CN106011747A - Preparation method of flexible thermosensitive films - Google Patents
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Abstract
本发明涉及一种柔性热敏薄膜的制备方法，该方法涉及的高真空镀膜装置是由靶材、衬底、衬底盘、真空腔体、靶托和激光器组成。采用室温固相法，制备颗粒小且粒径分布均匀的纳米级陶瓷氧化物粉体；将粉体进行压片、烧结处理，获得高致密度的陶瓷靶材；采用高真空镀膜技术在聚酰亚胺衬底表面沉积锰钴镍基氧化物薄膜；对沉积所得薄膜进行后退火处理。以实现高质量、电学性能稳定的柔性热敏薄膜的批量化、产业化生产。本发明实现了室温条件下制备柔性热敏薄膜。该方法操作简单，容易实现，成本低廉，适用于各种陶瓷薄膜的制备，且具有可靠性好、成品率高、平整度高、厚度精确可控、内部均匀等优势，因此非常适合批量化生产，具有很大的应用前景。
The invention relates to a method for preparing a flexible heat-sensitive film. The high-vacuum film coating device involved in the method is composed of a target material, a substrate, a substrate disc, a vacuum cavity, a target holder and a laser. The room temperature solid phase method is used to prepare nano-scale ceramic oxide powder with small particles and uniform particle size distribution; the powder is pressed and sintered to obtain high-density ceramic targets; A manganese-cobalt-nickel-based oxide film is deposited on the surface of the imide substrate; post-annealing is performed on the deposited film. In order to realize the batch and industrialized production of flexible heat-sensitive films with high quality and stable electrical properties. The invention realizes the preparation of flexible heat-sensitive films under room temperature conditions. The method is simple to operate, easy to implement, and low in cost. It is suitable for the preparation of various ceramic thin films, and has the advantages of good reliability, high yield, high flatness, precise and controllable thickness, and uniform interior, so it is very suitable for mass production. , has great application prospects.
Description
技术领域technical field
本发明涉及一种柔性热敏薄膜的制备方法。The invention relates to a preparation method of a flexible thermosensitive film.
背景技术：Background technique:
由于柔性电子材料具有轻便、安装方便、环境适应性好、抗冲击力强等优点，因此已成为现代光电子器件研发及自旋电子学领域不可或缺的一个研究方向。近年来，随着柔性可穿戴设备、柔性红外隐身薄膜、柔性光电二极管、柔性热电半导体及柔性太阳能电池等研究的开展，越来越多的研究人员致力于柔性氧化物薄膜的研究。然而，具有负温度系数热敏电阻特性的柔性热敏电阻薄膜的研究还不多见。Due to the advantages of light weight, convenient installation, good environmental adaptability, and strong impact resistance, flexible electronic materials have become an indispensable research direction in the research and development of modern optoelectronic devices and spintronics. In recent years, with the development of flexible wearable devices, flexible infrared stealth films, flexible photodiodes, flexible thermoelectric semiconductors, and flexible solar cells, more and more researchers have devoted themselves to the research of flexible oxide films. However, studies on flexible thermistor films with negative temperature coefficient thermistor properties are rare.
Mn1.56Co0.96Ni0.48O4±δ材料是研究最为广泛的负温度系数(Negative TemperatureCoefficient，NTC)热敏电阻材料之一，相比于其他锰钴镍基氧化物陶瓷材料，它具有更高的电阻温度系数(>3％/K)，更低的室温电阻率(250Ω·cm)，且在高温环境下具有更稳定的电学性能，因而被广泛地用于制备成商用负温度系数热敏电阻元件。其中，Mn1.56Co0.96Ni0.48O4±δ薄膜材料是制备快响应温度传感器和非浸没式红外探测器的常见基础元件之一。当下，受薄膜制备技术和元件生产手段的限制，敏感薄膜通常被制备在Si/SiOx，玻璃，非晶Al2O3,Si/SiOx/Ti/Pt,SrTiO3(100)等刚性衬底上。而对于柔性热敏薄膜的研究，也大多是先在刚性衬底上沉积一层聚酰亚胺膜材料，再在聚酰亚胺膜材料表面生长热敏薄膜，最后将刚性衬底去除，保留以柔性聚酰亚胺为衬底的柔性薄膜材料。采用这种方法尽管可以获得柔性热敏薄膜，但工艺复杂且成本高，并不利于柔性热敏薄膜的产业化发展。Mn 1.56 Co 0.96 Ni 0.48 O 4±δ material is one of the most widely studied negative temperature coefficient (Negative Temperature Coefficient, NTC) thermistor materials. Compared with other manganese-cobalt-nickel-based oxide ceramic materials, it has higher Temperature coefficient of resistance (>3%/K), lower room temperature resistivity (250Ω cm), and more stable electrical properties in high temperature environments, so it is widely used to prepare commercial negative temperature coefficient thermistors element. Among them, Mn 1.56 Co 0.96 Ni 0.48 O 4±δ thin film material is one of the common basic components for the preparation of fast response temperature sensors and non-immersion infrared detectors. At present, due to the limitations of thin film preparation technology and component production methods, sensitive thin films are usually prepared on rigid substrates such as Si/SiO x , glass, amorphous Al 2 O 3 , Si/SiO x /Ti/Pt, SrTiO 3 (100), etc. on the bottom. For the research on flexible heat-sensitive films, most of them first deposit a layer of polyimide film material on the rigid substrate, then grow a heat-sensitive film on the surface of the polyimide film material, and finally remove the rigid substrate, leaving Flexible film material based on flexible polyimide substrate. Although flexible heat-sensitive films can be obtained by using this method, the process is complicated and the cost is high, which is not conducive to the industrial development of flexible heat-sensitive films.
