CN106048527B - 一种制备柔性热敏薄膜材料的方法 - Google Patents

一种制备柔性热敏薄膜材料的方法 Download PDF

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CN106048527B
CN106048527B CN201610405808.7A CN201610405808A CN106048527B CN 106048527 B CN106048527 B CN 106048527B CN 201610405808 A CN201610405808 A CN 201610405808A CN 106048527 B CN106048527 B CN 106048527B
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吴敬
黄志明
周炜
江林
欧阳程
高艳卿
张飞
褚君浩
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Shanghai Institute of Technical Physics of CAS
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Abstract

本发明公开了一种制备柔性热敏薄膜的方法，该方法以MnCO3、Co2O3、Ni2O3粉末为原料经研磨、过筛、合成、细磨、预压成型、在富氧氛围下烧结成陶瓷靶材，然后以聚对苯二甲酸乙二醇酯和聚酰亚胺薄片为衬底片，采用射频磁控溅射方法室温下溅射沉积MCNO薄膜。本发明优点在于：1.在室温下完成溅射沉积，实现在聚对苯二甲酸乙二醇酯和聚酰亚胺等有机柔性衬底上沉积MCNO热敏薄膜。2.该方法制备的MCNO薄膜电阻率低，而负温度电阻系数高，有利提高器件的响应率和降低器件噪声。3.常温下制备，无需高温热处理，耗能低、节能环保。4.溅射沉积温度低，易于与Si基半导体工艺兼容，可以实现在Si基读出电路芯片上直接制备热敏元件，大大降低制作热敏型非制冷红外焦平面阵列成本。

Description

一种制备柔性热敏薄膜材料的方法
技术领域
本发明属于热敏红外探测薄膜材料制备方法领域，具体涉及到降低薄膜沉积温度、同时实现热敏材料的低电阻率和高负温度电阻系数的技术，从而满足在柔性衬底上沉积条件，实现柔性热敏薄膜材料制备。
背景技术
锰钴镍氧(MCNO)是一种尖晶石结构的负温度电阻系数(NTC)热敏材料，因其高的负温度电阻系数和良好的化学稳定性、宽广的使用温区而被广泛应用于热敏电阻器和微测热辐射计中，其应用领域包括温度传感、非制冷红外探测、夜视、地平仪、地球辐射收支探测等领域。用它所制备的器件具有200nm-50μm极宽阔的光响应波段，灵敏度高、时间常数小、寿命长和价格便宜等优点。
虽然目前有较多制备MCNO薄膜材料的方法，例如脉冲激光沉积、化学溶液法、屏幕印刷法等等，但这些方法通常需要600-1200℃的高温热处理来实现材料具有较高负温度电阻系数的同时保持较低的电阻率。高温热处理工艺严重制约了MCNO薄膜材料的制备工艺与工业化的半导体工艺的兼容性，也阻碍了在有机柔性衬底上沉积MCNO材料制备柔性热敏电阻元器件从而实现可穿戴设备的发展。
长期以来人们认为MCNO三元系材料具有一个最低电阻率值250Ωcm，本发明展示了一种常温下制备低电阻率(110Ωcm@295K)高负温度系数(-3.1％@295K)MCNO薄膜材料的方法，直接在柔性有机衬底上沉积MCNO薄膜材料，实现柔性热敏薄膜材料的高效制备。
发明内容
本发明包括靶材制备工艺，衬底选择，薄膜溅射沉积工艺,具体工艺方法如下：
1靶材制备
以纯度高于99.5％的MnCO3、Co2O3、Ni2O3粉末为原料，按原子比Mn：Co：Ni＝13:8:4充分混合，球磨混料8小时以上,烘干，过筛，装入氧化铝坩埚中合成，900℃，2小时。合成好的料加入玛瑙球和水，经24小时细磨，烘干。烘干后的粉料加入粘结剂，然后预压成型。将胚体放入高温炉中经过1170℃，8小时烧结，期间炉内保持富氧气氛(氧气分压0.06MPa)，机械打磨、清洗、烘干。
2衬底选择
厚度为0.06-0.2mm的柔性衬底为聚对苯二甲酸乙二醇酯和聚酰亚胺薄片。
3薄膜溅射沉积
采用射频磁控溅射方法沉积MCNO热敏薄膜。本底真空抽至3x10-7—8x10-8Torr之间，溅射时气压成分氩氧比20<Ar：O2<200，溅射压强3—10mTorr。有机柔性衬底片(聚对苯二甲酸乙二醇酯和聚酰亚胺)被置于样品托盘中距离靶材约20cm处，样品托盘自转速率2—20转/分钟，衬底温度为室温。溅射功率50—120W。所沉积获得的柔性衬底热敏薄膜材料在室温下(295K)其电阻率为100—200Ωcm，负温度电阻系数为-3.0—-4.0％。
本制备方法具有以下优点：
1、在室温下完成溅射沉积，实现在聚对苯二甲酸乙二醇酯和聚酰亚胺等有机柔性衬底上沉积MCNO热敏薄膜。
2、该方法制备的MCNO薄膜电阻率低，而负温度电阻系数高，有利提高器件的响应率和降低器件噪声。
3、常温下制备，无需高温热处理，耗能低、节能环保。
4、溅射沉积温度低，易于与Si基半导体工艺兼容，可以实现在Si基读出电路芯片上直接制备热敏元件，大大降低制作热敏型非制冷红外焦平面阵列成本。
附图说明
图1为柔性MCNO热敏材料实物图。
图2为温度-电阻率曲线。
图3为温度-负温度电阻系数曲线。
具体实施方式
下面提供通过实验研究得到的实施实例，并对本发明作进一步的详细说明。
实施例1：
按三种金属原子比为Mn:Co:Ni＝13:8:4把纯度高于99.5％的MnCO3、Co2O3、Ni2O3粉末进行充分搅拌混合，球磨混料8小时，过筛，装入氧化铝坩埚中合成，900℃，2小时。合成好的料加入玛瑙球和水，经24小时细磨，烘干。烘干后的粉料加入粘结剂，然后预压成型。将胚体放入高温炉中经过1170℃，8小时烧结，期间炉内保持富氧气氛，氧气分压0.06MPa，机械打磨、清洗、烘干。把制备好的靶材装入磁控溅射沉积设备，本底真空抽至2E-7Torr，溅射时气压成分氩氧比Ar：O2＝50：1，溅射压强3.7mTorr。有机柔性衬底片聚对苯二甲酸乙二醇酯被置于距离靶材20cm处。衬底自转速率5转/分钟，衬底温度为室温(～293K)。溅射功率50W。溅射沉积时间120小时，热敏薄膜材料厚度约9μm。所沉积获得的柔性热敏薄膜材料在室温下(295K)其电阻率为112.0Ωcm，负温度电阻系数为-3.1％。
实施例2：
按三种金属原子比为Mn:Co:Ni＝13:8:4把纯度高于99.5％的MnCO3、Co2O3、Ni2O3粉末进行充分搅拌混合，球磨混料8小时，过筛，装入氧化铝坩埚中合成，900℃，2小时。合成好的料加入玛瑙球和水，经24小时细磨，烘干。烘干后的粉料加入粘结剂，然后预压成型。将胚体放入高温炉中经过1170℃，8小时烧结，期间炉内保持富氧气氛，氧气分压0.06MPa，机械打磨、清洗、烘干。把制备好的靶材装入磁控溅射沉积设备，本底真空抽至2E-7Torr，溅射时气压成分氩氧比Ar：O2＝50：1，溅射压强3.7mTorr。有机柔性衬底片聚对苯二甲酸乙二醇酯被置于距离靶材20cm处。衬底自转速率5转/分钟，衬底温度为室温(～293K)。溅射功率80W。溅射沉积时间72小时，热敏薄膜材料厚度约9μm。所沉积获得的柔性热敏薄膜材料在室温下(295K)其电阻率为152.0Ωcm，负温度电阻系数为-3.4％。
实施例3：
按三种金属原子比为Mn:Co:Ni＝13:8:4把纯度高于99.5％的MnCO3、Co2O3、Ni2O3粉末进行充分搅拌混合，球磨混料8小时，过筛，装入氧化铝坩埚中合成，900℃，2小时。合成好的料加入玛瑙球和水，经24小时细磨，烘干。烘干后的粉料加入粘结剂，然后预压成型。将胚体放入高温炉中经过1170℃，8小时烧结，期间炉内保持富氧气氛，氧气分压0.06MPa，机械打磨、清洗、烘干。把制备好的靶材装入磁控溅射沉积设备，本底真空抽至2E-7Torr，溅射时气压成分氩氧比Ar：O2＝50：1，溅射压强10mTorr。有机柔性衬底片聚对苯二甲酸乙二醇酯被置于距离靶材20cm处。衬底自转速率5转/分钟，衬底温度为室温(～293K)。溅射功率50W。溅射沉积时间80小时，热敏薄膜材料厚度约9μm。所沉积获得的柔性热敏薄膜材料在室温下(295K)其电阻率为121.0Ωcm，负温度电阻系数为-3.3％。

