CN115207111A - 一种HfO2基铁电薄膜及其制备方法 - Google Patents
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Abstract
本发明提供了一种HfO2基铁电薄膜,包括衬底层,衬底层的上表面从下到上依次设置有底电极层、第一HfO2基薄膜层、HfSe2散片层、第二HfO2基薄膜层和顶电极层,本发明还提供了上述HfO2基铁电薄膜的制备方法,与现有技术相比,本发明具有如下优点:本发明通过将二维HfSe2嵌入层界面固定氧空位,规律晶格错位引入非对称性铁电相核,显著提高HfO2铁电薄膜的极化强度,具体表现为将HfO2铁电薄膜的极化值提高至接近于理论值。
Description
技术领域
本发明涉及铁电薄膜领域,具体而言,涉及一种HfO2基铁电薄膜及其制备方法。
背景技术
近年来,作为一种新型的铁电氧化物,HfO2受到越来越多的关注。与传统的钙钛矿铁电材料相比,HfO2具有更小的介电常数和超薄的纳米级厚度。HfO2的铁电性可以在超薄状态下存在,这对集成电路的微缩化非常诱人。同时,众所周知HfO2在微电子工艺中具有广泛的应用,如高k绝缘栅、非易失性存储器等,在此过程中,HfO2形成了与COMS工业工艺的良好兼容性和非常成熟的超薄共形制造技术。因此,在HfO2中观察到的这种新的铁电现象将大大拓宽铁电极化领域的应用范围。
一般来说,非中心对称的晶体结构是铁电形成的原因。氧空位缺陷有助于形成非中心对称的晶体结构。然而,具有较多氧空位的HfO2薄膜往往对氧化很敏感这导致铁电性能的下降和不稳定。
发明内容
本发明的目的是提供一种HfO2基铁电薄膜,通过将二维HfSe2嵌入层界面固定氧空位,规律晶格错位引入非对称性铁电相核,显著提高HfO2铁电薄膜的极化强度,将HfO2铁电薄膜的极化值提高至接近于理论值。
为达到上述目的,本发明提供一种HfO2基铁电薄膜,包括衬底层,所述衬底层的上表面从下到上依次设置有底电极层、第一HfO2基薄膜层、HfSe2散片层、第二HfO2基薄膜层和顶电极层。
本发明的另一个目的还在于提供一种制备所述HfO2基铁电薄膜的方法,所述方法具体包括如下步骤:S1、预先对衬底层进行清洗;
S2、在步骤S1清洗后的衬底层上沉积底电极层;
S3、在步骤S2中沉积的底电极层上沉积第一HfO2基薄膜层;
S4、在步骤S3中沉积的第一HfO2基薄膜层上覆盖HfSe2散片层;
S5、在步骤S4中的覆盖的HfSe2散片层上沉积第二HfO2基薄膜层;
S6、对步骤S5中沉积的第二HfO2基薄膜层表面进行退火处理;
S7、在步骤S6中经退火处理后的第二HfO2基薄膜层上沉积顶电极层得HfO2基铁电薄膜。
作为优选,所述步骤S1中,衬底层的材料为硅,采用RCA清洗法对衬底层进行清洗。
作为优选,所述步骤S2和步骤S7中,底电极层和顶电极层的材料均为Pt,且所述底电极层和所述顶电极层均采用电子束蒸发法沉积,电子束蒸发法的工艺参数如下:真空度为7Pa、束流电流为10A。
作为优选,所述步骤S2和步骤S7中,底电极层和顶电极层的厚度均为30nm。
作为优选,所述步骤S3中,第一HfO2基薄膜层采用原子层沉积法沉积,且工艺参数如下:沉积温度为250℃,沉积时间为15-30min,沉积厚度为3-5nm。
作为优选,原子层沉积过程中,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3。
作为优选,所述步骤S4中,HfSe2单层散片的购置的化学气相传输(CVT)方法合成的块状HfSe2进行机械剥离,通过标准的机械剥离HfSe2薄片,具体步骤为:片状的HfSe2并以丙酮/丙醇浸泡的方式进行清洗,然后在氮气环境下在O2和H2O<3ppm手套箱中使用低残留的热脱模带(Nitto-Denko Revalpha)进行脱离。
