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SnSb/Si多层相变薄膜材料及其制备方法 【EN】SnSb/Si multilayer phase-change film material and preparation method thereof

申请(专利)号:CN201810684530.0国省代码:江苏 32
申请(专利权)人:【中文】江苏理工学院【EN】JIANGSU University OF TECHNOLOGY
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摘要:
【中文】本发明提供一种Sn20Sb80/Si多层相变薄膜材料,其为多层复合膜结构,由Sn20Sb80层和Si层交替沉积复合而成,将一层Sn20Sb80层和一层Si层作为一个交替周期,后一个交替周期的Sn20Sb80层沉积在前一个交替周期的Si层上方;所述Sn20Sb80层是以Sn20Sb80靶材通过磁控溅射法得到,所述Si层是以Si靶材通过磁控溅射法得到;所述Sn20Sb80/Si多层相变薄膜材料的结构用通式[Sn20Sb80(a)/Si(b)]x表示,其中a为单层Sn20Sb80层的厚度,a=1nm~50nm;b为单层Si层的厚度,b=1nm~50nm,x为Sn20Sb80层和Si层的交替周期数,x为正整数。本发明提供的Sn20Sb80/Si多层相变薄膜材料能够改善现有存储器的热稳定性和操作功耗。 【EN】The invention provides Sn20Sb80the/Si multilayer phase-change thin film material is of a multilayer composite film structure and is formed by Sn20Sb80The layers and Si layers are alternately deposited and compounded, and one layer of Sn is formed20Sb80A layer and a Si layerSn as one alternate period followed by one alternate period20Sb80The layer is deposited over the Si layer of the previous alternating period; the Sn20Sb80The layer is Sn20Sb80The target material is obtained by a magnetron sputtering method, and the Si layer is obtained by a Si target material by the magnetron sputtering method; the Sn20Sb80The structural general formula of the/Si multilayer phase-change film material [ Sn20Sb80(a)/Si(b)]xWherein a is a single layer of Sn20Sb80The thickness of the layer, a ═ 1nm to 50 nm; b is the thickness of a single Si layer, b is 1nm to 50nm, and x is Sn20Sb80The number of alternating periods of the layers and the Si layer, x being a positive integer. Sn provided by the invention20Sb80the/Si multilayer phase-change thin film material can improve the thermal stability and the operation power consumption of the existing memory.

主权项:
【中文】1.一种SnSb/Si多层相变薄膜材料,其特征在于,SnSb/Si多层相变薄膜材料为多层复合膜结构,由SnSb层和Si层交替沉积复合而成,将一层SnSb层和一层Si层作为一个交替周期,后一个交替周期的SnSb层沉积在前一个交替周期的Si层上方;所述SnSb层是以SnSb靶材通过磁控溅射法得到,所述Si层是以Si靶材通过磁控溅射法得到; 所述SnSb/Si多层相变薄膜材料的结构用通式[SnSb(a)/Si(b)]表示,其中a为单层SnSb层的厚度,a=3nm~6nm;b为单层Si层的厚度,b=4nm~7nm,x为SnSb层和Si层的交替周期数,x为正整数; 所述SnSb/Si多层相变薄膜材料的总厚度的数值根据(a+b)*x计算所得;所述SnSb/Si多层相变薄膜材料的总厚度为50nm; SnSb层中含有Sn和Sb两种元素,Sn和Sb的原子比为20∶80。 【EN】1. Sn (tin)Sbthe/Si multilayer phase-change thin film material is characterized in that SnSbthe/Si multilayer phase-change thin film material is of a multilayer composite film structure and is composed of SnSbThe layers and Si layers are alternately deposited and compounded, and one layer of Sn is formedSbLayers and one Si layer as one alternating period, Sn of the latter alternating periodSbThe layer is deposited over the Si layer of the previous alternating period; the SnSbThe layer is SnSbThe target material is obtained by a magnetron sputtering method, and the Si layer is obtained by a Si target material by the magnetron sputtering method; the SnSbThe structural general formula of the/Si multilayer phase-change film material [ SnSb(a)/Si(b)]Wherein a is a single layer of SnSbThe thickness of the layer, a being 3nm to 6 nm; b is the thickness of a single Si layer, b is 4nm to 7nm, and x is SnSbThe number of alternating periods of the layers and the Si layer, x being a positive integer; the SnSbThe total thickness of the/Si multilayer phase-change film material is calculated according to (a + b) ×; the SnSbThe total thickness of the/Si multilayer phase change film material is 50 nm; SnSbthe layer contains two elements of Sn and Sb, and the atomic ratio of Sn to Sb is 20: 80.


