CN110676377A - 一种铈掺杂二氧化钛忆阻器薄膜的制备方法 - Google Patents
一种铈掺杂二氧化钛忆阻器薄膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种铈掺杂二氧化钛忆阻器薄膜的制备方法,具体按照以下步骤实施:步骤1,制备铈金属氧化物溶胶;步骤2,制备二氧化钛溶胶;步骤3,将步骤1制备的铈金属氧化物溶胶和二氧化钛溶胶混合,待搅拌均匀后进行陈化得到铈掺杂二氧化钛溶胶,其中钛离子与铈离子的摩尔比为(200‑2000):1;步骤4,采用浸渍‑提拉法,以铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行铈掺杂二氧化钛凝胶薄膜的提拉,铈掺杂二氧化钛凝胶薄膜在室温下干燥后,再进行热处理得到铈掺杂氧化钛薄膜。该铈掺杂二氧化钛忆阻器薄膜的制备方法具有制备成本低、工艺简单、容易控制等优点。
Description
技术领域
本发明属于微电子材料阻变存储器薄膜制备技术领域,特别是涉及一种铈掺杂二氧化钛忆阻器薄膜的制备方法。
背景技术
作为下一代非易失性存储器,忆阻器薄膜材料由于结构简单、兼容性好、读写速度快、耐久性高、能耗低和成本低等优势正在被广泛研究。对于忆阻器薄膜器件来说,氧空位在氧化物中的迁移机制,为氧化物忆阻器薄膜的阻变机理研究提供新的思路,通过精确的引入杂质,可以调控氧空位的产生,进而提高忆阻器的性能,降低工作电压。而利用溶胶凝胶法可以实现分子水平的掺杂,以此为基础进行研究就能够不断提高开关比,提升忆阻器薄膜器件性能。
发明内容
本发明的目的在于提供了一种铈掺杂二氧化钛忆阻器薄膜的制备方法,用以提升忆阻器薄膜器件性能。
为了达到上述目的,本发明所采用的技术方案是,一种铈掺杂二氧化钛忆阻器薄膜的制备方法,具体按照以下步骤实施:
步骤1,制备铈金属氧化物溶胶;
步骤2,制备二氧化钛溶胶;
步骤3,将步骤1制备的铈金属氧化物溶胶和二氧化钛溶胶混合,待搅拌均匀后进行陈化得到铈掺杂二氧化钛溶胶,其中钛离子与铈离子的摩尔比为(200-2000):1;
步骤4,采用浸渍-提拉法,以铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行铈掺杂二氧化钛凝胶薄膜的提拉,铈掺杂二氧化钛凝胶薄膜在室温下干燥后,再进行热处理得到铈掺杂氧化钛薄膜。
本发明的技术方案,还具有以下特点,
在所述步骤1中,制备铈金属氧化物溶胶具体为:以乙醇为溶剂,以硝酸铈为前驱体,两者混合后于室温下搅拌6h~8h并陈化24h,配制得到摩尔比为0.04mol/l的氧化铈稀溶胶。
在所述步骤2中,制备氧化钛溶胶具体为:以乙醇为溶剂,以钛酸丁酯作为前驱体,钛酸丁酯和乙醇按1:10的摩尔比混合后,采用硝酸调节PH值为2~3,于室温下搅拌6h~8h后陈化24h得到二氧化钛溶胶。
在所述步骤3中,搅拌的时间为8h,陈化时间为24h。
在所述步骤3中,热处理在氩气或空气或氧气气氛下进行。
本发明的有益效果是:本发明的一种铈掺杂二氧化钛忆阻器薄膜的制备方法具有制备成本低、工艺简单、容易控制等优点,不仅提高了铈掺杂氧化钛忆阻器薄膜的制备效率,而且制备得到的铈掺杂氧化钛忆阻器薄膜还具有良好的电阻反转特性。
附图说明
图1是采用原子力显微镜(AFM)分别对实施例1制备得到的铈掺杂二氧化钛忆阻器薄膜进行微观形貌的观察图;
图2是采用原子力显微镜(AFM)分别对实施例2制备得到的铈掺杂二氧化钛忆阻器薄膜进行微观形貌的观察图;
图3是采用原子力显微镜(AFM)分别对实施例3制备得到的铈掺杂二氧化钛忆阻器薄膜进行微观形貌的观察图;
图4是采用原子力显微镜(AFM)分别对实施例4制备得到的铈掺杂二氧化钛忆阻器薄膜进行微观形貌的观察图;
图5是采用原子力显微镜(AFM)分别对实施例5制备得到的无铈掺杂二氧化钛忆阻器薄膜进行微观形貌的观察图;
图6是实施例1-5制备得到的产物的透过率光谱图;
