性自支撑ZnO紫外探测器,如图1、2所示,包括:The present invention provides a flexible self-supporting ZnO UV detector, as shown in Figures 1 and 2, comprising:
四足状ZnO纳米结构层、设置于所述四足状ZnO纳米结构层表面的两个电极及柔性衬底;A tetrapod-shaped ZnO nanostructure layer, two electrodes disposed on the surface of the tetrapod-shaped ZnO nanostructure layer, and a flexible substrate;
所述四足状ZnO纳米结构层独立存在实现自支撑,通过转移置于所述柔性衬底上。The tetrapod-shaped ZnO nanostructure layer exists independently to realize self-support, and is placed on the flexible substrate by transferring.
其中,四足状ZnO纳米结构具有特殊的四足状结构,以四根纳米线为一个结构单元,四足直径为50~100nm,四足长度为2~5μm。每个结构单元紧密连接,结构相对牢固,当厚度足够大时可脱离衬底独立存在,堆叠成絮状自支撑结构,即四足状ZnO纳米结构层,厚度为50~1000μm。Among them, the tetrapod-shaped ZnO nanostructure has a special tetrapod-shaped structure, with four nanowires as a structural unit, the diameter of the tetrapods is 50-100 nm, and the length of the tetrapods is 2-5 μm. Each structural unit is closely connected, and the structure is relatively firm. When the thickness is large enough, it can exist independently from the substrate and stack into a floc-like self-supporting structure, that is, a tetrapod-like ZnO nanostructure layer with a thickness of 50-1000 μm.
其中,所述两个电极独立设计,采用本领域技术人员熟知的紫外探测器用电极即可。优选地,两个电极独立地选自In电极、Au电极、Ag电极或Al电极中的任意一种;电极厚度优选为30~50nm,更优选为35~45nm,最优选为40nm。两个电极的形状优选为圆形电极,直径优选为1~2mm,更优选为1.2~1.8mm,最优选为1.5mm。两个电极之间的距离优选≤1mm,更优选为0.2~1mm,最优选为0.5mm。Wherein, the two electrodes are designed independently, and electrodes for ultraviolet detectors well known to those skilled in the art may be used. Preferably, the two electrodes are independently selected from any of In electrodes, Au electrodes, Ag electrodes or Al electrodes; the thickness of the electrodes is preferably 30-50 nm, more preferably 35-45 nm, and most preferably 40 nm. The shape of the two electrodes is preferably a circular electrode, and the diameter is preferably 1 to 2 mm, more preferably 1.2 to 1.8 mm, and most preferably 1.5 mm. The distance between the two electrodes is preferably ≤ 1 mm, more preferably 0.2 to 1 mm, and most preferably 0.5 mm.
由于四足状ZnO纳米结构层能够自支撑,可以直接拿起来转移到任意衬底上,为柔性紫外探测器的衬底选择上提供更多可能,优选地,所述柔性衬底为聚对苯二甲酸乙二酯衬底或织布衬底。Since the tetrapod-shaped ZnO nanostructure layer can be self-supporting, it can be directly picked up and transferred to any substrate, which provides more possibilities for the substrate selection of flexible UV detectors. Preferably, the flexible substrate is polyparaphenylene Ethylene diformate backing or woven backing.
本发明还提供了上述柔性自支撑ZnO紫外探测器的制备方法,包括以下步骤:The present invention also provides a method for preparing the above flexible self-supporting ZnO UV detector, comprising the following steps:
S1:制备所述四足状ZnO纳米结构层;S1: preparing the tetrapod-shaped ZnO nanostructure layer;
S2:采用粘接的方式将所述两个电极固定于所述四足状ZnO纳米结构层上;S2: fixing the two electrodes on the tetrapod-shaped ZnO nanostructure layer by means of bonding;
S3:将粘接有所述两个电极的四足状ZnO纳米结构层转移到所述柔性衬底上,并压实固定,在压实前先铺上硫酸纸避免所述四足状ZnO纳米结构层在压实过程中受损伤、沾污,得到柔性自支撑ZnO紫外探测器。S3: Transfer the tetrapod-shaped ZnO nanostructure layer bonded with the two electrodes to the flexible substrate, and compact and fix it, and lay sulfuric acid paper before compaction to avoid the tetrapod-shaped ZnO nanostructure layer. The structural layer was damaged and stained during the compaction process, and a flexible self-supporting ZnO UV detector was obtained.
