CN114420925A - 一种n型磷化亚铜的制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011889 copper foil Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000011787 zinc oxide Substances 0.000 claims abstract description 20
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 40
- 239000010431 corundum Substances 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 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 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract
本发明公开了一种n型磷化亚铜的制备方法，包括如下步骤：S1、制备表面生长有磷化亚铜的铜箔；S2、将表面生长有磷化亚铜的铜箔作为基底，在其表面沉积氧化锌薄膜；S3、将步骤S2制备的产物在惰性气体中加热，热处理温度为650‑750℃，保温时长60‑300min。采用上述技术方案，在铜箔表面生长磷化亚铜连续薄膜，使用磁控溅射在磷化亚铜表面沉积氧化锌薄膜，高温下氧化锌与磷化亚铜相互作用，锌、氧元素扩散进入磷化亚铜晶格，形成n型掺杂磷化亚铜，该制备方法简单，重复性好，成本低，并且电阻率低、温差电动势高和光电响应快。
Description
技术领域
本发明涉及半导体材料技术领域，具体指一种n型磷化亚铜的制备方法。
背景技术
磷化亚铜是一种半导体材料，在锂离子电池电极材料、光催化分解有机物和电催化制氢等领域均有应用。半导体材料通过掺杂可改变载流子浓度、导电类型和其它性能，比如研究发现硼、硫、钴、氧掺杂能够提高其催化性能。但是目前市面上只有p型磷化亚铜，以及对p型磷化亚铜的研究和改善。至今还尚未有n型磷化亚铜的相关报道。
发明内容
本发明根据现有技术的不足，提出一种n型磷化亚铜的制备方法，通过掺杂制备了n型磷化亚铜，具有电阻率低、温差电动势高和光电反应快的优点。
本发明的技术方案为：
一种n型磷化亚铜制备方法，包括如下步骤：
S1、制备表面生长有磷化亚铜的铜箔；
S2、将表面生长有磷化亚铜的铜箔作为基底，在其表面沉积氧化锌薄膜；
S3、将步骤S2制备的产物在惰性气体中加热，热处理温度为650-750℃，保温时长60-300min。
作为优选，所述步骤S2中，所述表面生长有磷化亚铜的铜箔表面通过磁控溅射法沉积氧化锌薄膜。
作为优选，所述磁控溅射法所用设备的真空度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。
作为优选，所述磁控溅射法制备的氧化锌薄膜厚度为50-200nm。
作为优选，所述步骤S1的制备方法如下：
S1-1、将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖1-5平方厘米，厚度为250-1000微米的铜箔；
S1-2、将步骤S1-1的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；
S1-3、将步骤S1-2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，然后取出产物表面生长有磷化亚铜的铜箔。
作为优选，所述铜箔的厚度为600微米。
本发明具有以下的特点和有益效果：
采用上述技术方案，在铜箔表面沉积生长磷化亚铜连续薄膜，使用磁控溅射在磷化亚铜表面沉积氧化锌薄膜，高温下氧化锌与磷化亚铜相互作用，锌、氧元素扩散进入磷化亚铜晶格，形成n型掺杂磷化亚铜，该制备方法简单，重复性好，循环性能优异，稳定性好，成本低，并且电阻率低、温差电动势高和光电反应快，电化学性能整体有了明显的改善。
附图说明
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性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例所制备的n型磷化亚铜的X光衍射图；
图2为本发明实施例所制备的磷化亚铜温差电势随加热情况的变化图。
具体实施方式
实施例1
本实施例提供了一种n型磷化亚铜的制备方法，包括如下步骤：
S1、制备表面生长有磷化亚铜的铜箔；
S1-1、将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖1平方厘米，厚度为250微米的铜箔；
S1-2、将步骤S1-1的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；
S1-3、将步骤S1-2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，然后取出产物表面生长有磷化亚铜的铜箔；
