CN114883488A - 一种氧化亚铜-磷化亚铜异质结的制备方法 - Google Patents
一种氧化亚铜-磷化亚铜异质结的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011787 zinc oxide Substances 0.000 claims abstract description 25
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 24
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
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- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 16
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- 229910052593 corundum Inorganic materials 0.000 claims description 56
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000010453 quartz Substances 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 239000011889 copper foil Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
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- 238000004544 sputter deposition Methods 0.000 claims description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
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- 238000004321 preservation Methods 0.000 claims description 4
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 3
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- 229910052737 gold Inorganic materials 0.000 abstract description 3
- 238000002207 thermal evaporation Methods 0.000 abstract description 3
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- 239000002184 metal Substances 0.000 description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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Abstract
本发明公开了一种氧化亚铜‑磷化亚铜异质结的制备方法，本发明先生成磷化亚铜薄膜，之后，在磷化亚铜表面沉积氧化锌薄膜，然后进行热处理，获得p型氧化亚铜。其次，采用模板法在磷化亚铜表面通过磁控溅射沉积氧化锌薄膜，氧化锌薄膜呈叉指形图案，热处理后，表面沉积有氧化锌的部分转变成p型氧化亚铜，形成p型氧化亚铜与p型磷化亚铜的面内异质结。通过热蒸发法在氧化亚铜和磷化亚铜区沉积金电极，制备成异质结器件。本发明制备的由p型氧化亚铜和p型磷化亚铜形成的异质结，成本低，重复性好，忆阻性能好。
Description
技术领域
本发明属于材料制备技术领域，具体涉及一种氧化亚铜-磷化亚铜异质结的制备方法。
背景技术
无机非金属半导体材料大多数表现出n型导电性能，如氧化锌，二氧化钛，铟掺杂氧化锡等，相对而言p型半导体材料相对较少。氧化亚铜与多数金属氧化物不同，通常表现出p型导电性质，因为理论分析表明，氧化亚铜本征缺陷的存在或引入不会形成n型磷化亚铜。氧化亚铜表现出较好的光电和荧光性能，随着忆阻器的认识和发展，氧化亚铜在忆阻器领域的应用研究也在发展中。相对于n型半导体材料，基于p型半导体材料忆阻器的研究相对少一些，导电类型的不同将有可能影响到器件忆阻性能，本专利通过构建全同型p型材料异质结，获得了忆阻器。
发明内容
本发明针对现有研究不足，首先提出了一种p型氧化亚铜-p型磷化亚铜异质结的制备方法。
本发明一种氧化亚铜-磷化亚铜异质结的制备方法，具体为：铜磷化后生成磷化亚铜薄膜，之后，在磷化亚铜表面沉积氧化锌薄膜，然后进行热处理，获得p型氧化亚铜。其次，采用模板法在磷化亚铜表面通过磁控溅射沉积氧化锌薄膜，氧化锌薄膜呈叉指形图案，热处理后，表面沉积有氧化锌的部分转变成p型氧化亚铜，形成p型氧化亚铜与p型磷化亚铜的面内异质结。通过热蒸发法在氧化亚铜和磷化亚铜区沉积金电极，制备成异质结器件。