其中,所述步骤S1中制备所述四足状ZnO纳米结构层的方法为火焰传输法、化学气相沉积法、水热法中的任意一种。当采用化学气相沉积法制备所述四足状ZnO纳米结构层时,制备步骤如下:Wherein, the method for preparing the tetrapod-shaped ZnO nanostructure layer in the step S1 is any one of a flame transmission method, a chemical vapor deposition method, and a hydrothermal method. When using chemical vapor deposition to prepare the tetrapod-shaped ZnO nanostructure layer, the preparation steps are as follows:
S10:将ZnO粉末与石墨粉末按照1:1的质量比研磨混合均匀,之后置于化学气相沉积设备中作为生长源;S10: The ZnO powder and the graphite powder are ground and mixed uniformly according to the mass ratio of 1:1, and then placed in a chemical vapor deposition device as a growth source;
S11:在惰性气体保护下对化学气相沉积设备进行升温,升温控制参数为:(50±1)min从室温升至1000℃,(30±1)min从1000℃升至1130℃~1150℃;当温度上升至1000℃通入氧气,控制氧气流量为15~20sccm;S11: Heat up the chemical vapor deposition equipment under the protection of inert gas. The temperature control parameters are: (50±1)min from room temperature to 1000℃, (30±1)min from 1000℃ to 1130℃~1150℃ ; When the temperature rises to 1000°C, oxygen is introduced, and the oxygen flow rate is controlled to be 15-20sccm;
S12:在1130℃~1150℃温度下保温(60±1)min,用于生长沉积四足状ZnO纳米结构;S12: keep the temperature at 1130℃~1150℃ for (60±1)min to grow and deposit tetrapod-like ZnO nanostructures;
S13:沉积完成后降温至室温,用镊子直接分离取出即得述四足状ZnO纳米结构层。S13: After the deposition is completed, the temperature is lowered to room temperature, and the tetrapod-shaped ZnO nanostructure layer is obtained by directly separating and taking out with tweezers.
其中,所述惰性气体可以选择为氩气或氮气。当所述惰性气体为氩气时,氩气流量优选为90~110sccm。Wherein, the inert gas can be selected as argon or nitrogen. When the inert gas is argon, the flow rate of argon is preferably 90-110 sccm.
实施例1Example 1
本发明一实施例的柔性自支撑ZnO紫外探测器的制备方法,包括以下步骤:A method for preparing a flexible self-supporting ZnO UV detector according to an embodiment of the present invention includes the following steps:
S1:制备所述四足状ZnO纳米结构层,具体步骤为:S1: preparing the tetrapod-shaped ZnO nanostructure layer, the specific steps are:
S10:将ZnO粉末与石墨粉末按照1:1的质量比研磨混合均匀,之后置于化学气相沉积设备中作为生长源;S10: The ZnO powder and the graphite powder are ground and mixed uniformly according to the mass ratio of 1:1, and then placed in a chemical vapor deposition device as a growth source;
S11:在氩气的保护下对化学气相沉积设备进行升温,升温控制参数为:50min从室温升至1000℃,30min从1000℃升至1150℃;当温度上升至1000℃左右时通入氧气,控制氧气流量为16sccm;S11: The chemical vapor deposition equipment is heated under the protection of argon gas. The temperature control parameters are: from room temperature to 1000 °C in 50 minutes, and from 1000 °C to 1150 °C in 30 minutes; when the temperature rises to about 1000 °C, oxygen is introduced , control the oxygen flow to 16sccm;
S12:在1150℃温度下保温60min,用于生长沉积四足状ZnO纳米结构;S12: Incubate at 1150°C for 60min for growing and depositing tetrapod-like ZnO nanostructures;
S13:沉积完成后降温至室温,用镊子直接分离取出即得述四足状ZnO纳米结构层,厚度为50μm。S13: After the deposition is completed, the temperature is lowered to room temperature, and the tetrapod-shaped ZnO nanostructure layer is obtained by directly separating and taking out with tweezers, and the thickness is 50 μm.