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说明书

【中文】

Sn20Sb80/Si多层相变薄膜材料及其制备方法

技术领域

本发明涉及微电子材料领域,特别涉及一种Sn20Sb80/Si多层相变薄膜材料。

背景技术

相变存储技术是一种应用硫系化合物材料来存储数据的随机存储技术,基本原理是利用电能或者光能致使材料在晶态(低阻/高反射率)与非晶态(高阻/低反射率)之间互逆转换从而实现信息的写入与擦除,信息的读出则依靠测量晶态与非晶态之间电阻或反射率的显著差异而实现。相变存储器因同时具备低功耗、抗辐照、高密度、高速擦写、高循环次数以及与集成电路硅工艺的良好匹配性能等优点,被广泛认为是取代Flash等存储器的下一代非易失性随机存储器。对各类相变存储材料的研究表明,Ge2Sb2Te5化合物被认为是最合适的相变材料,已在可擦写光盘等产业中得到了广泛应用。随着相变存储器的快速发展,近年来越来越多基于Ge2Sb2Te5的新材料开始被广泛研究。

传统相变材料(如Ge2Sb2Te5)存在一些问题,如热稳定性低,功耗偏高,结晶速度较慢等,所以针对不同应用迫切需要新型相变存储材料。

因此,如何开发出一种能够改善现有存储器热稳定性和操作功耗的新型相变存储材料,成为亟需解决的问题。

发明内容

本发明解决的问题是提供一种Sn20Sb80/Si多层相变薄膜材料,所述 Sn20Sb80/Si多层相变薄膜材料为多层复合膜结构,由Sn20Sb80层和Si层交替沉积复合而成,将一层Sn20Sb80层和一层Si层作为一个交替周期,后一个交替周期的 Sn20Sb80层沉积在前一个交替周期的Si层上方;所述Sn20Sb80层是以Sn20Sb80靶材通过磁控溅射法得到,所述Si层是以Si靶材通过磁控溅射法得到;

所述Sn20Sb80/Si多层相变薄膜材料的结构用通式[Sn20Sb80(a)/Si(b)]x表示,其中a为单层Sn20Sb80层的厚度,a=1nm~50nm;b为单层Si层的厚度,b=1nm~50nm, x为Sn20Sb80层和Si层的交替周期数,x为正整数。

可选的,所述Sn20Sb80/Si多层相变薄膜材料的总厚度的数值根据(a+b)*x 计算所得。

可选的,所述Sn20Sb80/Si多层相变薄膜材料的总厚度为50nm。

可选的,Sn20Sb80层中含有Sn和Sb两种元素,Sn和Sb的原子比为20∶80。

可选的,包括以下步骤:

①基片的准备,将基片洗净烘干待用;

②磁控溅射的准备,将步骤①洗净的待溅射的基片放置在基托上,将Sn20Sb80靶材和Si靶材分别安装在磁控射频溅射靶中,并将磁控溅射镀膜系统的溅射腔室进行抽真空,使用高纯氩气作为溅射气体;

③磁控溅射制备[Sn20Sb80(a)/Si(b)]x多层相变薄膜:

a、将空基托旋转到Sn20Sb80靶位,打开Sn20Sb80靶上的射频电源,依照设定的溅射时间,开始对Sn20Sb80靶材表面进行溅射,清洁Sn20Sb80靶位表面;

b、Sn20Sb80靶位表面清洁完成后,关闭Sn20Sb80靶位上所施加的射频电源,将空基托旋转到Si靶位,开启Si靶上的射频电源,依照设定的溅射时间,开始对 Si靶材表面进行溅射,清洁Si靶位表面;

c、将已经溅射了GeTe层的基片旋转到Sb靶位,开启Sb靶位上的射频电源,溅射结束后得到Sb层;Si靶位表面清洁完成后,将待溅射的基片旋转到Sn20Sb80靶位,打开Sn20Sb80靶位上的射频电源,依照设定的溅射时间,开始溅射Sn20Sb80薄膜;

d、Sn20Sb80薄膜溅射完成后,关闭Sn20Sb80靶上所施加的射频电源,将基片旋转到Si靶位,开启Si靶位射频电源,依照设定的溅射时间,开始溅射Si薄膜;

e、重复上述步骤c、d,溅射结束得到Sn20Sb80/Si多层相变薄膜材料。

可选的,步骤②中高纯氩气的体积百分比≥99.999%,Ar气流量在 25SCCM~30SCCM范围内,氩气溅射气压在0.15Pa~0.35Pa范围内。

可选的,步骤③中磁控溅射采用射频电源的功率在25W~35W范围内。

与现有技术相比,本发明提供的技术方案具有以下优点:

本发明提供一种Sn20Sb80/Si多层相变薄膜材料,通过将Sn20Sb80层与Si层交替沉积复合而成,从而使得所述Sn20Sb80/Si多层相变薄膜材料成为多层复合膜结构,有利于提高相变存储器的热稳定性,降低相变存储器的功耗,进而有利于提升相变存储器的综合性能。