步骤(1).制备磷化亚铜薄膜；
步骤(2).磷化亚铜薄膜表面放置掩膜版，通过磁控溅射法沉积氧化锌薄膜，氧化锌薄膜呈叉指电极形状；磁控溅射设备真空度0.1-1.0Pa，氧气流量1-5sccm，氩气流量20-50sccm，溅射电压300-450V，电流30-60mA，溅射时间20-40min，靶材为金属锌靶；制备的氧化锌薄膜厚度50-200nm；
步骤(3).步骤(3)产物放入管式炉的石英管中，充入惰性气体氩气，加热石英管，石英管升温速率20℃/min，升至760-850℃，并保温60-120min，之后石英管自然冷却至室温，获得由p型氧化亚铜和p型磷化亚铜形成的异质结。
作为优选，所述的制备磷化亚铜薄膜，具体包括以下步骤：
步骤(1).将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖厚度为250-1000微米的铜箔；
步骤(2).将刚玉舟放入刚玉管中，抽真空后，充入1个大气压的氩气，然后刚玉管两端密封；
步骤(3).将刚玉管通过管式炉加热至280～300℃，升温速率10℃/min；温度升至280～300℃后保温，保温时间为30～60min；然后自然冷却至室温，刚玉管抽真空去除管内残留气体，然后取出产物磷化亚铜薄膜。
作为优选，所述的铜箔替换为生长在氧化铝或氧化硅表面的铜薄膜。
作为优选，所述的铜箔的面积为1-5平方厘米。
作为优选，所述的铜箔厚度为600微米。
本发明的优点是：通过铜磷化法获得磷化亚铜薄膜；通过测控溅射法在磷化亚铜表面局部区域沉积氧化锌薄膜，氧化锌与磷化亚铜两者之间结合紧密，且不会改变磷化亚铜的组成和晶体结构。磷化亚铜薄膜局部沉积有氧化锌的部分，在高温下，经过原子扩散、化学反应以及锌、磷元素的高温挥发，形成p型氧化亚铜区域，n型氧化亚铜区与邻近的磷化亚铜区形成面内异质结。本发明制备的由p型氧化亚铜和p型磷化亚铜形成的异质结，成本低，重复性好，忆阻性能好。
附图说明
图1为本发明产物的结构示意图。
具体实施方式
实施例一：步骤(1).制备磷化亚铜薄膜；具体包括以下步骤：
步骤①.将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖面积为1平方厘米、厚度为250微米的铜箔；
步骤②.将刚玉舟放入刚玉管中，抽真空后，充入1个大气压的氩气，然后刚玉管两端密封；
步骤③.将刚玉管通过管式炉加热至280℃，升温速率10℃/min；温度升至280℃后保温，保温时间为30min；然后自然冷却至室温，刚玉管抽真空去除管内残留气体，然后取出产物磷化亚铜薄膜。
步骤(2).磷化亚铜薄膜表面放置掩膜版，通过磁控溅射法沉积氧化锌薄膜，氧化锌薄膜呈叉指电极形状；磁控溅射设备真空度0.1Pa，氧气流量2sccm，氩气流量20sccm，溅射电压300V，电流30mA，溅射时间20min，靶材为金属锌靶；制备的氧化锌薄膜厚度50nm；
步骤(3).步骤(2)产物放入管式炉的石英管中，充入惰性气体氩气，加热石英管，石英管升温速率20℃/min，升至760℃，并保温60min，之后石英管自然冷却至室温，获得由p型氧化亚铜和p型磷化亚铜形成的异质结；
步骤(4)、通过热蒸发法在氧化亚铜和磷化亚铜区沉积金电极，制备成异质结器件，如图1所示。
实施例二：
步骤(1).制备磷化亚铜薄膜；具体包括以下步骤：
步骤①.将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖面积为3平方厘米、厚度为600微米的铜箔；
步骤②.将刚玉舟放入刚玉管中，抽真空后，充入1个大气压的氩气，然后刚玉管两端密封；
步骤③.将刚玉管通过管式炉加热至290℃，升温速率10℃/min；温度升至290℃后保温，保温时间为40min；然后自然冷却至室温，刚玉管抽真空去除管内残留气体，然后取出产物磷化亚铜薄膜。
步骤(2).磷化亚铜薄膜表面放置掩膜版，通过磁控溅射法沉积氧化锌薄膜，氧化锌薄膜呈叉指电极形状；磁控溅射设备真空度0.5Pa，氧气流量3sccm，氩气流量30sccm，溅射电压400V，电流40mA，溅射时间30min，靶材为金属锌靶；制备的氧化锌薄膜厚度100nm；
步骤(3).步骤(3)产物放入管式炉的石英管中，充入惰性气体氩气，加热石英管，石英管升温速率20℃/min，升至790℃，并保温80min，之后石英管自然冷却至室温，获得由p型氧化亚铜和p型磷化亚铜形成的异质结。
实施例三：
步骤(1).制备磷化亚铜薄膜；具体包括以下步骤：
步骤①.将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖面积为5平方厘米、厚度为1000微米的铜箔；
步骤②.将刚玉舟放入刚玉管中，抽真空后，充入1个大气压的氩气，然后刚玉管两端密封；
步骤③.将刚玉管通过管式炉加热至300℃，升温速率10℃/min；温度升至300℃后保温，保温时间为60min；然后自然冷却至室温，刚玉管抽真空去除管内残留气体，然后取出产物磷化亚铜薄膜。