图7是实施例1-5制备得到的产物的反射率光谱图;
图8是采用X射线光电子能谱分别对实施例1-4制备得到的铈掺杂二氧化钛忆阻器薄膜进行化学状态的分析图;
图9是实施例3的二氧化钛薄忆阻器薄膜的I-V曲线图。
图中:0表示实施例5制备得到的无铈掺杂二氧化钛忆阻器薄膜,200:1表示实施例1制备得到的铈掺杂二氧化钛忆阻器薄膜,800:1表示实施例2制备得到的铈掺杂二氧化钛忆阻器薄膜,1200:1表示实施例3制备得到的铈掺杂二氧化钛忆阻器薄膜,2000:1表示实施例4制备得到的铈掺杂二氧化钛忆阻器薄膜。
具体实施方式
下面结合附图说明和具体实施方式对本发明的技术方案作进一步的详细说明。
一种铈掺杂二氧化钛忆阻器薄膜的制备方法,具体按照以下步骤实施:
步骤1,以乙醇为溶剂,以硝酸铈为前驱体,两者混合后于室温下搅拌6h~8h并陈化24h,配制得到摩尔比为0.04mol/l的氧化铈溶胶;
步骤2,以乙醇为溶剂,以钛酸丁酯作为前驱体,钛酸丁酯和乙醇按1:10的摩尔比混合后,采用硝酸调节PH值为2~3,于室温下搅拌6h~8h后陈化24h得到二氧化钛溶胶;
步骤3,将步骤1制备的氧化铈溶胶和二氧化钛溶胶混合,待搅拌8h后进行24h陈化得到铈掺杂二氧化钛溶胶,其中钛离子与铈离子的摩尔比为(200-2000):1;
步骤4,采用浸渍-提拉法,以铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行铈掺杂二氧化钛凝胶薄膜的提拉,铈掺杂二氧化钛凝胶薄膜在室温下干燥后,在氩气或空气或氧气气氛下进行热处理得到铈掺杂二氧化钛薄膜。
实施例1
一种铈掺杂二氧化钛忆阻器薄膜的制备方法,具体按照以下步骤实施:
步骤1,以乙醇为溶剂,以硝酸铈为前驱体,两者混合后于室温下搅拌8h并陈化24h,配制得到摩尔比为0.04mol/l的氧化铈溶胶;
步骤2,以乙醇为溶剂,以钛酸丁酯作为前驱体,钛酸丁酯和乙醇按1:10的摩尔比混合后,采用硝酸调节PH值为3,于室温下搅拌6h~8h后陈化24h得到氧化钛溶胶;
步骤3,将步骤1制备的氧化铈溶胶和氧化钛溶胶混合,待搅拌8h后进行24h陈化得到铈掺杂二氧化钛溶胶,其中钛离子与铈离子的摩尔比为200:1;
步骤4,采用浸渍-提拉法,以铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行铈掺杂二氧化钛凝胶薄膜的提拉,铈掺杂二氧化钛凝胶薄膜在室温下干燥后,在氧气气氛下进行热处理得到铈掺杂氧化钛薄膜。
实施例2
一种铈掺杂二氧化钛忆阻器薄膜的制备方法,具体按照以下步骤实施:
步骤1,以乙醇为溶剂,以硝酸铈为前驱体,两者混合后于室温下搅拌6h~8h并陈化24h,配制得到摩尔比为0.04mol/l的氧化铈溶胶;
步骤2,以乙醇为溶剂,以钛酸丁酯作为前驱体,钛酸丁酯和乙醇按1:10的摩尔比混合后,采用硝酸调节PH值为3,于室温下搅拌6h~8h后陈化24h得到氧化钛溶胶;
步骤3,将步骤1制备的氧化铈溶胶和氧化钛溶胶混合,待搅拌8h后进行24h陈化得到铈掺杂二氧化钛溶胶,其中钛离子与铈离子的摩尔比为800:1;
步骤4,采用浸渍-提拉法,以铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行铈掺杂二氧化钛凝胶薄膜的提拉,铈掺杂二氧化钛凝胶薄膜在室温下干燥后,在氧气气氛下进行热处理得到铈掺杂氧化钛薄膜。
实施例3
一种铈掺杂二氧化钛忆阻器薄膜的制备方法,具体按照以下步骤实施:
步骤1,以乙醇为溶剂,以硝酸铈为前驱体,两者混合后于室温下搅拌8h并陈化24h,配制得到摩尔比为0.04mol/l的氧化铈溶胶;
步骤2,以乙醇为溶剂,以钛酸丁酯作为前驱体,钛酸丁酯和乙醇按1:10的摩尔比混合后,采用硝酸调节PH值为3,于室温下搅拌6h~8h后陈化24h得到氧化钛溶胶;