本发明Sn20Sb80/Si多层相变薄膜材料通过磁控溅射法进行制备,进一步通过控制溅射时间来实现控制Sn20Sb80层与Si层的厚度。所述Sn20Sb80/Si多层相变薄膜材料的结构用通式为[Sn20Sb80(a)/Si(b)]x,其中a为单层Sn20Sb80层的厚度, a=1nm~50nm;b为单层Si层的厚度,b=1nm~50nm,x为Sn20Sb80层和Si层的交替周期数,x为正整数。

附图说明

图1是本发明实施例1至实施例4的Sn20Sb80/Si多层相变薄膜材料和对比例 1的相变薄膜材料的原位电阻与温度的关系曲线,图中横坐标的Temperature为温度,纵坐标的Resistance为电阻;

图2是本发明实施例1至实施例4的Sn20Sb80/Si多层相变薄膜材料和对比例 1的相变薄膜材料的Kubelka-Munk函数图,图中Energy为能量,Absorbance 为吸收率。

具体实施方式

由背景技术可知,传统相变材料(如Ge2Sb2Te5)的综合性能有待提高。

为了解决上述问题,本发明提供一种Sn20Sb80/Si多层相变薄膜材料,能够提高相变存储器的综合性能。

为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。

实施例1

本实施例中,所述Sn20Sb80/Si多层相变薄膜材料为多层复合膜结构,由 Sn20Sb80层和Si层交替沉积复合而成,将一层Sn20Sb80层和一层Si层作为一个交替周期,后一个交替周期的Sn20Sb80层沉积在前一个交替周期的Si层上方;所述 Sn20Sb80层是以Sn20Sb80靶材通过磁控溅射法得到,所述Si层是以Si靶材通过磁控溅射法得到。

本实施例中,所述Sn20Sb80/Si多层相变薄膜材料的结构通式为 [Sn20Sb80(3nm)/Si(7nm)]5,即单层Sn20Sb80层的厚度为3nm,单层Si层的厚度为 7nm,Sn20Sb80层和Si层的交替周期数为5。

本实施例中,所述Sn20Sb80/Si多层相变薄膜材料的总厚度为50nm。Sn20Sb80层中含有Sn和Sb两种元素,Sn和Sb的原子比为20∶80。

本实施例的Sn20Sb80/Si多层相变薄膜材料采用磁控溅射法获得,具体制备方法包括以下步骤:

①基片的准备,清洗SiO2/Si(100)基片,目的是通过清洗表面、背面,去除灰尘颗粒、有机和无机杂质。先在丙酮溶液中强超声清洗3-5分钟,接着用去离子水冲洗;后在乙醇溶液中强超声清洗3-5分钟,接着用去离子水冲洗,后用高纯N2吹干表面和背面;再在120℃烘箱内烘干水汽,烘干约20分钟。

②磁控溅射的准备,将步骤①洗净的待溅射的基片放置在基托上,分别装好Sn20Sb80靶材和Si靶材,靶材的纯度均达到99.999%(原子百分比),并将本底真空抽至1×10-4Pa;设定溅射功率为30W;使用高纯Ar作为溅射气体(体积百分比达到99.999%),设定Ar气流量为30SCCM,并将溅射气压调节至0.3Pa。

③采用磁控溅射制备[Sn20Sb80(a)/Si(b)]x多层相变薄膜:

a)将空基托旋转到Sn20Sb80靶位,打开Sn20Sb80靶上的射频电源,依照设定的溅射时间(如100s),开始对Sn20Sb80靶材表面进行溅射,清洁Sn20Sb80靶位表面;

b)Sn20Sb80靶位表面清洁完成后,关闭Sn20Sb80靶位上所施加的射频电源,将空基托旋转到Si靶位,开启Si靶上的射频电源,依照设定的溅射时间(如100s),开始对Si靶材表面进行溅射,清洁Si靶位表面;

c)Si靶位表面清洁完成后,将待溅射的基片旋转到Sn20Sb80靶位,打开 Sn20Sb80靶位上的射频电源,依照设定的溅射时间,开始溅射Sn20Sb80薄膜;

d)Sn20Sb80薄膜溅射完成后,关闭Sn20Sb80靶上所施加的射频电源,将基片旋转到Si靶位,开启Si靶位射频电源,依照设定的溅射时间,开始溅射Si薄膜;

重复c)和d)两步,得到SiO2/Si(100)基片上制备[Sn20Sb80(3nm)/Si(7nm)]5多层复合相变薄膜材料。本实施例中,所述Sn20Sb80/Si多层相变薄膜材料的厚度通过溅射时间来控制,Sn20Sb80的溅射速率为3.74953s/nm,Si的溅射速率为 15.57632s/nm。