本发明中，我们采用高真空镀膜技术直接在市场上有售的聚酰亚胺薄膜材料上沉积一层热敏氧化物薄膜。由于高真空镀膜沉积可实现材料低温结晶，因此能够解决有机衬底无法耐受薄膜结晶过程中需高温处理的缺点，一步制备出具有负温度系数热敏电阻特性的柔性薄膜材料。这种方法同时由于具有操作简便，成本低廉等优势，实现了柔性热敏薄膜的产业化成产。In the present invention, we use high vacuum coating technology to directly deposit a layer of heat-sensitive oxide film on the commercially available polyimide film material. Because high-vacuum coating deposition can achieve low-temperature crystallization of materials, it can solve the shortcomings of organic substrates that cannot withstand high-temperature treatment during the film crystallization process, and prepare flexible film materials with negative temperature coefficient thermistor characteristics in one step. At the same time, due to the advantages of simple operation and low cost, this method realizes the industrial production of flexible heat-sensitive films.
发明内容Contents of the invention
本发明目的在于，提供一种柔性热敏薄膜的制备方法，该方法涉及的高真空镀膜装置是由靶材、衬底、衬底盘、真空腔体、靶托和激光器组成。制备颗粒小且粒径分布均匀的纳米级陶瓷氧化物粉体；将粉体进行压片、烧结处理，获得高致密度的陶瓷靶材；采用高真空镀膜设备在聚酰亚胺衬底表面沉积锰钴镍基氧化物薄膜，对沉积所得薄膜进行后退火处理。以实现高质量、电学性能稳定的柔性热敏薄膜的批量化、产业化生产。本发明实现了室温条件下制备柔性热敏薄膜。该方法操作简单，容易实现，成本低廉，适用于各种陶瓷薄膜的制备，且具有可靠性好、成品率高、平整度高、厚度精确可控、内部均匀等优势，因此非常适合批量化生产，具有很大的应用前景。The object of the present invention is to provide a method for preparing a flexible heat-sensitive film. The high-vacuum coating device involved in the method is composed of a target material, a substrate, a substrate disc, a vacuum cavity, a target holder and a laser. Prepare nanoscale ceramic oxide powder with small particles and uniform particle size distribution; press the powder into tablets and sinter to obtain high-density ceramic targets; use high-vacuum coating equipment to deposit on the surface of polyimide substrates For the manganese-cobalt-nickel-based oxide thin film, post-annealing is performed on the deposited thin film. In order to realize the batch and industrialized production of flexible heat-sensitive films with high quality and stable electrical properties. The invention realizes the preparation of flexible heat-sensitive films under room temperature conditions. The method is simple to operate, easy to implement, and low in cost. It is suitable for the preparation of various ceramic thin films, and has the advantages of good reliability, high yield, high flatness, precise and controllable thickness, and uniform interior, so it is very suitable for mass production. , has great application prospects.
本发明所述的一种柔性热敏薄膜的制备方法，该方法涉及的高真空镀膜装置是由靶材、衬底、衬底盘、真空腔体、靶托和激光器组成，在真空腔体(4)内将衬底(2)粘贴在衬底盘(3)上，将靶材(1)安装在靶托(5)上，具体操作按下列步骤进行：A method for preparing a flexible heat-sensitive film according to the present invention, the high vacuum coating device involved in the method is composed of a target material, a substrate, a substrate disk, a vacuum cavity, a target holder and a laser, and is placed in the vacuum cavity (4 ), paste the substrate (2) on the substrate plate (3), and install the target (1) on the target support (5), the specific operation is carried out according to the following steps:
a、制备氧化物纳米粉体：采用室温固相法制备锰钴镍基氧化物纳米粉体，按摩尔比Mn:Co:Ni＝52:32:16称取Mn2O3、Co2O3和NiO2粉体，放入玛瑙球磨罐中，并在罐内放入玛瑙球，球料体积比为1:1-3，将球磨罐安置在行星式球磨机上，研磨3-8h，使原料在研磨的过程中充分反应，然后将研磨产物粉体取出，放在马弗炉中，于温度850℃预烧1h，自然降温至室温，取出，再经手动研磨后得到锰钴镍基氧化物纳米粉体；a. Preparation of oxide nano-powder: Manganese-cobalt-nickel-based oxide nano-powder was prepared by room temperature solid-phase method, and Mn 2 O 3 and Co 2 O 3 were weighed according to the molar ratio Mn:Co:Ni=52:32:16 and NiO 2 powder, put into the agate ball mill jar, and put the agate ball in the jar, the volume ratio of ball to material is 1:1-3, put the ball mill jar on the planetary ball mill, grind for 3-8h, make the raw material Fully react during the grinding process, then take out the ground product powder, put it in a muffle furnace, pre-fire it at a temperature of 850°C for 1 hour, cool it down to room temperature naturally, take it out, and then manually grind it to obtain a manganese-cobalt-nickel-based oxide Nano powder;