S2:采用粘接的方式将所述两个电极固定于所述四足状ZnO纳米结构层上;所述两个电极均为圆形In粒电极,圆形直径为1.5mm,厚度为40nm,两个电极之间的间距为0.5mm。S2: The two electrodes are fixed on the tetrapod-shaped ZnO nanostructure layer by means of bonding; the two electrodes are circular In particle electrodes, the circular diameter is 1.5 mm, and the thickness is 40 nm, The spacing between the two electrodes is 0.5 mm.
S3:将粘接有所述两个电极的四足状ZnO纳米结构层转移到聚对苯二甲酸乙二酯柔性衬底上,并压实固定,在压实前先铺上硫酸纸避免所述四足状ZnO纳米结构层在压实过程中受损伤、沾污,得到柔性自支撑ZnO紫外探测器。S3: Transfer the tetrapod-shaped ZnO nanostructure layer with the two electrodes bonded to the polyethylene terephthalate flexible substrate, and compact and fix it. Before compaction, cover with sulfuric acid paper to avoid any The tetrapod-shaped ZnO nanostructure layer was damaged and stained during the compaction process, and a flexible self-supporting ZnO UV detector was obtained.
本实施例制备的四足状ZnO纳米结构层的扫描电子显微镜(SEM)照片如图3所示,四足直径为50nm,四足长度为3μm。The scanning electron microscope (SEM) photo of the tetrapod-shaped ZnO nanostructure layer prepared in this example is shown in FIG. 3 , the diameter of the tetrapod is 50 nm, and the length of the tetrapod is 3 μm.
性能测试:Performance Testing:
1)对处于平直状态下的本实施例制备的柔性自支撑ZnO紫外探测器,进行暗态下和365nm光照下的电压-电流(I-V)特性曲线测试,具体测试方法为:1) For the flexible self-supporting ZnO UV detector prepared by the present embodiment in a flat state, carry out the voltage-current (I-V) characteristic curve test under dark state and under 365nm illumination, and the specific test method is:
采用Agilent B1500型半导体分析仪设备对本实施例的柔性自支撑ZnO紫外探测器进行暗态和光态下的电压-电流性能测试。首先,用探针台将本实施例制备的柔性自支撑ZnO紫外探测器的两个电极与半导体分析仪连接,仪器与器件连接完毕后,将器件与整套系统暗态静置30分钟,然后进行测试。电压输出设定为-15V至+15V,取样间隔为100mV,得到数据即为器件暗态下的I-V特性图。之后利用一个中心波长365nm的紫外LED照射到本实施例制备的柔性自支撑ZnO紫外探测器的表面,在相同电压参数下再次进行测试得到器件光态下I-V特性图。The voltage-current performance test of the flexible self-supporting ZnO ultraviolet detector of this embodiment was carried out in the dark state and the light state by using the Agilent B1500 semiconductor analyzer equipment. First, use a probe station to connect the two electrodes of the flexible self-supporting ZnO UV detector prepared in this example to the semiconductor analyzer. After the connection between the instrument and the device is completed, the device and the whole system are left in a dark state for 30 minutes, and then the test. The voltage output is set from -15V to +15V, and the sampling interval is 100mV, and the obtained data is the I-V characteristic diagram of the device in the dark state. Then, a UV LED with a central wavelength of 365 nm was used to irradiate the surface of the flexible self-supporting ZnO UV detector prepared in this example, and the I-V characteristic diagram of the device under the optical state was obtained by testing again under the same voltage parameters.
