CN110224064A - 一种基于BN(Al)薄膜的电阻开关及制备方法 - Google Patents
一种基于BN(Al)薄膜的电阻开关及制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 72
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 56
- 239000010703 silicon Substances 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000009977 dual effect Effects 0.000 claims abstract description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 9
- 238000004544 sputter deposition Methods 0.000 claims description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000007547 defect Effects 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 6
- 238000011105 stabilization Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005019 vapor deposition process Methods 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 abstract 4
- 230000000694 effects Effects 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 59
- 229910052582 BN Inorganic materials 0.000 description 58
- 239000000523 sample Substances 0.000 description 24
- 230000005611 electricity Effects 0.000 description 6
- 230000015654 memory Effects 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
- H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
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Abstract
本发明公开一种基于BN(Al)薄膜的电阻开关及制备方法,所述电阻开关,包括硅衬底,硅衬底的一面镀有金属层作为下电极,硅衬底的另一面设有BN(Al)薄膜,BN(Al)薄膜表面设有上电极;构成上电极/BN(Al)/下电极三明治结构电阻开关。本发明首次发现了BN(Al)薄膜具有电阻开关效应,制备成In/BN(Al)/Al三明治结构电阻开关具有良好的开关特性,且稳定性较好。本发明中利用双电源磁控溅射的方式制备BN(Al)薄膜工艺简单,能够实现大面积均匀制备,易实现产业化生产,为制备电阻开关阻变存储器(RRAM)提供一种新的材料及结构原型。
Description
技术领域
本发明属于微电子器件和功能薄膜技术领域,具体涉及一种基于BN(Al)薄膜的电阻开关及其制备方法。
背景技术
随着对计算机运行速度以及硬件要求越来越高,与之相对应的就是对其中元器件存储器读取速度、存储密度、功耗、单元尺寸、稳定性等性能的需求。目前,在众多的存储器中阻变存储器(RRAM)相比较于传统的非挥发性闪存存储器具有与CMOS工艺兼容性高、低功耗、结构简单、可高密度集成等优点,而被广泛研究和开发。电阻开关是阻变式存储器的元器件,寻找性能优异的电阻开关材料是制备稳定存储器的关键。
发明内容
本发明的目的在于提供一种基于BN(Al)薄膜的电阻开关及制备方法,给电阻开关提供一种新的制备材料,所获得的电阻开关性能优异,稳定性好。
为了实现上述目的,本发明采用如下技术方案:
一种基于BN(Al)薄膜的电阻开关,包括硅衬底,硅衬底的一面镀有金属层作为下电极,硅衬底的另一面设有BN(Al)薄膜,BN(Al)薄膜表面设有上电极;构成上电极/BN(Al)/下电极三明治结构电阻开关。