S2、将步骤S1产物作为基底，通过磁控溅射法沉积氧化锌薄膜；磁控溅射设备真空度0.1Pa，氧气流量1sccm，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；
S3、将步骤S2的产物在惰性气体中加热，形成n型半导体磷化亚铜；热处理温度为650℃，保温时间120min。
上述技术方案中，在铜箔表面沉积生长磷化亚铜连续薄膜，使用磁控溅射在磷化亚铜表面沉积氧化锌薄膜，高温下氧化锌与磷化亚铜相互作用，锌、氧元素扩散进入磷化亚铜晶格，形成n型掺杂磷化亚铜，该制备方法简单，重复性好，循环性能优异，稳定性好，成本低，并且电阻率低、温差电动势高和光电反应快，电化学性能整体有了明显的改善。
需要说明的是，本实施例中的铜箔基底也可以为硅基底。
本实施例中采用磁控溅射法在磷化亚铜表面沉积氧化锌，也可以为溶胶凝胶法，化学气相沉积法，激光脉冲沉积法等物理方法。
实施例2
本实施例与实施例1的区别在于，包括如下步骤：
S1、制备表面生长有磷化亚铜的铜箔；
S1-1、将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖3平方厘米，厚度为500微米的铜箔；
S1-2、将步骤S1-1的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；
S1-3、将步骤S1-2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，然后取出产物表面生长有磷化亚铜的铜箔；
S2、将步骤S1产物作为基底，通过磁控溅射法沉积氧化锌薄膜；磁控溅射设备真空度0.6Pa，氧气流量3sccm，氩气流量40sccm，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120nm；
S3、将步骤S2的产物在惰性气体中加热，最后形成n型半导体磷化亚铜；热处理温度为700℃，保温时间180min。
实施例3
本实施例与实施例1的区别在于，包括如下步骤：
S1、制备表面生长有磷化亚铜的铜箔；
S1-1、将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖5平方厘米，厚度为1000微米的铜箔；
S1-2、将步骤S1-1的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；
S1-3、将步骤S1-2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，然后取出产物表面生长有磷化亚铜的铜箔；
S2、将步骤S1产物作为基底，通过磁控溅射法沉积氧化锌薄膜；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；
S3、将步骤S2的产物在惰性气体中加热，形成n型半导体磷化亚铜；热处理温度为750℃，保温时间300min。
结合实施例1-3制备的n型磷化亚铜，如图1所示，可以明显看出，通过实施例1-3制备n型磷化亚铜的X光衍射峰，其中43、74、90°为铜晶体的衍射峰，其他位置衍射峰来自n型磷化亚铜，由此可见本实施例所提供的技术方案制备出n型磷化亚铜，制备方法简单，重复性好，成本低，并且电阻率低、温差电动势高和光电响应快。
另外，通过图2可知，制备的n型磷化亚铜温差电动势随着加热时间的变化，图中，横坐标表示时间，纵坐标表示电势数值。正极加热后，电势为正值，表明掺杂后的磷化亚铜为n型半导体，即n型磷化亚铜。
Claims (6)
1.一种n型磷化亚铜的制备方法，其特征在于，包括如下步骤：
S1、制备表面生长有磷化亚铜的铜箔；
S2、将表面生长有磷化亚铜的铜箔作为基底，在其表面沉积氧化锌薄膜；
S3、将步骤S2制备的产物在惰性气体中加热，热处理温度为650-750℃，保温时长60-300min。
2.根据权利要求1所述的n型磷化亚铜的制备方法，其特征在于，所述步骤S2中，所述表面生长有磷化亚铜的铜箔表面通过磁控溅射法沉积氧化锌薄膜。
3.根据权利要求2所述的n型磷化亚铜的制备方法，其特征在于，所述磁控溅射法所用设备的真空度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。
4.根据权利要求2所述的n型磷化亚铜的制备方法，其特征在于，所述磁控溅射法制备的氧化锌薄膜厚度为50-200nm。
5.根据权利要求1所述的n型磷化亚铜的制备方法，其特征在于，所述步骤S1的制备方法如下：
S1-1、将次磷酸钠放入刚玉舟中，然后在刚玉舟表面覆盖1-5平方厘米，厚度为250-1000微米的铜箔；
S1-2、将步骤S1-1的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；
S1-3、将步骤S1-2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，然后取出产物表面生长有磷化亚铜的铜箔。
6.根据权利要求1所述的n型磷化亚铜的制备方法，其特征在于，所述铜箔的厚度为600微米。
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