作为优选,所述步骤S5中,第二HfO2基薄膜层采用原子层沉积法沉积,且工艺参数如下:沉积温度为250℃,沉积时间为15-30min,厚度为3-5nm。
作为优选,原子层沉积过程中,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3。
作为优选,所述步骤S6中,退火处理具体包括如下步骤:在氮气保护气氛下以5℃/min的升温速率加热到150℃后保温5min、以3℃/min的升温速率加热到250℃后保温5min、以23℃/min的升温速率加热到400℃后保温5min、以10℃/min的升温速率加热到450℃后保温5min,最后再以10℃/min的升温速率加热到800℃并保温2min,最后冷却至室温。
与现有技术相比,本发明具有如下优点:本发明通过将二维HfSe2嵌入层界面固定氧空位,规律晶格错位引入非对称性铁电相核,显著提高HfO2铁电薄膜的极化强度,具体表现为将HfO2铁电薄膜的极化值提高至接近于理论值。
附图说明
图1为本发明HfO2基铁电薄膜的结构示意图;
图2为制备本发明HfO2基铁电薄膜的流程图;
图3为本发明实施例2制得的HfO2基铁电薄膜的投射电镜结构TEM结构图;
图4为本发明实施例2制得的HfO2基铁电薄膜的压电力显微镜(PFM)响应图;
图5为本发明实施例2制得的HfO2基铁电薄膜的极化特性图。
附图标记说明:
1-衬底层;2-底电极层;3-第一HfO2基薄膜层;4-HfSe2散片层、5-第二HfO2基薄膜层;6-顶电极层。
具体实施方式
为使本发明的上述目的、特征和优点能够更为明显易懂,下面结合附图对本发明的具体实施例做详细的说明。
实施例1
如图1所示,一种HfO2基铁电薄膜,包括衬底层1,衬底层1的上表面从下到上依次设置有底电极层2、第一HfO2基薄膜层3、HfSe2散片层4、第二HfO2基薄膜层5和顶电极层6。
本发明中,HfSe2是一种Hf基二维半导体材料,HfSe2/HfO2具有类比Si/SiO2的界面特性。即,HfO2作为HfSe2的天然氧化物层,两者具有良好的接触界面。同时由于Se的引入,可以较好的固定氧空位,并与周围Hf-O化学结构形成应力,促成非中心对称晶体结构相的形成。
如图2所示,上述HfO2基铁电薄膜的制备方法具体包括如下步骤:
S1、预先对衬底层1进行清洗,衬底层1的材料为硅,采用RCA清洗法对衬底层1进行清洗;
S2、在步骤S1清洗后的衬底层1上沉积底电极层2;
S3、在步骤S2中沉积的底电极层2上采用原子层沉积法沉积第一HfO2基薄膜层3,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3,且原子层沉积的工艺参数如下:沉积温度为250℃,沉积时间为15min,沉积厚度为3nm;
S4、在步骤S3中沉积的第一HfO2基薄膜层3上覆盖HfSe2散片层4;
S5、在步骤S4中覆盖的HfSe2散片层4上采用原子层沉积法沉积第二HfO2基薄膜层5,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3,且原子层沉积的工艺参数如下:沉积温度为250℃,沉积时间为15min,沉积厚度为3-5nm;
S6、对步骤S5中沉积的第二HfO2基薄膜层5表面进行退火处理,具体为:在氮气保护气氛下以5℃/min的升温速率加热到150℃后保温5min、以3℃/min的升温速率加热到250℃后保温5min、以23℃/min的升温速率加热到400℃后保温5min、以10℃/min的升温速率加热到450℃后保温5min,最后再以10℃/min的升温速率加热到800℃并保温2min,最后冷却至室温。