进一步的,硅衬底的一面镀有的金属层为金属Al;BN(Al)薄膜表面设有的上电极为In 电极。
进一步的,BN(Al)薄膜为BN薄膜中掺杂了金属Al,金属Al的掺杂质量百分比≥0%。
一种电阻开关的制备方法,包括以下步骤:
(1)硅衬底清洗干净;
(2)在硅衬底一面蒸镀金属薄膜作为下电极;
(3)将硅衬底放入溅射腔室内溅射一层BN(Al)薄膜;
(4)溅射完成后,待硅衬底在溅射腔室内自然冷却至室温后取出;
(5)在溅射制备的BN(Al)薄膜表面制备上电极,形成上电极/BN(Al)/下电极的三明治结构电阻开关。
进一步的,步骤(2)中:在洁净的硅衬底上蒸镀厚度为150-300nm的金属薄膜作为下电极。
进一步的,步骤(3)中:将硅衬底放入溅射腔室内,对溅射腔室以及硅衬底进行加热,达到预设温度时,硅衬底温度稳定后采用双电源磁控溅射法,以六方BN靶材和金属Al靶材作为靶源,氩气作为放电气体,在硅衬底另一面上沉积BN(Al)薄膜。
进一步的,溅射BN靶源的功率为400-600W,溅射金属Al的功率为0-150W,溅射总压强为0.3-0.6Pa,沉积温度为室温-600℃,靶基距为100-150mm,薄膜制备过程中引入氮气对衬底表面进行轰击,补充N空位缺陷,诱导薄膜出现,溅射时间大于等于1.5h。
进一步的,步骤(3)中溅射时溅射腔室的真空度为5×10-4Pa。
进一步的,溅射金属Al靶材的功率为60-150W。
进一步的,具体包括以下步骤:
(1)硅衬底清洗:将硅衬底在311溶液中加热至180℃,浸泡15min,然后在无水乙醇中超声清洗15min,使用去离子水冲洗三次,用氮气吹干,去除硅片表面附着的杂质;
(2)电蒸镀过程:在洁净的硅衬底上蒸镀厚度为150nm的铝膜;
(3)将样品放入溅射腔室内,首先对腔室以及衬底进行加热升温,升温速度不超过10℃ /min,当温度计显示达到预设温度时,持续保温1h以确保腔室和衬底温度的稳定;采用双电源磁控溅射法,以六方BN靶材和金属Al作为靶源,氩气作为放电气体,在衬底上沉积BN (Al)薄膜;其中溅射BN靶材的功率为400W,溅射Al靶材的功率为150W,溅射总压强为0.6Pa,沉积温度为600℃,靶基距为150mm,真空度为5×10-4Pa,薄膜制备过程中引入氮气对样品表面进行轰击,补充N空位缺陷,诱导薄膜成形,溅射时间为2h;形成样品中BN薄膜中掺入金属Al的比例为7.51%;
(4)溅射完成后,样品在真空中自然冷却至室温后取出真空室;
(5)在溅射制备的BN(Al)薄膜制备上In电极,制备成In/BN(Al)/Al三明治结构电阻开关元器件。
本发明的有益效果在于:
1.所述电阻开关结构简单,成本低廉,在阻变式存储器中有较强的实用价值;
2.利用BN薄膜作为电阻开关材料,具有良好的稳定性,电阻开关窗口大,电阻特性明显;
3.在BN薄膜制备过程中加入金属Al,生成BN(Al)薄膜作为电阻开关材料,具有良好的稳定性,电阻开关特性更加明显;
4.所述制备方法步骤简单,易于操作,具有很强的实用性,能够实现大面积均匀制备,易实现产业化生产;
5.BN(Al)薄膜利用双电源磁控溅射的方式制备,其厚度以及掺金属比例可以通过调节溅射时间和功率等参数进行调制,进而可以根据不同需要进行材料选择。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:
图1为BN(Al)薄膜的场发射扫描电子显微镜(SEM)表面形貌图;
图2为BN(Al)薄膜的场发射扫描电子显微镜(SEM)横截面形貌图;
图3为BN(Al)薄膜横截面电阻开关的电压-电流特性曲线图;
具体实施方式
下面将参考附图并结合实施例来详细说明本发明。需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互组合。
以下详细说明均是示例性的说明,旨在对本发明提供进一步的详细说明。除非另有指明,本发明所采用的所有技术术语与本申请所属领域的一般技术人员的通常理解的含义相同。本发明所使用的术语仅是为了描述具体实施方式,而并非意图限制根据本发明的示例性实施方式。
氮化硼(BN)薄膜具有宽带隙、高热稳定性、化学稳定性能和表面负电子亲和势,是一种具有良好开发前景的薄膜电阻开关材料。其相对于传统介电材料比如SiO2,BN薄膜表面化学稳定性可抑制与相邻层的相互作用,其高导热性有利于电子器件的热扩散。
有关利用金属掺杂的BN薄膜进行电阻开关的制备及电阻开关特性的研究尚未见报道。
本发明提供一种基于BN(Al)薄膜的电阻开关,包括硅衬底,硅衬底的一面镀有金属 Al层作为下电极,硅衬底的另一面设有BN(Al)薄膜,BN(Al)薄膜表面设有In上电极;形成In/BN(Al)/Al三明治结构电阻开关。