b、制备陶瓷靶材(1)：取60g锰钴镍氧化物纳米粉体，在49MPa下压制成直径为60mm，厚度为5mm的圆柱体，将圆柱体埋在预烧过的氧化铝粉体中，放入马弗炉内，以1℃/分钟的速度逐渐将温度从室温升高至1200℃，烘烧6h，然后以1℃/min的速率降温至室温，取出打磨，抛光，得到具有立方相尖晶石结构的直径为55mm，厚度为3mm的锰钴镍氧陶瓷靶材(1)；b. Preparation of ceramic target (1): Take 60g of manganese-cobalt-nickel oxide nanopowder, press it into a cylinder with a diameter of 60mm and a thickness of 5mm under 49MPa, and bury the cylinder in the pre-fired alumina powder Put it into a muffle furnace, gradually increase the temperature from room temperature to 1200 °C at a rate of 1 °C/min, bake for 6 hours, then cool down to room temperature at a rate of 1 °C/min, take it out, grind it, and polish it to obtain A manganese-cobalt-nickel oxide ceramic target (1) having a cubic phase spinel structure with a diameter of 55 mm and a thickness of 3 mm;
c、衬底清洗(2)：选择厚度为0.01cm-0.3cm，面积为1cm×1cm的聚酰亚胺薄膜作为衬底(2)，首先将衬底(2)于温度300℃条件下进行预烧，然后将衬底(2)放在丙酮溶液中超声清洗5min，取出后放入无水乙醇溶液中超声清洗5min，最后用去离子水进行冲洗，并用氮***吹干，得到清洁的聚酰亚胺薄膜衬底(2)；c. Substrate cleaning (2): Select a polyimide film with a thickness of 0.01cm-0.3cm and an area of 1cm×1cm as the substrate (2), and firstly carry out the substrate (2) at a temperature of 300°C pre-fired, then put the substrate (2) in an acetone solution for ultrasonic cleaning for 5 minutes, take it out and put it in an absolute ethanol solution for ultrasonic cleaning for 5 minutes, and finally rinse it with deionized water and dry it with a nitrogen gun to obtain a clean poly Imide film substrate (2);
d、靶材(1)及衬底(2)安装：用导电银胶将已清洗干净的聚酰亚胺薄膜衬底(2)粘贴在衬底盘(3)上，将锰钴镍氧陶瓷靶材(1)安装在真空腔体(4)内部的靶托(5)上，锰钴镍氧陶瓷靶材(1)与聚酰亚胺薄膜衬底(2)之间的距离为60-100mm；d. Target (1) and substrate (2) installation: Paste the cleaned polyimide film substrate (2) on the substrate disk (3) with conductive silver glue, and place the manganese-cobalt-nickel-oxygen ceramic target The material (1) is installed on the target holder (5) inside the vacuum chamber (4), and the distance between the manganese-cobalt-nickel oxide ceramic target (1) and the polyimide film substrate (2) is 60-100mm ;
e、锰钴镍基氧化物柔性薄膜的制备：采用高真空镀膜技术在聚酰亚胺薄膜衬底(2)上沉积步骤a得到的锰钴镍基氧化物薄膜，保持腔体(4)密封状态良好，用机械泵和分子泵抽取背景真空至5×10-4Pa，聚酰亚胺薄膜衬底(2)温度由室温升至250℃，在锰钴镍基氧化物薄膜沉积过程中，采用KrF 248nm激光器(6)，将能量为160-380mJ的激光(7)以1-4Hz的频率作用在锰钴镍氧陶瓷靶材(1)上，使得锰钴镍氧陶瓷靶材(1)被激光(7)烧蚀，产生形状为扇形的等离子体羽辉(8)，再将羽辉(8)溅射在聚酰亚胺薄膜衬底(2)上，溅射时间3-6h，沉积形成50nm-300nm薄膜，薄膜沉积完毕，依次关闭分子泵和机械泵，将聚酰亚胺衬底(2)温度缓慢降至室温，打开放气阀，将样品取出；e. Preparation of manganese-cobalt-nickel-based oxide flexible film: use high-vacuum coating technology to deposit the manganese-cobalt-nickel-based oxide film obtained in step a on the polyimide film substrate (2), and keep the cavity (4) sealed The condition is good, the background vacuum is pumped to 5×10 -4 Pa by mechanical pump and molecular pump, the temperature of polyimide film substrate (2) rises from room temperature to 250°C, during the deposition process of manganese-cobalt-nickel-based oxide film , using a KrF 248nm laser (6), the laser (7) with an energy of 160-380mJ acts on the manganese-cobalt-nickel-oxygen ceramic target (1) at a frequency of 1-4Hz, so that the manganese-cobalt-nickel-oxygen ceramic target (1 ) is ablated by the laser (7) to generate a fan-shaped plasma plume (8), and then the plume (8) is sputtered on the polyimide film substrate (2), and the sputtering time is 3-6h , deposit and form a 50nm-300nm thin film, after the thin film is deposited, turn off the molecular pump and the mechanical pump in turn, slowly lower the temperature of the polyimide substrate (2) to room temperature, open the vent valve, and take out the sample;
f、薄膜退火：将沉积所得薄膜放入快速退火炉中，在温度300℃条件下，空气中进行快速退火，时间为20秒，即得到柔性热敏薄膜。f. Film annealing: put the deposited film into a rapid annealing furnace, and perform rapid annealing in air at a temperature of 300° C. for 20 seconds to obtain a flexible heat-sensitive film.