结果如图4所示,可以看出,本实施例制备的柔性自支撑ZnO紫外探测器在平直状态下具有相对较低的暗电流,且光暗抑制比可达三个数量级。The results are shown in Fig. 4. It can be seen that the flexible self-supporting ZnO UV detector prepared in this example has a relatively low dark current in the flat state, and the light-dark suppression ratio can reach three orders of magnitude.
2)对处于弯曲状态下的本实施例制备的柔性自支撑ZnO紫外探测器,进行暗态下和365nm光照下的电压-电流(I-V)特性曲线测试,测试过程与上述测试一样,不同之处在于此时的柔性自支撑ZnO紫外探测器处于弯曲状态。2) For the flexible self-supporting ZnO UV detector prepared in the present embodiment in a bent state, a voltage-current (I-V) characteristic curve test in a dark state and under 365nm illumination is performed. The test process is the same as the above test, with the exception of At this time, the flexible self-supporting ZnO UV detector is in a bent state.
结果如图5所示,可以看出,本实施例制备的柔性自支撑ZnO紫外探测器在弯曲状态下同样具有相对较低的暗电流,且光暗抑制比可达三个数量级。The results are shown in Fig. 5. It can be seen that the flexible self-supporting ZnO UV detector prepared in this example also has a relatively low dark current in the bending state, and the light-dark suppression ratio can reach three orders of magnitude.
如图6所示,为本实施例的柔性自支撑ZnO紫外探测器在平直状态和弯曲状态时,暗态下和365nm光照下的电压-电流(I-V)特性曲线对比图,从图中可以看出,本实施例的柔性自支撑ZnO紫外探测器具有制备柔性器件的潜力。As shown in FIG. 6 , the voltage-current (I-V) characteristic curves of the flexible self-supporting ZnO UV detector of the present embodiment in the straight state and the bent state, under the dark state and under 365 nm illumination are compared. It can be seen that the flexible self-supporting ZnO UV detector of this embodiment has the potential to fabricate flexible devices.
本发明的柔性自支撑ZnO紫外探测器,采用四足状ZnO纳米结构层,具有特殊的四足状结构,以四根纳米线为一个单元,每个结构单元紧密连接,结构相对牢固,当厚度足够大时可脱离衬底独立存在,堆叠成絮状自支撑结构,为柔性紫外探测器的衬底选择上提供更多可能,有效解决现有ZnO微纳结构柔性紫外探测器中衬底不耐高温的问题;四足状ZnO纳米结构层结晶质量高、性能优异,光暗抑制比高,响应速度快,可以转移到柔性衬底上,简单且高效地获得响应速度快的柔性紫外探测器。本发明的柔性自支撑ZnO紫外探测器的制备方法简单、高效,四足状ZnO纳米结构层的制备过程可控可设计,可以实现对四足状ZnO纳米结构层的厚度进行设计。The flexible self-supporting ZnO ultraviolet detector of the present invention adopts a tetrapod-shaped ZnO nanostructure layer and has a special tetrapod-shaped structure. Four nanowires are used as a unit, each structural unit is closely connected, and the structure is relatively firm. When it is large enough, it can exist independently from the substrate, and can be stacked into a floc-like self-supporting structure, which provides more possibilities for the substrate selection of flexible UV detectors, and effectively solves the problem of substrate intolerance in the existing ZnO micro-nano structure flexible UV detectors. The problem of high temperature; the tetrapod-like ZnO nanostructure layer has high crystal quality, excellent performance, high light-dark suppression ratio, and fast response speed, which can be transferred to flexible substrates, and a flexible UV detector with fast response speed can be obtained simply and efficiently. The preparation method of the flexible self-supporting ZnO ultraviolet detector of the present invention is simple and efficient, the preparation process of the tetrapod ZnO nanostructure layer is controllable and can be designed, and the thickness of the tetrapod ZnO nanostructure layer can be designed.
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.
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