Claims (1)

1.一种制备柔性热敏薄膜的方法，其特征在于包括以下步骤：
(1)靶材制作：
①以纯度高于99.5％的MnCO3、Co2O3、Ni2O3粉末为原料，按Mn、Co、Ni三种元素的原子数比为13：8：4进行配比，混合球磨混料8小时以上,烘干，过筛；
②装入氧化铝坩埚中合成，900℃，2小时；
③合成好的料加入玛瑙球和水，经24小时细磨，烘干；
④烘干后的粉料加入粘结剂，然后预压成型；
⑤将胚体放入高温炉中经过1170℃，8小时烧结，期间炉内保持富氧气氛，氧气分压0.06MPa；
⑥机械打磨、清洗、烘干；
(2)衬底选择：
衬底选用厚度为0.06—0.2mm的聚对苯二甲酸乙二醇酯或聚酰亚胺薄片；
(3)薄膜溅射沉积工艺：
①本底真空：3×10-7-8×10-8Torr；
②溅射气压3—10mTorr，溅射气氛氧氩比在1：200—1：20区间；
③衬底温度：20—40℃；
④溅射功率：50—120W；
⑤衬底托盘自转速率2—20转/分钟；
⑥连续沉积至膜厚9μm。
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Citations (2)

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CN1908229A (zh) * 2006-08-17 2007-02-07 中国科学院上海技术物理研究所 锰钴镍薄膜热敏材料的制备方法
CN101555587A (zh) * 2009-05-13 2009-10-14 长春理工大学 具有Al2O3缓冲层的硅衬底MgxZn1-xO薄膜磁控溅射制备方法

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JP2007095338A (ja) * 2005-09-27 2007-04-12 Toppan Printing Co Ltd 有機電界発光素子及びその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1908229A (zh) * 2006-08-17 2007-02-07 中国科学院上海技术物理研究所 锰钴镍薄膜热敏材料的制备方法
CN101555587A (zh) * 2009-05-13 2009-10-14 长春理工大学 具有Al2O3缓冲层的硅衬底MgxZn1-xO薄膜磁控溅射制备方法

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