CN105742489A - A Zr-doped Ge2Sb2Te5 film material for phase change memory and its preparation method - Google Patents
A Zr-doped Ge2Sb2Te5 film material for phase change memory and its preparation method Download PDFInfo
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Abstract
本发明公开了一种用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料及其制备方法，特点是其化学结构式为Zrx(Ge2Sb2Te5)100?x，其中0<x<20，其制备方法具体步骤如下：采用高纯度圆块状Zr单质与Ge2Sb2Te5作为靶材，采用磁控溅射装置，采用双靶共溅射方法，以高纯氩气作为工作气体，采用石英片或硅片为衬底材料进行表面沉积，将Zr单质靶的直流溅射功率调整为3~9W，Ge2Sb2Te5靶的射频溅射功率调整为60W，于室温下共溅射15min后，得到Zr掺杂Ge2Sb2Te5薄膜材料，优点是具有较高的结晶温度和数据保持力，较快的结晶速度，较大的非晶态/晶态电阻比以及较好的热稳定性。
The invention discloses a Zr-doped Ge 2 Sb 2 Te 5 thin film material for phase-change memory and a preparation method thereof, which is characterized in that its chemical structural formula is Zr x (Ge 2 Sb 2 Te 5 ) 100? <x<20, the specific steps of its preparation method are as follows: using high-purity round Zr simple substance and Ge 2 Sb 2 Te 5 as targets, using a magnetron sputtering device, adopting a double-target co-sputtering method, using high-purity argon Gas is used as the working gas, and quartz wafer or silicon wafer is used as the substrate material for surface deposition. The DC sputtering power of the Zr single target is adjusted to 3~9W, and the RF sputtering power of the Ge 2 Sb 2 Te 5 target is adjusted to 60W. After co-sputtering at room temperature for 15 minutes, a Zr-doped Ge 2 Sb 2 Te 5 thin film material is obtained, which has the advantages of high crystallization temperature and data retention, fast crystallization speed, and large amorphous/crystalline state resistance ratio and good thermal stability.
Description
技术领域 technical field
本发明涉及相变存储材料领域，尤其是涉及一种用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料及其制备方法。 The invention relates to the field of phase-change memory materials, in particular to a Zr-doped Ge 2 Sb 2 Te 5 film material for phase-change memory and a preparation method thereof.
背景技术 Background technique
随着计算机技术、移动通信和数码产品的快速发展，对非易失性半导体存储器的需求显著增加。目前非易失存储器市场的主流是闪存，然而闪存自身存在的一些不足，如较长的写入时间(>10μs)和较低的循环次数(~106)，使其很难满足未来半导体存储器发展对更高擦写速度和存储密度的要求，另外由于存储电荷的基本要求，浮栅不能无限制的减薄，突破45nm半导体制程存在很大的技术困难。PCRAM日益引起科学界和业界的关注，不仅仅因为其满足非易失性存储器的各种要求，还因为其制造工艺相对简单。基于硫系化合物的PCRAM被广认为是最具前景的非易失存储器之一，有可能在市场上取代Flash成为下一代非易失存储器，因为PCRAM有近乎完美的性能，例如微缩性好、数据保持力强、成本低及与CMOS工艺兼容性好等特点。此外，PCRAM存储技术具有抗强震动、抗辐射性能，在航天航空领域具有极其重要的应用前景。 With the rapid development of computer technology, mobile communication and digital products, the demand for non-volatile semiconductor memory has increased significantly. At present, the mainstream of the non-volatile memory market is flash memory. However, some shortcomings of flash memory itself, such as long write time (>10μs) and low cycle times (~10 6 ), make it difficult to meet the needs of future semiconductor memory. The development requires higher erasing speed and storage density. In addition, due to the basic requirements for storing charges, the floating gate cannot be thinned without limit. There are great technical difficulties in breaking through the 45nm semiconductor process. PCRAM is increasingly attracting the attention of the scientific community and industry, not only because it meets the various requirements of non-volatile memory, but also because of its relatively simple manufacturing process. Chalcogenide-based PCRAM is widely regarded as one of the most promising non-volatile memories, and it is possible to replace Flash in the market as the next-generation non-volatile memory, because PCRAM has near-perfect performance, such as good miniaturization, data Strong retention, low cost and good compatibility with CMOS process. In addition, PCRAM storage technology has anti-strong vibration and anti-radiation performance, and has extremely important application prospects in the field of aerospace.