步骤e中所述的高真空镀膜为指激光分子束外延技术或激光脉冲沉积技术。The high vacuum coating described in step e refers to laser molecular beam epitaxy or laser pulse deposition technology.
步骤e中所述的薄膜沉积过程中，激光能量和频率为可调。During the film deposition process described in step e, laser energy and frequency are adjustable.
本发明所述一种柔性热敏薄膜的制备方法，其特点为：真空镀膜技术利用激光能量补偿了材料低温结晶过程中缺少的能量，有效地克服了聚酰亚胺有机材料无法耐受高于300℃温度的缺点，解决了有机衬底上沉积锰钴镍基氧化物薄膜后无法高温处理，难以结晶的技术瓶颈问题。再者，由于高真空镀膜技术具有高度可控的优势，因此可根据需要实现一致性好、厚度精确可控的氧化物薄膜的制备，实现该柔性薄膜的批量化、产业化生产。该方法适用于各种材料体系，对不同的氧化物陶瓷柔性薄膜均具有适用性。该方法容易实现，成本低廉，为制备高精度、高互换性微型器件和柔性可穿戴器件打下了良好的基础，可以实现产业化生产。The preparation method of a flexible heat-sensitive film according to the present invention is characterized in that the vacuum coating technology uses laser energy to compensate for the lack of energy in the low-temperature crystallization process of the material, effectively overcoming the inability of the polyimide organic material to withstand a temperature higher than The disadvantage of the temperature of 300°C solves the technical bottleneck problem that the manganese-cobalt-nickel-based oxide film cannot be processed at high temperature and is difficult to crystallize after depositing the manganese-cobalt-nickel oxide film on the organic substrate. Furthermore, due to the highly controllable advantages of high-vacuum coating technology, the preparation of oxide films with good consistency and precise and controllable thickness can be realized according to needs, and the batch and industrial production of this flexible film can be realized. The method is applicable to various material systems, and has applicability to different oxide ceramic flexible films. The method is easy to implement and low in cost, and lays a good foundation for preparing high-precision, highly interchangeable micro devices and flexible wearable devices, and can realize industrial production.
附图说明Description of drawings
图1为本发明高真空镀膜设备示意图。Fig. 1 is a schematic diagram of the high vacuum coating equipment of the present invention.
图2为本发明制备所得柔性热敏薄膜的示意图。Fig. 2 is a schematic diagram of the flexible heat-sensitive film prepared in the present invention.
图3为本发明制备所得柔性热敏薄膜的电阻-温度关系图。Fig. 3 is a resistance-temperature relationship diagram of the flexible thermosensitive film prepared in the present invention.
具体实施方式detailed description
实施例1Example 1
本发明所述的一种柔性热敏薄膜的制备方法，该方法涉及的高真空镀膜装置是由靶材、衬底、衬底盘、真空腔体、靶托和激光器组成，在真空腔体4内将衬底2粘贴在衬底盘3上，将靶材1安装在靶托5上(图1)，具体操作按下列步骤进行：A method for preparing a flexible heat-sensitive film according to the present invention, the high vacuum coating device involved in the method is composed of a target material, a substrate, a substrate plate, a vacuum cavity, a target holder and a laser, and in the vacuum cavity 4 Paste the substrate 2 on the substrate disc 3, install the target 1 on the target holder 5 (Fig. 1), the specific operation is carried out according to the following steps:
a、采用室温固相法制备锰钴镍基氧化物纳米粉体及陶瓷靶材：按摩尔比Mn:Co:Ni＝52:32:16称取Mn2O3、Co2O3和NiO2粉体，将三种氧化物原料放入玛瑙球磨罐中，并在罐内放入玛瑙球，球料体积比为1:1，将球磨罐安置在行星式球磨机上，研磨8h，使原料在研磨的过程中充分反应，然后将研磨产物粉体取出，放在马弗炉中，于温度850℃预烧1h，自然降温至室温，取出，再经手动研磨后得到锰钴镍基氧化物纳米粉体；a. Preparation of manganese-cobalt-nickel-based oxide nanopowder and ceramic target by room temperature solid-phase method: Weigh Mn 2 O 3 , Co 2 O 3 and NiO 2 according to the molar ratio of Mn:Co:Ni=52:32:16 Powder, put the three kinds of oxide raw materials into the agate ball mill jar, and put agate balls in the jar, the volume ratio of the ball to material is 1:1, place the ball mill jar on the planetary ball mill, grind for 8 hours, and make the raw materials in the Fully react during the grinding process, then take out the ground product powder, put it in a muffle furnace, pre-fire it at a temperature of 850°C for 1 hour, cool it down to room temperature naturally, take it out, and then manually grind it to obtain a manganese-cobalt-nickel-based oxide nanometer Powder;