步骤3,将步骤1制备的氧化铈溶胶和氧化钛溶胶混合,待搅拌8h后进行24h陈化得到铈掺杂二氧化钛溶胶,其中钛离子与铈离子的摩尔比为1200:1;
步骤4,采用浸渍-提拉法,以铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行铈掺杂二氧化钛凝胶薄膜的提拉,铈掺杂二氧化钛凝胶薄膜在室温下干燥后,在氧气气氛下进行热处理得到铈掺杂氧化钛薄膜。
实施例4
一种铈掺杂二氧化钛忆阻器薄膜的制备方法,具体按照以下步骤实施:
步骤1,以乙醇为溶剂,以硝酸铈为前驱体,两者混合后于室温下搅拌8h并陈化24h,配制得到摩尔比为0.04mol/l的氧化铈溶胶;
步骤2,以乙醇为溶剂,以钛酸丁酯作为前驱体,钛酸丁酯和乙醇按1:10的摩尔比混合后,采用硝酸调节PH值为3,于室温下搅拌6h~8h后陈化24h得到氧化钛溶胶;
步骤3,将步骤1制备的氧化铈溶胶和氧化钛溶胶混合,待搅拌8h后进行24h陈化得到铈掺杂二氧化钛溶胶,其中钛离子与铈离子的摩尔比为2000:1;
步骤4,采用浸渍-提拉法,以铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行铈掺杂二氧化钛凝胶薄膜的提拉,铈掺杂二氧化钛凝胶薄膜在室温下干燥后,在氧气气氛下进行热处理得到铈掺杂氧化钛薄膜。
实施例5
实施例5作为对比实施例,未掺杂铈,制备方法如下:
步骤1,以乙醇为溶剂,以钛酸丁酯作为前驱体,钛酸丁酯和乙醇按1:10的摩尔比混合后,采用硝酸调节PH值为3,于室温下搅拌8h后陈化24h得到氧化钛溶胶;
步骤2,将步骤1制备的氧化钛溶胶搅拌8h后进行24h陈化得到无铈掺杂二氧化钛溶胶;
步骤3,采用浸渍-提拉法,以无铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行无铈掺杂二氧化钛凝胶薄膜的提拉,无铈掺杂二氧化钛凝胶薄膜在室温下干燥后,在氧气气氛下进行热处理得到铈掺杂氧化钛薄膜。
采用原子力显微镜(AFM)分别对实施例1-5制备得到不同浓度铈掺杂的二氧化钛忆阻器薄膜进行微观形貌的观察。薄膜的测试扫描范围为1μm×1μm,扫描模式为接触式模式,从图1~5中可以看出,图1钛离子和铈离子的摩尔掺杂比分别为200:1的铈掺杂二氧化钛忆阻器薄膜面内起伏值为16.32nm;图2钛离子和铈离子的摩尔掺杂比800:1的铈掺杂二氧化钛忆阻器薄膜面内起伏值为11.92nm;图3钛离子和铈离子的摩尔掺杂比1200:1的铈掺杂二氧化钛忆阻器薄膜面内起伏值为9.24nm;图4钛离子和铈离子的摩尔掺杂比2000:1的铈掺杂二氧化钛忆阻器薄膜面内起伏值为15.54nm;图5无铈掺杂二氧化钛忆阻器薄膜的面内起伏值为7.57nm。通过观察微区的表面形貌可知四种不同铈浓度掺杂的铈掺杂二氧化钛薄膜以及无铈掺杂二氧化钛薄膜表面都比较均匀、致密平整,平均粗糙度也都较低。但是随着铈掺杂量浓度的增加,表面形成的颗粒越来越明显,并且随着铈掺杂量浓度的增加,面内起伏值是不断增大的。这是因为,并且随着铈掺杂量浓度的增加,铈取代Ti原子的数量在不断增加,由于铈原子半径为0.27nm大于Ti原子半径0.20nm,所以铈掺杂后会使得二氧化钛晶胞尺寸有所膨胀,表面颗粒变多、变大。
为了进一步研究铈掺杂后的对二氧化钛薄膜的禁带宽度的改变,使用紫外-可见光分光光度计对实施例1-5制备的产物进行光学性能的测试,即反射率(R)和透射率(T)的测试。表1为五种不同铈浓度掺杂的二氧化钛薄膜的光学禁带宽度,该禁带宽度可由反射率、膜厚和透过率计算得出,具体的计算公式为:
α=(1/d)×㏑[(1-R)/T] (1)
αhν=C(hν-Eg)1/2 (2)
式中:α—吸收常数;d—膜厚;R—反射率;T—透射率;hν—入射光能量;C—光速,3×108m/s。
表1
如图6为实施例1-5制备得到的产物的透过率光谱图,由图6可以看出,样品在350nm波长处有强烈的吸收边,铈掺杂二氧化钛忆阻器薄膜具有最高的透过率。