S7、在步骤S6中经退火处理后的第二HfO2基薄膜层5上沉积顶电极层6得HfO2基铁电薄膜。
步骤S1中,RCA标准清洗法是1965年由Kern和Puotinen等人在N.J.Princeton的RCA实验室首创的,并由此而得名,RCA清洗是一种典型的、普遍使用的湿式化学清洗法,是去除硅片表面各类玷污的有效方法,所用清洗装置大多是多槽处理式清洗系统。
该清洗系统主要包括以下几种药液:
(1)SPM:H2SO4/H2O2120~150℃SPM具有很高的氧化能力,可将金属氧化后溶于清洗液中,并能把有机物氧化生成CO2和H2O。用SPM清洗硅片可去除硅片表面的重有机沾污和部分金属,但是当有机物沾污特别严重时会使有机物碳化而难以去除。
(2)HF(DHF):HF(DHF)20~25℃DHF可以去除硅片表面的自然氧化膜,因此,附着在自然氧化膜上的金属将被溶解到清洗液中,同时DHF抑制了氧化膜的形成。因此可以很容易地去除硅片表面的Al,Fe,Zn,Ni等金属,DHF也可以去除附着在自然氧化膜上的金属氢氧化物。用DHF清洗时,在自然氧化膜被腐蚀掉时,硅片表面的硅几乎不被腐蚀。
(3)APM(SC-1):NH4OH/H2O2/H2O 30~80℃由于H2O2的作用,硅片表面有一层自然氧化膜(SiO2),呈亲水性,硅片表面和粒子之间可被清洗液浸透。由于硅片表面的自然氧化层与硅片表面的Si被NH 4OH腐蚀,因此附着在硅片表面的颗粒便落入清洗液中,从而达到去除粒子的目的。在NH4OH腐蚀硅片表面的同时,H2O 2又在氧化硅片表面形成新的氧化膜。
(4)HPM(SC-2):HCl/H2O2/H2O 65~85℃用于去除硅片表面的钠、铁、镁等金属沾污。在室温下HPM就能除去Fe和Zn。
本实施例中,步骤S2和步骤S7中,底电极层2和顶电极层6的材料均为Pt,且底电极层2和顶电极层6均采用电子束蒸发法沉积,电子束蒸发法的工艺参数如下:真空度为7Pa、束流电流为10A,底电极层2和顶电极层6的厚度均为30nm。
本实施例中,步骤S4中,HfSe2单层散片的购置的化学气相传输(CVT)方法合成的块状HfSe2进行机械剥离,通过标准的机械剥离HfSe2薄片,具体步骤为:片状的HfSe2并以丙酮/丙醇浸泡的方式进行清洗,然后在氮气环境下在O2和H2O<3ppm手套箱中使用低残留的热脱模带(Nitto-Denko Revalpha)进行脱离。
实施例2
如图1所示,本实施例的HfO2基铁电薄膜的结构与实施例1的HfO2基铁电薄膜的结构相同,区别在于制备方法,如图2所示,本实施例中的HfO2基铁电薄膜的制备方法包括如下步骤:
S1、预先对衬底层1进行清洗,衬底层1的材料为硅,采用RCA清洗法对衬底层1进行清洗;
S2、在步骤S1清洗后的衬底层1上沉积底电极层2;
S3、在步骤S2中沉积的底电极层2上采用原子层沉积法沉积第一HfO2基薄膜层3,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3,且原子层沉积的工艺参数如下:沉积温度为250℃,沉积时间为20min,沉积厚度为4nm;
S4、在步骤S3中沉积的第一HfO2基薄膜层3上覆盖HfSe2散片层4;
S5、在步骤S4中覆盖的HfSe2散片层4上采用原子层沉积法沉积第二HfO2基薄膜层5,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3,且原子层沉积的工艺参数如下:沉积温度为250℃,沉积时间为22min,沉积厚度为4nm;