b、制备陶瓷靶材1：取60g锰钴镍氧化物纳米粉末，在49MPa下压制成直径为60mm，厚度为5mm的圆柱体，将圆柱体埋在预烧过的氧化铝粉体中，放入马弗炉内，以1℃/分钟的速度逐渐将温度从室温升高至1200℃，烘烧6小时，然后以1℃/每分钟的速率降温至室温，取出后打磨，抛光，得到具有良好致密度，直径55mm，厚度为3mm的立方相尖晶石结构的锰钴镍氧陶瓷靶材1；b. Preparation of ceramic target material 1: Take 60g of manganese-cobalt-nickel oxide nano-powder, press it into a cylinder with a diameter of 60mm and a thickness of 5mm under 49MPa, bury the cylinder in pre-fired alumina powder, put Put it into a muffle furnace, gradually increase the temperature from room temperature to 1200 °C at a rate of 1 °C/min, bake for 6 hours, then cool down to room temperature at a rate of 1 °C/min, take it out, grind and polish, and get Manganese-cobalt-nickel-oxygen ceramic target with good density, 55mm in diameter and 3mm in thickness with cubic phase spinel structure;
c、选择尺寸为1cm×1cm×0.3cm的聚酰亚胺薄膜作为衬底2，首先将衬底2于温度300℃条件下进行预烧，然后将衬底2放在丙酮溶液中超声清洗5分钟，取出后放入无水乙醇溶液中超声清洗5分钟，最后用去离子水进行冲洗后用氮***吹干，得到聚酰亚胺薄膜衬底2；c. Select a polyimide film with a size of 1cm×1cm×0.3cm as the substrate 2, first pre-fire the substrate 2 at a temperature of 300°C, and then put the substrate 2 in an acetone solution for ultrasonic cleaning 5 Minutes, after taking it out, put it into an anhydrous ethanol solution and ultrasonically clean it for 5 minutes, finally rinse it with deionized water and dry it with a nitrogen gun to obtain a polyimide film substrate 2;
d、靶材1及衬底2安装：用导电银胶将已清洗干净的聚酰亚胺衬底2粘贴在衬底盘3上，将锰钴镍基陶瓷靶材1安装在真空腔体4内的靶托5上，锰钴镍氧陶瓷靶材1与聚酰亚胺衬底2之间的距离为100mm；d. Installation of target 1 and substrate 2: Paste the cleaned polyimide substrate 2 on the substrate disk 3 with conductive silver glue, and install the manganese-cobalt-nickel-based ceramic target 1 in the vacuum chamber 4 On the target holder 5, the distance between the manganese-cobalt-nickel-oxygen ceramic target 1 and the polyimide substrate 2 is 100 mm;
e、锰钴镍基氧化物柔性薄膜的制备：采用高真空镀膜为激光分子束外延技术在聚酰亚胺衬底2上沉积步骤a得到的锰钴镍基氧化物薄膜，保持腔体4密封状态良好，用机械泵和分子泵抽取背景真空至5×10-4Pa，聚酰亚胺衬底2温度由室温升至250℃，在薄膜沉积过程中，采用KrF(248nm)激光器6，将能量为160mJ之间的激光7以1Hz的激光频率作用在锰钴镍氧陶瓷靶材1上，使得锰钴镍氧陶瓷靶材1受热被烧蚀，产生形状为扇形的等离子体羽辉8，再将羽辉8溅射在聚酰亚胺衬底2上，溅射时间3h，沉积形成50nm薄膜，沉积完毕，依次关闭分子泵和机械泵，将聚酰亚胺衬底2温度缓慢降至室温，打开放气阀，将样品取出；e. Preparation of manganese-cobalt-nickel-based oxide flexible film: use high-vacuum coating as laser molecular beam epitaxy to deposit the manganese-cobalt-nickel-based oxide film obtained in step a on the polyimide substrate 2, and keep the cavity 4 sealed The condition is good, the background vacuum is pumped to 5×10 -4 Pa with mechanical pump and molecular pump, the temperature of polyimide substrate 2 is raised from room temperature to 250°C, and KrF (248nm) laser 6 is used during film deposition, A laser 7 with an energy between 160mJ and a laser frequency of 1 Hz is applied to the manganese-cobalt-nickel-oxygen ceramic target 1, so that the manganese-cobalt-nickel-oxygen ceramic target 1 is heated and ablated, and a fan-shaped plasma plume 8 is generated. , and then sputtered Yuhui 8 on the polyimide substrate 2, and the sputtering time was 3 hours to deposit and form a 50nm thin film. to room temperature, open the vent valve, and take out the sample;
f、薄膜退火：将沉积所得薄膜放入快速退火炉中，在温度300℃条件下，空气中进行快速退火，退火时间为20秒，即得到柔性热敏薄膜(图2)。f. Film annealing: put the deposited film into a rapid annealing furnace, and perform rapid annealing in air at a temperature of 300° C. for 20 seconds to obtain a flexible heat-sensitive film ( FIG. 2 ).