如图7为实施例1-5制备得到的产物的反射率光谱图,由图7可以看出,每个样品均有明显的光干涉现象,表明薄膜表面光滑并且均匀;光学禁带宽度如表1所示,图1是以(αhν)2对hν作图,对曲线进行线性外延后,与横轴(X轴)的交点就是样品的光学禁带宽度。五种铈不同掺杂浓度的二氧化钛薄膜的禁带宽度分别为3.3165eV、3.2562eV、3.2616eV、3.4.31和3.4462eV,随着掺杂浓度的增大,禁带宽度呈现先变小后变大的趋势。
采用X射线光电子能谱分别对实施例1-4制备得到的铈掺杂二氧化钛忆阻器薄膜进行化学状态的研究。从图8中可以看出,Ce3d的光电子峰对应的结合能值分别为898.1eV和903.6eV,使用X射线光电子能谱手册(Handbook of X-ray photoelectronspectroscopy)对其进行分析发现,它与Ce3d的标准峰值范围符合较好。由不同摩尔掺杂量的Ce3d谱可以看出,铈掺杂改变了薄膜中钛元素的化学态,当铈进行不同掺杂量的制备时,铈原子夺走了一部分氧原子。随着铈摩尔掺杂量的增加,Ce3d的光电子谱峰越来越明显。但当铈掺杂超过一定量时,即钛离子和铈离子的摩尔掺杂比2000:1的二氧化钛薄膜,其掺杂对薄膜电阻开关特性的影响就不明显。
在X射线光电子能谱探测深度范围内测得铈掺杂氧化钛薄膜中还含有Ti2p、O1s。
使用电学测试系统对制备好的铈掺杂二氧化钛忆阻器薄膜器件进行阻变特性的测试。图9为实施例3于500℃氧气气氛热处理钛离子和铈离子摩尔掺杂比1200:1的二氧化钛薄忆阻器薄膜的I-V曲线。该曲线具有完整的双极性电阻转变特性。可以看到忆阻器在电压为0.83V的位置时电阻有个明显突变的情况,器件从高阻态变为低阻态,即发生SET过程,并且在后续的测试中稳定地保持着低阻态。当施加反向电压,在电压为-1.76V时电阻从低阻态转变为高阻态,即发生复位RESET过程,并且在后续的测试中保持了高阻态的性能。
氧化物组成的忆阻器薄膜发生电阻转变的现象,主要是由于氧空位细丝的形成和断裂,在正向电压下,薄膜中大量的氧空位迁移到Pt底电极,由于引入了铈原子进行有效地掺杂,薄膜中产生了更多的氧空位,使得氧空位的迁移几率增大。氧空位随电场方向移动的阻力较小,致使器件的SET电压和RESET电压均较小,呈现低功耗性,显示出较好的电阻转变特性。
Claims (5)
1.一种铈掺杂二氧化钛忆阻器薄膜的制备方法,其特征在于,具体按照以下步骤实施:
步骤1,制备铈金属氧化物溶胶;
步骤2,制备氧化钛溶胶;
步骤3,将步骤1制备的铈金属氧化物溶胶和氧化钛溶胶混合,待搅拌均匀后进行陈化得到铈掺杂二氧化钛溶胶,其中钛离子与铈离子的摩尔比为(200-2000):1;
步骤4,采用浸渍-提拉法,以铈掺杂二氧化钛溶胶为原料在室温下使用提拉机在Pt铂金电极基板上进行铈掺杂二氧化钛凝胶薄膜的提拉,铈掺杂二氧化钛凝胶薄膜在室温下干燥后,再进行热处理得到铈掺杂氧化钛薄膜。
2.根据权利要求1所述的铈掺杂二氧化钛忆阻器薄膜的制备方法,其特征在于,在所述步骤1中,制备铈金属氧化物溶胶具体为:以乙醇为溶剂,以硝酸铈为前驱体,两者混合后于室温下搅拌6h~8h并陈化24h,配制得到摩尔比为0.04mol/l的氧化铈溶胶。
3.根据权利要求1所述的铈掺杂二氧化钛忆阻器薄膜的制备方法,其特征在于,在所述步骤2中,制备氧化钛溶胶具体为:以乙醇为溶剂,以钛酸丁酯作为前驱体,钛酸丁酯和乙醇按1:10的摩尔比混合后,采用硝酸调节PH值为2~3,于室温下搅拌6h~8h后陈化24h得到二氧化钛溶胶。
4.根据权利要求1所述的铈掺杂二氧化钛忆阻器薄膜的制备方法,其特征在于,在所述步骤3中,搅拌的时间为8h,陈化时间为24h。
5.根据权利要求1所述的铈掺杂二氧化钛忆阻器薄膜的制备方法,其特征在于,在所述步骤3中,热处理在氩气或空气或氧气气氛下进行。
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