根据对本发明中所制备的In/BN(Al)/Al三明治结构电阻开关样品特性分析,下面将基于BN(Al)薄膜的电阻开关的制备方法的最佳实施案例进行详细地说明:
实施案例1:
(1)硅衬底清洗:将硅衬底在311溶液中加热至180℃,浸泡15min,然后在无水乙醇中超声清洗15min,使用去离子水冲洗三次,用氮气吹干,以保证去除硅片表面附着的杂质;
(2)在洁净的硅衬底上蒸镀厚度为250nm的铝膜;
(3)将样品放入溅射腔室内,首先对腔室以及衬底进行加热升温,升温速度为10℃/min,当温度计显示达到预设温度时,持续保温1h以确保腔室和衬底温度的稳定。
采用磁控溅射法,以高纯六方BN靶材(99.99%)作为靶源,氩气(Ar)作为放电气体,在衬底上沉积BN薄膜,溅射BN靶材的功率为400W,溅射总压强为0.6Pa,沉积温度为600℃,靶基距为150mm,真空度为5×10-4Pa,薄膜制备过程中引入氮气对样品表面进行轰击,补充 N空位缺陷,诱导薄膜出现,溅射时间为2h。本组样品中掺金属Al的比例为0,进行的是单电源溅射,形成BN薄膜;
(4)溅射完成后,样品在真空中自然冷却至室温后取出真空室;
(5)在溅射制备的BN薄膜表面制备上电极(In),制备成In/BN/Al三明治结构电阻开关元器件。
对制备好的In/BN/Al三明治结构电阻开关进行电压-电流特性的测量,研究其电阻开关特性。
用电流源/电压表测量样品的电压-电流特性,分别将测试探针正极插在下电极Al上,负极插在上电极In上,电压变化过程为0→8V→0→-8V→0,每隔0.16V测量一个数据点,结果如图3中实线所示。可以看出在相同的电压下,对应着不同的电流,表现出了不同的电阻值,说明BN薄膜具有电阻开关特性。
实施案例2:
(1)硅衬底清洗:将硅衬底在311溶液中加热至180℃,浸泡15min,然后在无水乙醇中超声清洗15min,使用去离子水冲洗三次,用氮气吹干,以保证去除硅片表面附着的杂质;
(2)电蒸镀过程:在洁净的硅衬底上蒸镀厚度为150nm的铝膜;
(3)将样品放入溅射腔室内,首先对腔室以及衬底进行加热升温,升温速度不超过10℃ /min,当温度计显示达到预设温度时,持续保温1h以确保腔室和衬底温度的稳定。采用双电源磁控溅射法,以高纯六方BN靶材(99.99%)和金属Al作为靶源,氩气(Ar)作为放电气体,在衬底上沉积BN(Al)薄膜。其中溅射BN靶材的功率为400W,溅射Al靶材的功率为150W,溅射总压强为0.6Pa,沉积温度为600℃,靶基距为150mm,真空度为5×10-4Pa,薄膜制备过程中引入氮气对样品表面进行轰击,补充N空位缺陷,诱导薄膜成形,溅射时间为 2h。形成样品的表面及截面形貌如图1所示,本组样品中BN薄膜中掺入金属Al的比例为7.51%,采用的是双电源溅射。
(4)溅射完成后,样品在真空中自然冷却至室温后取出真空室。
(5)在溅射制备的BN(Al)薄膜制备上电极(In),制备成In/BN(Al)/Al三明治结构电阻开关元器件。
对制备好的In/BN/Al三明治结构电阻开关进行电压-电流特性的测量,研究其电阻开关特性。
用电流源/电压表测量样品的电压-电流特性,分别将测试探针正极插在下电极Al上,负极插在上电极In上,电压变化过程为0→8V→0→-8V→0,每隔0.16V测量一个数据点,结果如图3中虚线所示。可以看出在相同的电压下,对应着不同的电流,表现出了不同的电阻值,且高低阻态的比值(电阻窗口)高于没有掺入金属BN薄膜的,说明BN(Al)薄膜的电阻开关特性更明显。
实施案例3:
(1)硅衬底清洗:将硅衬底在311溶液中加热至180℃,浸泡15min,然后在无水乙醇中超声清洗15min,使用去离子水冲洗三次,用氮气吹干,以保证去除硅片表面附着的杂质;
(2)电蒸镀过程:在洁净的硅衬底上蒸镀厚度为250nm的铝膜;
(3)将样品放入溅射腔室内,首先对腔室以及衬底进行加热升温,升温速度不超过10℃ /min,当温度计显示达到预设温度时,持续保温1h以确保腔室和衬底温度的稳定。采用双电源磁控溅射法,以高纯六方BN靶材(99.99%)和金属Al作为靶源,氩气(Ar)作为放电气体,在衬底上沉积BN(Al)薄膜。其中溅射BN靶材的功率为500W,溅射Al靶材的功率为100W,溅射总压强为0.4Pa,沉积温度为200℃,靶基距为130mm,真空度为5×10-4Pa,薄膜制备过程中引入氮气对样品表面进行轰击,补充N空位缺陷,诱导薄膜成形,溅射时间为1.5h。
(4)溅射完成后,样品在真空中自然冷却至室温后取出真空室。
(5)在溅射制备的BN(Al)薄膜制备上电极(In),制备成In/BN(Al)/Al三明治结构电阻开关元器件。