实施例2

本实施例中,所述Sn20Sb80/Si多层相变薄膜材料的结构通式为 [Sn20Sb80(4nm)/Si(6nm)]5,即单层Sn20Sb80层的厚度为4nm,单层Si层的厚度为 6nm,Sn20Sb80层和Si层的交替周期数为5。所述Sn20Sb80/Si多层相变薄膜材料的总厚度为50nm。

本实施例的制备方法与实施例1类似,区别在于[Sn20Sb80(4nm)/Si(6nm)]5薄膜中单层Sn20Sb80层的厚度为4nm,单层Si层的厚度为6nm。

实施例3

本实施例中,所述Sn20Sb80/Si多层相变薄膜材料的结构通式为 [Sn20Sb80(6nm)/Si(4nm)]5,即单层Sn20Sb80层的厚度为6nm,单层Si层的厚度为 4nm,Sn20Sb80层和Si层的交替周期数为5。所述Sn20Sb80/Si多层相变薄膜材料的总厚度为50nm。

本实施例的制备方法与实施例1类似,区别在于[Sn20Sb80(6nm)/Si(4nm)]5薄膜中单层Sn20Sb80层的厚度为6nm,单层Si层的厚度为4nm。

实施例4

本实施例中,所述Sn20Sb80/Si多层相变薄膜材料的结构通式为 [Sn20Sb80(8nm)/Si(2nm)]5,即单层Sn20Sb80层的厚度为8nm,单层Si层的厚度为 2nm,Sn20Sb80层和Si层的交替周期数为5。所述Sn20Sb80/Si多层相变薄膜材料的总厚度为50nm。

本实施例的制备方法与实施例1类似,区别在于[Sn20Sb80(8nm)/Si(2nm)]5薄膜中单层Sn20Sb80层的厚度为8nm,单层Si层的厚度为2nm。

对比例1

本对比例中制备单层Sn20Sb80相变薄膜材料,厚度50nm。

制备步骤为:

1.清洗SiO2/Si(100)基片,清洗表面、背面,去除灰尘颗粒、有机和无机杂质;

a)在丙酮溶液中强超声清洗3-5分钟,去离子水冲洗;

b)在乙醇溶液中强超声清洗3-5分钟,去离子水冲洗,高纯N2吹干表面和背面;

c)在120℃烘箱内烘干水汽,约20分钟。

2.采用射频溅射方法制备Sn20Sb80薄膜前准备:

a)装好Sn20Sb80溅射靶材,靶材的纯度均达到99.999%(原子百分比),并将本底真空抽至1×10-4Pa;

b)设定溅射功率30W;

c)使用高纯Ar气作为溅射气体(体积百分比达到99.999%),设定Ar气流量为30SCCM,并将溅射气压调节至0.3Pa。

3.采用磁控溅射方法制备Sn20Sb80纳米相变薄膜材料:

a)将空基托旋转到Sn20Sb80靶位,打开Sn20Sb80靶上所施加的射频电源,依照设定的溅射时间(190s),开始对Sn20Sb80靶材进行溅射,清洁Sn20Sb80靶材表面;

b)Sn20Sb80靶材表面清洁完成后,关闭Sn20Sb80靶上所施加的射频电源,将代溅射基片旋转到Sn20Sb80靶位,开启Sn20Sb80靶位射频电源,依照设定的溅射时间(190s),开始溅射单层Sn20Sb80薄膜。

实验方法及结果

参考图1,将实施例1至实施例4制备的4种[Sn20Sb80(a)/Si(b)]x多层相变薄膜材料与对比例1的单层Sn20Sb80相变薄膜材料进行测试得到各相变薄膜材料的原位电阻与温度的关系曲线,图中横坐标的Temperature为温度,纵坐标的Resistance 为电阻。

参考图2,将上述实施例制备的4种[Sn20Sb80(a)/Si(b)]x多层相变薄膜材料与对比例的单层Sn20Sb80相变薄膜材料进行测试得到各相变薄膜材料的 Kubelka-Munk函数图像,图中Energy为能量,Absorbance为吸收率。

由图1可知,随着[Sn20Sb80(a)/Si(b)]x多层相变薄膜中Si层相对厚度的增加,相变薄膜的晶化温度提高,可以看到单层Sn20Sb80相变薄膜材料、 [Sn20Sb80(8nm)/Si(2nm)]5、[Sn20Sb80(6nm)/Si(4nm)]5、[Sn20Sb80(4nm)/Si(6nm)]5和 [Sn20Sb80(3nm)/Si(7nm)]5多层相变薄膜材料的晶化温度分别为192℃、181℃、 212℃、232℃和246℃,说明热稳定性提高。另外,随着[Sn20Sb80(a)/Si(b)]x多层相变薄膜中Si层相对厚度的增加,非晶态电阻增加,这有助于器件相变过程中操作功耗的降低。