步骤(2).磷化亚铜薄膜表面放置掩膜版，通过磁控溅射法沉积氧化锌薄膜，氧化锌薄膜呈叉指电极形状；磁控溅射设备真空度1.0Pa，氧气流量5sccm，氩气流量50sccm，溅射电压450V，电流60mA，溅射时间40min，靶材为金属锌靶；制备的氧化锌薄膜厚度200nm；
步骤(3).步骤(3)产物放入管式炉的石英管中，充入惰性气体氩气，加热石英管，石英管升温速率20℃/min，升至850℃，并保温120min，之后石英管自然冷却至室温，获得由p型氧化亚铜和p型磷化亚铜形成的异质结。
实施例四：
步骤(1).制备磷化亚铜薄膜；具体包括以下步骤：
步骤①.将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖面积为3平方厘米、厚度为500微米的铜箔；所述的铜箔为氧化硅表面的铜薄膜；
步骤②.将刚玉舟放入刚玉管中，抽真空后，充入1个大气压的氩气，然后刚玉管两端密封；
步骤③.将刚玉管通过管式炉加热至290℃，升温速率10℃/min；温度升至290℃后保温，保温时间为50min；然后自然冷却至室温，刚玉管抽真空去除管内残留气体，然后取出产物磷化亚铜薄膜。
步骤(2).磷化亚铜薄膜表面放置掩膜版，通过磁控溅射法沉积氧化锌薄膜，氧化锌薄膜呈叉指电极形状；磁控溅射设备真空度0.8Pa，氧气流量3sccm，氩气流量30sccm，溅射电压380V，电流50mA，溅射时间30min，靶材为金属锌靶；制备的氧化锌薄膜厚度120nm；
步骤(3).步骤(3)产物放入管式炉的石英管中，充入惰性气体氩气，加热石英管，石英管升温速率20℃/min，升至800℃，并保温90min，之后石英管自然冷却至室温，获得由p型氧化亚铜和p型磷化亚铜形成的异质结。
实施例五：
步骤(1).制备磷化亚铜薄膜；具体包括以下步骤：
步骤①.将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖面积为5平方厘米、厚度为800微米的铜箔；所述的铜箔为氧化铝表面的铜薄膜；
步骤②.将刚玉舟放入刚玉管中，抽真空后，充入1个大气压的氩气，然后刚玉管两端密封；
步骤③.将刚玉管通过管式炉加热至300℃，升温速率10℃/min；温度升至300℃后保温，保温时间为45min；然后自然冷却至室温，刚玉管抽真空去除管内残留气体，然后取出产物磷化亚铜薄膜。
步骤(2).磷化亚铜薄膜表面放置掩膜版，通过磁控溅射法沉积氧化锌薄膜，氧化锌薄膜呈叉指电极形状；磁控溅射设备真空度0.9Pa，氧气流量4sccm，氩气流量30sccm，溅射电压450V，电流60mA，溅射时间40min，靶材为金属锌靶；制备的氧化锌薄膜厚度180nm；
步骤(3).步骤(3)产物放入管式炉的石英管中，充入惰性气体氩气，加热石英管，石英管升温速率20℃/min，升至850℃，并保温120min，之后石英管自然冷却至室温，获得由p型氧化亚铜和p型磷化亚铜形成的异质结。
Claims (6)
1.一种氧化亚铜-磷化亚铜异质结的制备方法，其特征在于，该方法具体包括以下步骤：
步骤(1).制备磷化亚铜薄膜；
步骤(2).磷化亚铜薄膜表面放置掩膜版，通过磁控溅射法沉积氧化锌薄膜，氧化锌薄膜呈叉指电极形状；磁控溅射设备真空度0.1-1.0Pa，氧气流量1-5sccm，氩气流量20-50sccm，溅射电压300-450V，电流30-60mA，溅射时间20-40min，靶材为金属锌靶；制备的氧化锌薄膜厚度50-200nm；
步骤(3).步骤(2)产物放入管式炉的石英管中，充入惰性气体氩气，加热石英管，石英管升温速率20℃/min，升至760-850℃，并保温60-120min，之后石英管自然冷却至室温，获得由p型氧化亚铜和p型磷化亚铜形成的异质结。
2.根据权利要求1所述的一种氧化亚铜-磷化亚铜异质结的制备方法，其特征在于：所述的制备磷化亚铜薄膜，具体包括以下步骤：
步骤(1).将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖厚度为250-1000微米的铜箔；
步骤(2).将刚玉舟放入刚玉管中，抽真空后，充入1个大气压的氩气，然后刚玉管两端密封；
步骤(3).将刚玉管通过管式炉加热至280～300℃，升温速率10℃/min；温度升至280～300℃后保温，保温时间为30～60min；然后自然冷却至室温，刚玉管抽真空去除管内残留气体，然后取出产物磷化亚铜薄膜。
3.根据权利要求1或2所述的一种氧化亚铜-磷化亚铜异质结的制备方法，其特征在于：所述的铜箔替换为生长在氧化铝或氧化硅表面的铜薄膜。
4.根据权利要求2所述的一种氧化亚铜-磷化亚铜异质结的制备方法，其特征在于：所述的铜箔的面积为1-5平方厘米。
5.根据权利要求2所述的一种氧化亚铜-磷化亚铜异质结的制备方法，其特征在于：所述的铜箔厚度为600微米。
6.根据权利要求2所述的一种氧化亚铜-磷化亚铜异质结的制备方法，其特征在于：所述的磷化亚铜导电类型为p型，氧化亚铜导电类型为p型。
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