实施案例4:
(1)硅衬底清洗:将硅衬底在311溶液中加热至180℃,浸泡15min,然后在无水乙醇中超声清洗15min,使用去离子水冲洗三次,用氮气吹干,以保证去除硅片表面附着的杂质;
(2)电蒸镀过程:在洁净的硅衬底上蒸镀厚度为300nm的铝膜;
(3)将样品放入溅射腔室内,首先对腔室以及衬底进行加热升温,升温速度不超过10℃ /min,当温度计显示达到预设温度时,持续保温1h以确保腔室和衬底温度的稳定。采用双电源磁控溅射法,以高纯六方BN靶材(99.99%)和金属Al作为靶源,氩气(Ar)作为放电气体,在衬底上沉积BN(Al)薄膜。其中溅射BN靶材的功率为600W,溅射Al靶材的功率为150W,溅射总压强为0.3Pa,沉积温度为室温,靶基距为100mm,真空度为5×10-4Pa,薄膜制备过程中引入氮气对样品表面进行轰击,补充N空位缺陷,诱导薄膜成形,溅射时间为3h。
(4)溅射完成后,样品在真空中自然冷却至室温后取出真空室。
(5)在溅射制备的BN(Al)薄膜制备上电极(In),制备成In/BN(Al)/Al三明治结构电阻开关元器件。
由技术常识可知,本发明可以通过其它的不脱离其精神实质或必要特征的实施方案来实现。因此,上述公开的实施方案,就各方面而言,都只是举例说明,并不是仅有的。所有在本发明范围内或在等同于本发明的范围内的改变均被本发明包含。
Claims (9)
1.一种基于BN(Al)薄膜的电阻开关,其特征在于,包括硅衬底,硅衬底的一面镀有金属层作为下电极,硅衬底的另一面设有BN(Al)薄膜,BN(Al)薄膜表面设有上电极;构成上电极/BN(Al)/下电极三明治结构电阻开关。
2.根据权利要求1所述的电阻开关,其特征在于,硅衬底的一面镀有的金属层为金属Al;BN(Al)薄膜表面设有的上电极为In电极。
3.根据权利要求1所述的电阻开关,其特征在于,BN(Al)薄膜为BN薄膜中掺杂了金属Al,金属Al的掺杂质量百分比≥0%。
4.权利要求1至3中任一项所述电阻开关的制备方法,其特征在于,包括以下步骤:
(1)硅衬底清洗干净;
(2)在硅衬底一面蒸镀金属薄膜作为下电极;
(3)将硅衬底放入溅射腔室内溅射一层BN(Al)薄膜;
(4)溅射完成后,待硅衬底在溅射腔室内自然冷却至室温后取出;
(5)在溅射制备的BN(Al)薄膜表面制备上电极,形成上电极/BN(Al)/下电极的三明治结构电阻开关。
5.根据权利要求4所述的制备方法,其特征在于,步骤(2)中:在洁净的硅衬底上蒸镀厚度为150-300nm的金属薄膜作为下电极。
6.根据权利要求4所述的制备方法,其特征在于,步骤(3)中:将硅衬底放入溅射腔室内,对溅射腔室以及硅衬底进行加热,达到预设温度时,硅衬底温度稳定后采用双电源磁控溅射法,以六方BN靶材和金属Al靶材作为靶源,氩气作为放电气体,在硅衬底另一面上沉积BN(Al)薄膜。
7.根据权利要求6所述的制备方法,其特征在于,溅射BN靶源的功率为400-600W,溅射金属Al的功率为0-150W,溅射总压强为0.3-0.6Pa,沉积温度为室温-600℃,靶基距为100-150mm,薄膜制备过程中引入氮气对衬底表面进行轰击,补充N空位缺陷,诱导薄膜出现,溅射时间大于等于1.5h。
8.根据权利要求7所述的制备方法,其特征在于,溅射金属Al靶材的功率为60-150W。
9.根据权利要求4所述的制备方法,其特征在于,具体包括以下步骤:
(1)硅衬底清洗:将硅衬底在311溶液中加热至180℃,浸泡15min,然后在无水乙醇中超声清洗15min,使用去离子水冲洗三次,用氮气吹干,去除硅片表面附着的杂质;
(2)电蒸镀过程:在洁净的硅衬底上蒸镀厚度为150nm的铝膜;
(3)将样品放入溅射腔室内,首先对腔室以及衬底进行加热升温,升温速度不超过10℃/min,当温度计显示达到预设温度时,持续保温1h以确保腔室和衬底温度的稳定;采用双电源磁控溅射法,以六方BN靶材和金属Al作为靶源,氩气作为放电气体,在衬底上沉积BN(Al)薄膜;其中溅射BN靶材的功率为400W,溅射Al靶材的功率为150W,溅射总压强为0.6Pa,沉积温度为600℃,靶基距为150mm,真空度为5×10-4Pa,薄膜制备过程中引入氮气对样品表面进行轰击,补充N空位缺陷,诱导薄膜成形,溅射时间为2h;形成样品中BN薄膜中掺入金属Al的比例为7.51%;
(4)溅射完成后,样品在真空中自然冷却至室温后取出真空室;
(5)在溅射制备的BN(Al)薄膜制备上In电极,制备成In/BN(Al)/Al三明治结构电阻开关元器件。
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