图2显示,传统Sn20Sb80相变薄膜材料的能带间隙为0.201eV。当 [Sn20Sb80(a)/Si(b)]x多层相变薄膜中Si层相对厚度越来越大时,能带间隙也随之递增,[Sn20Sb80(8nm)/Si(2nm)]5、[Sn20Sb80(6nm)/Si(4nm)]5、 [Sn20Sb80(4nm)/Si(6nm)]5和[Sn20Sb80(3nm)/Si(7nm)]5多层相变薄膜的能带间隙分别为0.244eV、0.285eV、0.360eV和0.408eV。通常能带间隙是来衡量无机非金属材料非晶态电阻值的大小,当能带间隙越大的话,间隙中载流子浓度越低,薄膜导电性能就越差,非晶态电阻就越高,反之则非晶态电阻越低。因此,本发明的[Sn20Sb80(a)/Si(b)]x多层相变薄膜具有比传统Sn20Sb80相变薄膜材料更大的非晶态电阻,大大降低了在相变过程中的操作功耗。

虽然本发明披露如上,但本发明并非限定于此。任何本领域技术人员,在不脱离本发明的精神和范围内,均可作各种更动与修改,因此本发明的保护范围应当以权利要求所限定的范围为准。

【EN】

Sn20Sb80/Si multilayer phase-change film material and preparation method thereof

Technical Field

The invention relates to the field of microelectronic materials, in particular to Sn20Sb80the/Si multilayer phase-change thin film material.

Background

The phase change memory technology is a random memory technology for storing data by using chalcogenide compound material, and the basic principle is that electric energy or light energy is used to cause the material to be inversely converted between crystalline state (low resistance/high reflectivity) and amorphous state (high resistance/low reflectivity) so as to realize the writing and erasing of information, and the reading of information is realized by measuring the obvious difference of resistance or reflectivity between the crystalline state and the amorphous state. The phase change memory has the advantages of low power consumption, radiation resistance, high density, high erasing speed, high cycle number, good matching performance with an integrated circuit silicon process and the like, and is widely considered as a next-generation nonvolatile random access memory for replacing memories such as Flash memories and the like. Research on various phase change memory materials shows that Ge2Sb2Te5The compound is considered to be the most suitablePhase change materials have been widely used in the rewritable optical disc industry. With the rapid development of phase change memories, more and more Ge is based on in recent years2Sb2Te5Are beginning to be widely studied.

Conventional phase change materials (e.g., Ge)2Sb2Te5) There are some problems, such as low thermal stability, high power consumption, slow crystallization speed, etc., so that a new phase change memory material is urgently needed for different applications.

Therefore, how to develop a new phase change memory material capable of improving the thermal stability and the operation power consumption of the existing memory becomes a problem to be solved urgently.

Disclosure of Invention

The invention solves the problem of providing Sn20Sb80a/Si multilayer phase change thin film material, the Sn20Sb80the/Si multilayer phase-change thin film material is of a multilayer composite film structure and is composed of Sn20Sb80The layers and Si layers are alternately deposited and compounded, and one layer of Sn is formed20Sb80Layers and one Si layer as one alternating period, Sn of the latter alternating period20Sb80The layer is deposited over the Si layer of the previous alternating period; the Sn20Sb80The layer is Sn20Sb80The target material is obtained by a magnetron sputtering method, and the Si layer is obtained by a Si target material by the magnetron sputtering method;

the Sn20Sb80The structural general formula of the/Si multilayer phase-change film material [ Sn20Sb80(a)/Si(b)]xWherein a is a single layer of Sn20Sb80The thickness of the layer, a ═ 1nm to 50 nm; b is the thickness of a single Si layer, b is 1nm to 50nm, and x is Sn20Sb80The number of alternating periods of the layers and the Si layer, x being a positive integer.

Optionally, the Sn20Sb80The total thickness of the/Si multilayer phase-change film material is calculated according to (a + b) x.

Optionally, the Sn20Sb80The total thickness of the/Si multilayer phase change film material is 50 nm.

Optionally, Sn20Sb80The layer contains two elements of Sn and Sb, and the atomic ratio of Sn to Sb is 20: 80.