实施例2Example 2
本发明所述方法中涉及的高真空镀膜装置与实施例1相同，具体操作按下列步骤进行：The high vacuum coating device involved in the method of the present invention is the same as that of Example 1, and the specific operation is carried out according to the following steps:
a、采用室温固相法制备锰钴镍基氧化物纳米粉体及陶瓷靶材：按摩尔比Mn:Co:Ni＝52:32:16称取Mn2O3、Co2O3和NiO2粉体，将三种氧化物原料放入玛瑙球磨罐中，并在罐内放入玛瑙球，球料体积比为1:2，将球磨罐安置在行星式球磨机上，研磨3h，使原料在研磨的过程中充分反应，然后将研磨产物粉体取出，放在马弗炉中，于温度850℃预烧1h，自然降温至室温，取出，再经手动研磨后得到锰钴镍基氧化物纳米粉体；a. Preparation of manganese-cobalt-nickel-based oxide nanopowder and ceramic target by room temperature solid-phase method: Weigh Mn 2 O 3 , Co 2 O 3 and NiO 2 according to the molar ratio of Mn:Co:Ni=52:32:16 powder, put the three kinds of oxide raw materials into the agate ball mill jar, and put agate balls in the jar, the volume ratio of the ball to material is 1:2, place the ball mill jar on the planetary ball mill, grind for 3 hours, and make the raw materials in the Fully react during the grinding process, then take out the ground product powder, put it in a muffle furnace, pre-fire it at a temperature of 850°C for 1 hour, cool it down to room temperature naturally, take it out, and then manually grind it to obtain a manganese-cobalt-nickel-based oxide nanometer Powder;
b、制备陶瓷靶材1：取60g锰钴镍氧化物纳米粉末，在49MPa下压制成直径为60mm，厚度为5mm的圆柱体，将圆柱体埋在预烧过的氧化铝粉体中，放入马弗炉内，以1℃/分钟的速度逐渐将温度从室温升高至1200℃，烘烧6小时，然后以1℃/每分钟的速率降温至室温，取出后打磨，抛光，得到具有良好致密度，直径55mm，厚度为3mm的立方相尖晶石结构的锰钴镍氧陶瓷靶材1；b. Preparation of ceramic target material 1: Take 60g of manganese-cobalt-nickel oxide nano-powder, press it into a cylinder with a diameter of 60mm and a thickness of 5mm under 49MPa, bury the cylinder in pre-fired alumina powder, put Put it into a muffle furnace, gradually increase the temperature from room temperature to 1200 °C at a rate of 1 °C/min, bake for 6 hours, then cool down to room temperature at a rate of 1 °C/min, take it out, grind and polish, and get Manganese-cobalt-nickel-oxygen ceramic target with good density, 55mm in diameter and 3mm in thickness with cubic phase spinel structure;
c、选择尺寸为1cm×1cm×0.01cm的聚酰亚胺薄膜作为衬底2，首先将衬底2于温度300℃条件下进行预烧，然后将衬底2放在丙酮溶液中超声清洗5分钟，取出后放入无水乙醇溶液中超声清洗5分钟，最后用去离子水进行冲洗后用氮***吹干，得到聚酰亚胺衬底2；c. Select a polyimide film with a size of 1cm×1cm×0.01cm as the substrate 2, first pre-fire the substrate 2 at a temperature of 300°C, and then put the substrate 2 in an acetone solution for ultrasonic cleaning 5 Minutes, after taking it out, put it into an anhydrous ethanol solution and ultrasonically clean it for 5 minutes, finally rinse it with deionized water and dry it with a nitrogen gun to obtain a polyimide substrate 2;
d、靶材1及衬底2安装：用导电银胶将已清洗干净的聚酰亚胺衬底2粘贴在衬底盘3上，将锰钴镍氧陶瓷靶材1安装在真空腔体4内的靶托5上，锰钴镍氧陶瓷靶材1与聚酰亚胺衬底2之间的距离为60mm；d. Installation of target 1 and substrate 2: Paste the cleaned polyimide substrate 2 on the substrate disk 3 with conductive silver glue, and install the manganese-cobalt-nickel-oxygen ceramic target 1 in the vacuum chamber 4 On the target holder 5, the distance between the manganese-cobalt-nickel-oxygen ceramic target 1 and the polyimide substrate 2 is 60 mm;
e、锰钴镍基氧化物柔性薄膜的制备：采用高真空镀膜为激光脉冲沉积技术在聚酰亚胺柔性衬底2上沉积步骤a得到的锰钴镍基氧化物薄膜，保持腔体4密封状态良好，用机械泵和分子泵抽取背景真空至5×10-4Pa，聚酰亚胺衬底2温度由室温升至250℃，在薄膜沉积过程中，采用KrF(248nm)激光器6，将能量为380mJ之间的激光7以1Hz的激光频率作用在锰钴镍氧陶瓷靶材1上，使得锰钴镍氧陶瓷靶材1受热被烧蚀，产生形状为扇形的等离子体羽辉8，再让羽辉8溅射在聚酰亚胺衬底2上，溅射时间6h，沉积形成300nm薄膜，沉积完毕，依次关闭分子泵和机械泵，将聚酰亚胺衬底2温度缓慢降至室温，打开放气阀，将样品取出；e. Preparation of manganese-cobalt-nickel-based oxide flexible film: use high-vacuum coating as a laser pulse deposition technique to deposit the manganese-cobalt-nickel-based oxide film obtained in step a on the polyimide flexible substrate 2, and keep the cavity 