PCRAM的综合性能主要取决于存储介质的相变特性。在所有的相变硫系化合物中，Ge2Sb2Te5（GST）是应用在PCRAM中最常用的材料。然而，较高的熔点和较低的晶态电阻率使得GST不可避免地出现较高的RESET电流和功耗。另外在汽车电子等领域对数据保持力有特殊要求：数据在120℃的环境下能保持10年。传统GST材料因为其结晶温度低，热稳性不佳，以GST材料为存储介质的PRAM存储单元的数据只能够在80℃左右保存10年，高温下的数据保存寿命短，所以GST不能满足此要求。为优化PCRAM的性能，通常在GST中掺杂其他元素，来提高相变材料晶态电阻率，降低RESET电流以及提高数据保持力，使掺杂后GST材料应用于相变存储器中成为可能。 The overall performance of PCRAM mainly depends on the phase change characteristics of the storage medium. Among all phase change chalcogenides, Ge 2 Sb 2 Te 5 (GST) is the most commonly used material in PCRAM. However, higher melting point and lower crystalline resistivity make GST inevitably suffer from higher RESET current and power consumption. In addition, in the fields of automotive electronics and other fields, there are special requirements for data retention: data can be maintained for 10 years in an environment of 120 °C. Due to the low crystallization temperature and poor thermal stability of traditional GST materials, the data of PRAM memory cells using GST materials as storage media can only be stored for 10 years at about 80°C, and the data storage life at high temperatures is short, so GST cannot meet this requirement. Require. In order to optimize the performance of PCRAM, GST is usually doped with other elements to increase the crystalline resistivity of the phase change material, reduce the RESET current and improve the data retention, making it possible to apply the doped GST material to the phase change memory.
发明内容 Contents of the invention
本发明所要解决的技术问题是提供一种具有较高的结晶温度和数据保持力，较快的结晶速度，较大的非晶态/晶态电阻比以及较好的热稳定性的用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料及其制备方法，该方法成本低，工艺可控性强，易于大规模生产。 The technical problem to be solved by the present invention is to provide a kind of phase with higher crystallization temperature and data retention, faster crystallization speed, larger amorphous/crystalline resistance ratio and better thermal stability. A Zr-doped Ge 2 Sb 2 Te 5 thin film material for a variable memory and a preparation method thereof. The method has low cost, strong process controllability, and is easy for large-scale production.
本发明解决上述技术问题所采用的技术方案为：一种用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料，其化学结构式为Zrx(Ge2Sb2Te5)100-x，其中0<x<20。 The technical scheme adopted by the present invention to solve the above-mentioned technical problems is: a Zr-doped Ge 2 Sb 2 Te 5 thin film material for phase change memory, whose chemical structural formula is Zr x (Ge 2 Sb 2 Te 5 ) 100-x , where 0<x<20.
所述的相变薄膜材料的结晶温度为150-300℃。 The crystallization temperature of the phase change film material is 150-300°C.
所述的相变薄膜材料的非晶电阻在106~108Ω，晶态电阻103~104Ω。 The amorphous resistance of the phase change thin film material is 10 6 -10 8 Ω, and the crystalline resistance is 10 3 -10 4 Ω.
所述的薄膜材料的化学结构式为Zr12(Ge2Sb2Te5)88。该相变薄膜材料的数据保持力能够在120.9℃下保存十年。 The chemical structural formula of the thin film material is Zr 12 (Ge 2 Sb 2 Te 5 ) 88 . The data retention of the phase change thin film material can be stored at 120.9°C for ten years.