Optionally, the method comprises the following steps:

firstly, preparing a substrate, namely cleaning and drying the substrate for later use;

preparing magnetron sputtering, namely placing the substrate to be sputtered cleaned in the step I on a base, and placing Sn20Sb80The target material and the Si target material are respectively arranged in a magnetron radio frequency sputtering target, a sputtering chamber of a magnetron sputtering coating system is vacuumized, and high-purity argon is used as sputtering gas;

(iii) preparation of [ Sn ] by magnetron sputtering20Sb80(a)/Si(b)]xMultilayer phase change film:

a. rotating the empty base to Sn20Sb80Target site, turn on Sn20Sb80Starting to sputter Sn by the radio frequency power supply on the target according to the set sputtering time20Sb80Sputtering the surface of the target material and cleaning Sn20Sb80A target surface;

b、Sn20Sb80after the target surface is cleaned, Sn is turned off20Sb80Rotating the hollow base support to the Si target position by the radio frequency power supply applied to the target position, starting the radio frequency power supply on the Si target, starting sputtering the surface of the Si target according to the set sputtering time, and cleaning the surface of the Si target position;

c. rotating the substrate sputtered with the GeTe layer to an Sb target position, starting a radio frequency power supply on the Sb target position, and obtaining an Sb layer after sputtering is finished; after the surface of the Si target is cleaned, the substrate to be sputtered is rotated to Sn20Sb80Target site, turn on Sn20Sb80The radio frequency power supply on the target position starts to sputter Sn according to the set sputtering time20Sb80A film;

d、Sn20Sb80after the film sputtering is finished, Sn is switched off20Sb80The radio frequency power supply applied on the target rotates the substrate to the Si target position, the radio frequency power supply of the Si target position is started, and the sputtering of the Si film is started according to the set sputtering time;

e. repeating the steps c and d, and obtaining Sn after the sputtering is finished20Sb80the/Si multilayer phase-change thin film material.

Optionally, in the step II, the volume percentage of the high-purity argon is more than or equal to 99.999 percent, the flow of the Ar gas is within the range of 25 SCCM-30 SCCM, and the sputtering pressure of the argon is within the range of 0.15 Pa-0.35 Pa.

Optionally, in the step (c), the power of the radio frequency power supply used for magnetron sputtering is in the range of 25W-35W.

Compared with the prior art, the technical scheme provided by the invention has the following advantages:

the invention provides Sn20Sb80a/Si multilayer phase-change thin film material prepared by mixing Sn20Sb80The layers and the Si layers are alternately deposited and compounded, so that the Sn20Sb80the/Si multilayer phase change film material is of a multilayer composite film structure, so that the thermal stability of the phase change memory is improved, the power consumption of the phase change memory is reduced, and the comprehensive performance of the phase change memory is improved.

Sn of the invention20Sb80the/Si multilayer phase-change film material is prepared by a magnetron sputtering method, and the control of Sn is further realized by controlling the sputtering time20Sb80Thickness of the layer and the Si layer. The Sn20Sb80The structural general formula of the/Si multilayer phase-change film material is [ Sn ]20Sb80(a)/Si(b)]xWherein a is a single layer of Sn20Sb80The thickness of the layer, a ═ 1nm to 50 nm; b is the thickness of a single Si layer, b is 1nm to 50nm, and x is Sn20Sb80The number of alternating periods of the layers and the Si layer, x being a positive integer.

Drawings

FIG. 1 is Sn of examples 1 to 4 of the present invention20Sb80The relationship curve of the in-situ Resistance and the Temperature of the/Si multilayer phase change film material and the phase change film material of the comparative example 1 is shown in the figure, wherein the Temperature of the abscissa is the Temperature, and the Resistance of the ordinate is the Resistance;

FIG. 2 shows Sn obtained in examples 1 to 4 of the present invention20Sb80/Si multilayer phase-change thin film material and pairThe Kubelka-Munk function diagram of the phase-change film material in the proportion 1 shows that Energy is Energy and Absorbance is absorptivity.

Detailed Description

As is known in the art, conventional phase change materials (e.g., Ge)2Sb2Te5) The overall performance of the composition needs to be improved.

In order to solve the above problems, the present invention provides Sn20Sb80the/Si multilayer phase change film material can improve the comprehensive performance of the phase change memory.

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1

In this embodiment, Sn is20Sb80the/Si multilayer phase-change thin film material is of a multilayer composite film structure and is composed of Sn20Sb80The layers and Si layers are alternately deposited and compounded, and one layer of Sn is formed20Sb80Layers and one Si layer as one alternating period, Sn of the latter alternating period20Sb80The layer is deposited over the Si layer of the previous alternating period; the Sn20Sb80The layer is Sn20Sb80The target material is obtained by a magnetron sputtering method, and the Si layer is obtained by a Si target material by the magnetron sputtering method.

In this embodiment, Sn is20Sb80The structural general formula of the/Si multilayer phase-change film material is [ Sn ]20Sb80(3nm)/Si(7nm)]5I.e. single layer of Sn20Sb80The thickness of the layer was 3nm, the thickness of the single Si layer was 7nm, Sn20Sb80The number of alternating periods of layers and Si layers was 5.

In this embodiment, Sn is20Sb80The total thickness of the/Si multilayer phase change film material is 50 nm. Sn (tin)20Sb80The layer contains two elements of Sn and Sb, and the atomic ratio of Sn to Sb is 20: 80.