4 sealed The condition is good, the background vacuum is pumped to 5×10 -4 Pa with mechanical pump and molecular pump, the temperature of polyimide substrate 2 is raised from room temperature to 250°C, and KrF (248nm) laser 6 is used during film deposition, A laser 7 with an energy between 380mJ and a laser frequency of 1 Hz is applied to the manganese-cobalt-nickel-oxygen ceramic target 1, so that the manganese-cobalt-nickel-oxygen ceramic target 1 is heated and ablated, and a fan-shaped plasma plume 8 is generated. , and then let Yuhui 8 be sputtered on the polyimide substrate 2, and the sputtering time is 6h, and a 300nm thin film is formed. to room temperature, open the vent valve, and take out the sample;
f、薄膜退火：将沉积所得薄膜放入快速退火炉中，在温度300℃条件下，空气中进行快速退火，退火时间为20秒，即得到柔性热敏薄膜(图2)。f. Film annealing: put the deposited film into a rapid annealing furnace, and perform rapid annealing in air at a temperature of 300° C. for 20 seconds to obtain a flexible heat-sensitive film ( FIG. 2 ).
实施例3Example 3
本发明所述方法中涉及的高真空镀膜装置与实施例1相同，具体操作按下列步骤进行：The high vacuum coating device involved in the method of the present invention is the same as that of Example 1, and the specific operation is carried out according to the following steps:
a、采用室温固相法制备锰钴镍基氧化物纳米粉体及陶瓷靶材：按摩尔比Mn:Co:Ni＝52:32:16称取Mn2O3、Co2O3和NiO2粉体，将三种氧化物原料放入玛瑙球磨罐中，并在罐内放入玛瑙球，球料体积比为1:3，将球磨罐安置在行星式球磨机上，研磨3h，使原料在研磨的过程中充分反应，然后将研磨产物粉体取出，放在马弗炉中，于温度850℃预烧1h，自然降温至室温，取出，再经手动研磨后得到锰钴镍基氧化物纳米粉体；a. Preparation of manganese-cobalt-nickel-based oxide nanopowder and ceramic target by room temperature solid-phase method: Weigh Mn 2 O 3 , Co 2 O 3 and NiO 2 according to the molar ratio of Mn:Co:Ni=52:32:16 Powder, put the three kinds of oxide raw materials into the agate ball mill jar, and put agate balls in the jar, the volume ratio of the ball to material is 1:3, place the ball mill jar on the planetary ball mill, grind for 3 hours, and make the raw materials in the Fully react during the grinding process, then take out the ground product powder, put it in a muffle furnace, pre-fire it at a temperature of 850°C for 1 hour, cool it down to room temperature naturally, take it out, and then manually grind it to obtain a manganese-cobalt-nickel-based oxide nanometer Powder;
b、制备陶瓷靶材1：取60g锰钴镍氧化物纳米粉末，在49MPa下压制成直径为60mm，厚度为5mm的圆柱体，将圆柱体埋在预烧过的氧化铝粉体中，放入马弗炉内，以1℃/分钟的速度逐渐将温度从室温升高至1200℃，烘烧6小时，然后以1℃/每分钟的速率降温至室温，取出后打磨，抛光，得到具有良好致密度，直径55mm，厚度为3mm的立方相尖晶石结构的锰钴镍氧陶瓷靶材1；b. Preparation of ceramic target material 1: Take 60g of manganese-cobalt-nickel oxide nano-powder, press it into a cylinder with a diameter of 60mm and a thickness of 5mm under 49MPa, bury the cylinder in pre-fired alumina powder, put Put it into a muffle furnace, gradually increase the temperature from room temperature to 1200 °C at a rate of 1 °C/min, bake for 6 hours, then cool down to room temperature at a rate of 1 °C/min, take it out, grind and polish, and get Manganese-cobalt-nickel-oxygen ceramic target with good density, 55mm in diameter and 3mm in thickness with cubic phase spinel structure;
c、选择尺寸为1cm×1cm×0.1cm的聚酰亚胺薄膜作为衬底2，首先将衬底2于温度300℃条件下进行预烧，然后将衬底2放在丙酮溶液中超声清洗5分钟，取出后放入无水乙醇溶液中超声清洗5分钟，最后用去离子水进行冲洗后用氮***吹干，得到聚酰亚胺衬底2；c. Select a polyimide film with a size of 1cm×1cm×0.1cm as the substrate 2, first pre-fire the substrate 2 at a temperature of 300°C, and then put the substrate 2 in an acetone solution for ultrasonic cleaning 5 Minutes, after taking it out, put it into an anhydrous ethanol solution and ultrasonically clean it for 5 minutes, finally rinse it with deionized water and dry it with a nitrogen gun to obtain a polyimide substrate 2;