S6、对步骤S5中沉积的第二HfO2基薄膜层5表面进行退火处理,具体为:在氮气保护气氛下以5℃/min的升温速率加热到150℃后保温5min、以3℃/min的升温速率加热到250℃后保温5min、以23℃/min的升温速率加热到400℃后保温5min、以10℃/min的升温速率加热到450℃后保温5min,最后再以10℃/min的升温速率加热到800℃并保温2min,最后冷却至室温。
S7、在步骤S6中经退火处理后的第二HfO2基薄膜层5上沉积顶电极层6得HfO2基铁电薄膜。
本实施例中,步骤S2和步骤S7中,底电极层2和顶电极层6的材料均为Pt,且底电极层2和顶电极层6均采用电子束蒸发法沉积,电子束蒸发法的工艺参数如下:真空度为7Pa、束流电流为10A,底电极层2和顶电极层6的厚度均为30nm。
实施例3
如图1所示,本实施例的HfO2基铁电薄膜的结构与实施例1的HfO2基铁电薄膜的结构相同,区别在于制备方法,如图2所示,本实施例中的HfO2基铁电薄膜的制备方法包括如下步骤:
S1、预先对衬底层1进行清洗,衬底层1的材料为硅,采用RCA清洗法对衬底层1进行清洗;
S2、在步骤S1清洗后的衬底层1上沉积底电极层2;
S3、在步骤S2中沉积的底电极层2上采用原子层沉积法沉积第一HfO2基薄膜层3,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3,且原子层沉积的工艺参数如下:沉积温度为250℃,沉积时间为30min,沉积厚度为5nm;
S4、在步骤S3中沉积的第一HfO2基薄膜层3上覆盖HfSe2散片层4;
S5、在步骤S4中覆盖的HfSe2散片层4上采用原子层沉积法沉积第二HfO2基薄膜层5,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3,且原子层沉积的工艺参数如下:沉积温度为250℃,沉积时间为30min,沉积厚度为5nm;
S6、对步骤S5中沉积的第二HfO2基薄膜层5表面进行退火处理,具体为:在氮气保护气氛下以5℃/min的升温速率加热到150℃后保温5min、以3℃/min的升温速率加热到250℃后保温5min、以23℃/min的升温速率加热到400℃后保温5min、以10℃/min的升温速率加热到450℃后保温5min,最后再以10℃/min的升温速率加热到800℃并保温2min,最后冷却至室温。
S7、在步骤S6中经退火处理后的第二HfO2基薄膜层5上沉积顶电极层6得HfO2基铁电薄膜。
本实施例中,步骤S2和步骤S7中,底电极层2和顶电极层6的材料均为Pt,且底电极层2和顶电极层6均采用电子束蒸发法沉积,电子束蒸发法的工艺参数如下:真空度为7Pa、束流电流为10A,底电极层2和顶电极层6的厚度均为30nm。
发明人对实施例2制得的HfO2基铁电薄膜进行性能表征,表征结果分别如图3、图4和图5所示,其中图3为实施例2制得的HfO2基铁电薄膜的投射电镜结构(TEM)图,用镓离子在TEM表征之前进行铣削,在300千伏的条件下使用校正的FEI Titan获得TEM图像,从图3中可以观察到良好的HfSe2/HfO2接触界面特性;图4为实施例2制得的HfO2基铁电薄膜的压电力显微镜(PFM)响应图,其中,横坐标为顶电极施加电压幅值,右纵坐标为HfO2基铁电薄膜的PFM响应振幅值,左纵坐标为HfO2薄膜的PFM响应相位值,从图4可以看出,本发明HfO2基铁电薄膜的PFM振幅、相位响应滞回清晰,证明畴极化翻转的存在,从PFM振幅响应可知极化切换的最大位移,从PFM相位响应可知畴的类型为多畴结构;图5为实施例2制得的HfO2基铁电薄膜的极化特性图,横坐标为顶电极施加电压,纵坐标为HfO2基铁电薄膜的极化值,从图5可以看出,本发明HfO2基铁电薄膜具有十分优异的极化性能,加载8V时剩余极化强度为接近60μC/cm2,远高于大多数的制备水平(约接近50μC/cm2),通过本发明工艺方法所制备的HfO2基铁电薄膜极化性能得到了明显增强。