Sn of the present example20Sb80the/Si multilayer phase-change film material is obtained by adopting a magnetron sputtering method, and the specific preparation method comprises the following steps:

firstly, preparing a substrate and cleaning SiO2the/Si (100) substrate is used for removing dust particles, organic and inorganic impurities by cleaning the surface and the back surface. Firstly, carrying out strong ultrasonic cleaning in an acetone solution for 3-5 minutes, and then washing with deionized water; then washing in ethanol solution by strong ultrasonic for 3-5 min, washing with deionized water, and then washing with high-purity N2Drying the surface and the back; and drying the water vapor in a drying oven at 120 ℃ for about 20 minutes.

Preparing magnetron sputtering, namely placing the substrate to be sputtered cleaned in the step I on a base, and respectively loading Sn20Sb80The purity of the target material and the Si target material reach 99.999 percent (atomic percent), and the background is vacuumized to 1 x 10 < -4 > Pa; setting the sputtering power to be 30W; high-purity Ar was used as a sputtering gas (99.999% by volume), the Ar gas flow was set at 30SCCM, and the sputtering gas pressure was adjusted to 0.3 Pa.

Preparing [ Sn ] by magnetron sputtering20Sb80(a)/Si(b)]x multilayer phase change film:

a) rotating the empty base to Sn20Sb80Target site, turn on Sn20Sb80The RF power supply on the target starts to perform the sputtering process for Sn according to the set sputtering time (e.g. 100s)20Sb80Sputtering the surface of the target material and cleaning Sn20Sb80A target surface;

b)Sn20Sb80after the target surface is cleaned, Sn is turned off20Sb80Rotating the hollow base support to the Si target position by the radio frequency power supply applied to the target position, starting the radio frequency power supply on the Si target, starting sputtering the surface of the Si target according to the set sputtering time (such as 100s), and cleaning the surface of the Si target;

c) after the surface of the Si target is cleaned, the substrate to be sputtered is rotated to Sn20Sb80Target site, turn on Sn20Sb80The radio frequency power supply on the target position starts to sputter Sn according to the set sputtering time20Sb80A film;

d)Sn20Sb80after the film sputtering is finished, Sn is switched off20Sb80The radio frequency power supply applied on the target rotates the substrate to the Si target position, the radio frequency power supply of the Si target position is started, and the sputtering of the Si film is started according to the set sputtering time;

repeating the steps c) and d) to obtain SiO2Preparation of [ Sn ] on/Si (100) substrates20Sb80(3nm)/Si(7nm)]5Multilayer composite phase change film material. In this embodiment, Sn is20Sb80The thickness of the/Si multilayer phase-change film material is controlled by sputtering time, Sn20Sb80The sputtering rate of (2) was 3.74953s/nm, and the sputtering rate of Si was 15.57632 s/nm.

Example 2

In this embodiment, Sn is20Sb80The structural general formula of the/Si multilayer phase-change film material is [ Sn ]20Sb80(4nm)/Si(6nm)]5I.e. single layer of Sn20Sb80The thickness of the layer was 4nm, the thickness of the single Si layer was 6nm, Sn20Sb80The number of alternating periods of layers and Si layers was 5. The Sn20Sb80The total thickness of the/Si multilayer phase change film material is 50 nm.

The preparation method of this example is similar to example 1, except that [ Sn ]20Sb80(4nm)/Si(6nm)]5Single layer of Sn in thin film20Sb80The thickness of the layer was 4nm and the thickness of the single Si layer was 6 nm.

Example 3

In this embodiment, Sn is20Sb80The structural general formula of the/Si multilayer phase-change film material is [ Sn ]20Sb80(6nm)/Si(4nm)]5I.e. single layer of Sn20Sb80The thickness of the layer was 6nm, the thickness of the single Si layer was 4nm, Sn20Sb80The number of alternating periods of layers and Si layers was 5. The Sn20Sb80The total thickness of the/Si multilayer phase change film material is 50 nm.

The preparation method of this example is similar to example 1, except that [ Sn ]20Sb80(6nm)/Si(4nm)]5Single layer of Sn in thin film20Sb80The thickness of the layer was 6nm and the thickness of the single Si layer was 4 nm.

Example 4

In this embodiment, Sn is20Sb80The structural general formula of the/Si multilayer phase-change film material is [ Sn ]20Sb80(8nm)/Si(2nm)]5I.e. single layer of Sn20Sb80The thickness of the layer is 8nm, the thickness of the single-layer Si layer is 2nm, Sn20Sb80The number of alternating periods of layers and Si layers was 5. The Sn20Sb80The total thickness of the/Si multilayer phase change film material is 50 nm.

The preparation method of this example is similar to example 1, except that [ Sn ]20Sb80(8nm)/Si(2nm)]5Single layer of Sn in thin film20Sb80The thickness of the layer was 8nm and the thickness of the single Si layer was 2 nm.