d、靶材1及衬底2安装：用导电银胶将已清洗干净的聚酰亚胺衬底2粘贴在衬底盘3上，将锰钴镍氧陶瓷靶材1安装在真空腔体4内的靶托5上，锰钴镍氧陶瓷靶材1与聚酰亚胺衬底2之间的距离为80mm；d. Installation of target 1 and substrate 2: Paste the cleaned polyimide substrate 2 on the substrate disk 3 with conductive silver glue, and install the manganese-cobalt-nickel-oxygen ceramic target 1 in the vacuum chamber 4 On the target holder 5, the distance between the manganese-cobalt-nickel-oxygen ceramic target 1 and the polyimide substrate 2 is 80mm;
e、锰钴镍基氧化物柔性薄膜的制备：采用高真空镀膜为激光分子束外延技术在聚酰亚胺薄膜衬底2上沉积步骤a得到的锰钴镍基氧化物薄膜，保持腔体4密封状态良好，用机械泵和分子泵抽取背景真空至5×10-4Pa，聚酰亚胺衬底2温度由室温升至250℃，在薄膜沉积过程中，采用KrF(248nm)激光器6，将能量为250mJ之间的激光7以2Hz的激光频率作用在锰钴镍氧陶瓷靶材1上，使得锰钴镍氧陶瓷靶材1受热被烧蚀，产生形状为扇形的等离子体羽辉8，再让羽辉8溅射在聚酰亚胺衬底2上，溅射时间4h，沉积形成150nm薄膜，沉积完毕，依次关闭分子泵和机械泵，将聚酰亚胺衬底2温度缓慢降至室温，打开放气阀，将样品取出；e. Preparation of manganese-cobalt-nickel-based oxide flexible film: use high-vacuum coating as laser molecular beam epitaxy to deposit the manganese-cobalt-nickel-based oxide film obtained in step a on the polyimide film substrate 2, and keep the cavity 4 The sealing state is good, the background vacuum is pumped to 5×10 -4 Pa by mechanical pump and molecular pump, the temperature of polyimide substrate 2 is raised from room temperature to 250°C, and KrF (248nm) laser 6 is used in the process of film deposition , the laser 7 with an energy between 250mJ and a laser frequency of 2 Hz is applied to the manganese-cobalt-nickel-oxygen ceramic target 1, so that the manganese-cobalt-nickel-oxygen ceramic target 1 is heated and ablated, and a fan-shaped plasma plume is generated. 8. Then let Yuhui 8 be sputtered on the polyimide substrate 2. The sputtering time is 4 hours, and a 150nm thin film is deposited. Cool down to room temperature, open the vent valve, and take out the sample;
f、薄膜退火：将沉积所得薄膜放入快速退火炉中，在温度300℃条件下，空气中进行快速退火，退火时间为20秒，即得到柔性热敏薄膜(图2)。f. Film annealing: put the deposited film into a rapid annealing furnace, and perform rapid annealing in air at a temperature of 300° C. for 20 seconds to obtain a flexible heat-sensitive film ( FIG. 2 ).
实施例4Example 4
薄膜表征：将实施例1-3任意制备所得柔性热敏薄膜进行电学性能测试，薄膜的电阻随着测试温度的升高而呈指数关系降低(图3)。Film characterization: The electrical properties of the flexible heat-sensitive film prepared in any of Examples 1-3 were tested, and the resistance of the film decreased exponentially with the increase of the test temperature (Figure 3).
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| CN107192469A (en) * | 2017-06-07 | 2017-09-22 | 昆明理工大学 | A kind of low temperature temperature element based on layered cobalt oxide |
| CN110438567A (en) * | 2019-07-22 | 2019-11-12 | 中国科学院上海微***与信息技术研究所 | A kind of preparation method of semiconductor bismuth selenium oxide single crystal thin film material |
| CN111731517A (en) * | 2020-07-02 | 2020-10-02 | 北京卫星环境工程研究所 | A multi-layer thermal insulation component internal air release device |
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| CN107192469A (en) * | 2017-06-07 | 2017-09-22 | 昆明理工大学 | A kind of low temperature temperature element based on layered cobalt oxide |
| CN110438567A (en) * | 2019-07-22 | 2019-11-12 | 中国科学院上海微***与信息技术研究所 | A kind of preparation method of semiconductor bismuth selenium oxide single crystal thin film material |
| CN111731517A (en) * | 2020-07-02 | 2020-10-02 | 北京卫星环境工程研究所 | A multi-layer thermal insulation component internal air release device |
| CN111731517B (en) * | 2020-07-02 | 2021-10-08 | 北京卫星环境工程研究所 | A multi-layer thermal insulation component internal air release device |
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| CN106011747B (en) | 2019-06-28 |
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