虽然本公开披露如上,但本公开的保护范围并非仅限于此。本领域技术人员,在不脱离本公开的精神和范围的前提下,可进行各种变更与修改,这些变更与修改均将落入本发明的保护范围。
Claims (10)
1.一种HfO2基铁电薄膜,其特征在于,包括衬底层(1),所述衬底层(1)的上表面从下到上依次设置有底电极层(2)、第一HfO2基薄膜层(3)、HfSe2散片层(4)、第二HfO2基薄膜层(5)和顶电极层(6)。
2.一种制备如权利要求1所述的HfO2基铁电薄膜的方法,其特征在于,所述方法具体包括如下步骤:S1、预先对衬底层(1)进行清洗;
S2、在步骤S1清洗后的衬底层(1)上沉积底电极层(2);
S3、在步骤S2中沉积的底电极层(2)上沉积第一HfO2基薄膜层(3);
S4、在步骤S3中沉积的第一HfO2基薄膜层(3)上覆盖HfSe2散片层(4);
S5、在步骤S4中的覆盖的HfSe2散片层(4)上沉积第二HfO2基薄膜层(5);
S6、对步骤S5中沉积的第二HfO2基薄膜层(5)表面进行退火处理;
S7、在步骤S6中经退火处理后的第二HfO2基薄膜层(5)上沉积顶电极层(6)得HfO2基铁电薄膜。
3.如权利要求2所述的制备HfO2基铁电薄膜的方法,其特征在于,所述步骤S1中,衬底层(1)的材料为硅,采用RCA清洗法对衬底层(1)进行清洗。
4.如权利要求3所述的制备HfO2基铁电薄膜的方法,其特征在于,所述步骤S2和所述步骤S7中,底电极层(2)和顶电极层(6)的材料均为Pt,且所述底电极层(2)和所述顶电极层(6)均采用电子束蒸发法沉积,电子束蒸发法的工艺参数如下:真空度为7Pa、束流电流为10A。
5.如权利要求4所述的制备HfO2基铁电薄膜的方法,其特征在于,所述步骤S2和所述步骤S7中,底电极层(2)和顶电极层(6)的厚度均为30nm。
6.如权利要求2所述的制备HfO2基铁电薄膜的方法,其特征在于,所述步骤S3中,第一HfO2基薄膜层(3)采用原子层沉积法沉积,且工艺参数如下:沉积温度为250℃,沉积时间为15-30min,沉积厚度为3-5nm。
7.如权利要求6所述的制备HfO2基铁电薄膜的方法,其特征在于,原子层沉积过程中,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3。
8.如权利要求2所述的制备HfO2基铁电薄膜的方法,其特征在于,所述步骤S5中,第二HfO2基薄膜层(5)采用原子层沉积法沉积,且工艺参数如下:沉积温度为250℃,沉积时间为15-30min,厚度为3-5nm。
9.如权利要求8所述的制备HfO2基铁电薄膜的方法,其特征在于,原子层沉积过程中,前驱体为Hf[N(CH3)C2H5]4,氧化源前驱为O3。
10.如权利要求2所述的制备HfO2基铁电薄膜的方法,其特征在于,所述步骤S6中,退火处理具体包括如下步骤:在氮气保护气氛下以5℃/min的升温速率加热到150℃后保温5min、以3℃/min的升温速率加热到250℃后保温5min、以23℃/min的升温速率加热到400℃后保温5min、以10℃/min的升温速率加热到450℃后保温5min,最后再以10℃/min的升温速率加热到800℃并保温2min,最后冷却至室温。
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