Comparative example 1

Single layer Sn was prepared in this comparative example20Sb80And the thickness of the phase-change thin film material is 50 nm.

The preparation steps are as follows:

1. cleaning SiO2a/Si (100) substrate, cleaning the surface and the back, and removing dust particles, organic and inorganic impurities;

a) carrying out strong ultrasonic cleaning in an acetone solution for 3-5 minutes, and washing with deionized water;

b) strong ultrasonic cleaning in alcohol solution for 3-5 min, washing with deionized water, and high-purity N2Drying the surface and the back;

c) the water vapor was dried in an oven at 120 c for about 20 minutes.

2. Preparation of Sn by radio frequency sputtering method20Sb80Preparing a film:

a) filled with Sn20Sb80Sputtering target material, the purity of the target material reaches 99.999% (atomic percent), and vacuumizing the background to 1 x 10 < -4 > Pa;

b) setting sputtering power 30W;

c) high-purity Ar gas was used as the sputtering gas (99.999% by volume), the Ar gas flow was set at 30SCCM, and the sputtering gas pressure was adjusted to 0.3 Pa.

3. Preparing Sn by adopting magnetron sputtering method20Sb80Nano phase change film material:

a) rotating the empty base to Sn20Sb80Target site, turn on Sn20Sb80The RF power applied to the target starts to sputter Sn for a predetermined sputtering time (190s)20Sb80Sputtering the target material and cleaning Sn20Sb80The surface of the target material;

b)Sn20Sb80after the surface of the target material is cleaned, Sn is turned off20Sb80RF power applied to the target rotates the sputtering target to Sn20Sb80Target position, turn on Sn20Sb80The target position radio frequency power supply starts to sputter single-layer Sn according to the set sputtering time (190s)20Sb80A film.

Experimental methods and results

Referring to fig. 1, 4 kinds of [ Sn ] prepared in examples 1 to 420Sb80(a)/Si(b)]xMultilayer phase change thin film material and single layer Sn of comparative example 120Sb80The phase change film materials are tested to obtain a relation curve of the in-situ Resistance and the Temperature of each phase change film material, wherein the Temperature of the abscissa in the graph is the Temperature, and the Resistance of the ordinate is the Resistance.

Referring to FIG. 2, 4 kinds of [ Sn ] prepared in the above example20Sb80(a)/Si(b)]xMultilayer phase change thin film material and single layer Sn of comparative example20Sb80The phase change film materials are tested to obtain Kubelka-Munk function images of the phase change film materials, wherein Energy is Energy, and Absorbance is absorption rate.

As can be seen from FIG. 1, the following is [ Sn ]20Sb80(a)/Si(b)]xThe relative thickness of the Si layer in the multi-layer phase change film is increased, the crystallization temperature of the phase change film is increased, and single-layer Sn can be seen20Sb80Phase change thin film material, [ Sn ]20Sb80(8nm)/Si(2nm)]5、[Sn20Sb80(6nm)/Si(4nm)]5、[Sn20Sb80(4nm)/Si(6nm)]5And [ Sn20Sb80(3nm)/Si(7nm)]5The crystallization temperatures of the multi-layer phase-change film material are 192 ℃, 181 ℃, 212 ℃, 232 ℃ and 246 ℃, respectively, which shows that the thermal stability is improved. In addition, with [ Sn20Sb80(a)/Si(b)]xThe relative thickness of the Si layer in the multi-layer phase change film is increased, and the resistance of an amorphous state is increased, so that the reduction of operation power consumption in the phase change process of the device is facilitated.

FIG. 2 shows that conventional Sn20Sb80The band gap of the phase change film material is 0.201 eV. When [ Sn ]20Sb80(a)/Si(b)]xThe relative thickness of Si layer in the multi-layer phase-change film increases, the band gap increases accordingly, [ Sn ]20Sb80(8nm)/Si(2nm)]5、[Sn20Sb80(6nm)/Si(4nm)]5、 [Sn20Sb80(4nm)/Si(6nm)]5And [ Sn20Sb80(3nm)/Si(7nm)]5The band gaps of the multilayer phase change film are 0.244eV, 0.285eV, 0.360eV, and 0.408eV, respectively. Generally, the energy band gap is a measure of the amorphous resistance of an inorganic nonmetallic material, and when the energy band gap is larger, the lower the carrier concentration in the gap, the poorer the conductivity of the film, the higher the amorphous resistance, and vice versa, the lower the amorphous resistance. Thus, [ Sn ] of the present invention20Sb80(a)/Si(b)]xThe multi-layer phase-change film has Sn higher than that of the conventional Sn20Sb80The phase-change film material has larger amorphous resistance, thereby greatly reducing the operation power consumption in the phase-change process.

Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

图1
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