上述用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料的制备方法，采用高纯度圆块状Zr单质与Ge2Sb2Te5作为靶材，采用磁控溅射装置，采用双靶共溅射方法，以高纯氩气作为工作气体，采用石英片或硅片为衬底材料进行表面沉积，具体步骤如下： The above-mentioned preparation method of Zr-doped Ge 2 Sb 2 Te 5 thin film material for phase change memory adopts high-purity round block Zr simple substance and Ge 2 Sb 2 Te 5 as target material, adopts magnetron sputtering device, adopts double The target co-sputtering method uses high-purity argon as the working gas, and uses quartz wafers or silicon wafers as the substrate material for surface deposition. The specific steps are as follows:
（1）将Ge2Sb2Te5圆块状玻璃靶材和Zr单质靶材背面，完全贴合一块与玻璃靶材直径相同，厚度为1mm的铜片，制得磁控溅射镀膜靶材；将Zr单质靶材安装在磁控直流直流溅射靶中，将Ge2Sb2Te5靶材安装在磁控射频溅射靶中； (1) The Ge 2 Sb 2 Te 5 round bulk glass target and the back of the Zr simple target are completely attached to a copper sheet with the same diameter as the glass target and a thickness of 1mm to obtain a magnetron sputtering coating target ; The Zr single target is installed in the magnetron DC sputtering target, and the Ge 2 Sb 2 Te 5 target is installed in the magnetron RF sputtering target;
（2）将石英片或硅片衬底材料放入去离子水中，超声清洗20分钟，然后放入无水乙醇中超声清洗20分钟，取出后用高纯氮气吹干，放入溅射腔室； (2) Put the quartz wafer or silicon wafer substrate material into deionized water, ultrasonically clean it for 20 minutes, then put it into anhydrous ethanol and ultrasonically clean it for 20 minutes, take it out and dry it with high-purity nitrogen, and put it into the sputtering chamber ;
（3）将磁控溅射室进行抽真空，直至溅射室内真空度达到2×10-4Pa时，向室内通入高纯氩气，氩气流量为50ml/min，直至溅射腔室内气压达到溅射所需的起辉气压0.3Pa； (3) Vacuumize the magnetron sputtering chamber until the vacuum degree in the sputtering chamber reaches 2×10 -4 Pa, then introduce high-purity argon gas into the chamber at a flow rate of 50ml/min until the sputtering chamber The pressure reaches the starting pressure of 0.3Pa required for sputtering;
（4）开启射频电源，待辉光稳定后，将Zr单质靶的直流溅射功率调整为3~9W，Ge2Sb2Te5靶的射频溅射功率调整为60W，于室温下进行溅射镀膜，共溅射15min后，得到用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料。 (4) Turn on the RF power supply, and after the glow is stable, adjust the DC sputtering power of the Zr single target to 3~9W, and adjust the RF sputtering power of the Ge 2 Sb 2 Te 5 target to 60W, and perform sputtering at room temperature Coating and co-sputtering for 15 minutes, a Zr-doped Ge 2 Sb 2 Te 5 thin film material for phase change memory is obtained.
所述的Zr靶材和所述Ge2Sb2Te5靶材的纯度均为99.99%。 The purity of the Zr target and the Ge 2 Sb 2 Te 5 target are both 99.99%.
将步骤（4）步骤得到的沉积态的Zr掺杂Ge2Sb2Te5薄膜材料放入快速退火炉中，在高纯氩气氛围保护下，迅速升温至200~350℃下进行退火，即得到热处理后的Zr掺杂GST相变存储薄膜材料。 Put the as-deposited Zr-doped Ge 2 Sb 2 Te 5 film material obtained in step (4) into a rapid annealing furnace, and under the protection of high-purity argon atmosphere, rapidly raise the temperature to 200~350°C for annealing, that is The heat-treated Zr-doped GST phase-change memory film material is obtained.
与现有技术相比，本发明的优点在于：本发明一种用于相变存储器的Zr掺杂GST薄膜材料及其制备方法，其化学式结构为Zrx(Ge2Sb2Te5)100-x，其中0<x<20，该薄膜的结晶温度为165~200℃，数据保存10年的最高温度为84.4~120.9℃；测试结果表明，随着Zr掺杂含量的增加，样品的晶态电阻也在增加，有利于降低PRAM的功耗。本发明具有工艺可控性强，生产成本低，重复性好，制备得到的Zr掺杂GST薄膜材料不仅具有组分偏差小、附着强度高、膜质均匀致密的优点，而且具有较高的结晶温度，较快的结晶速度，较大的非晶态/晶态电阻比以及较好的热稳定性，可以用于工业化规模制备大面积的相变薄膜，从而满足未来相变存储材料的应用需求。 Compared with the prior art, the present invention has the advantages of: a Zr-doped GST film material for phase change memory and its preparation method, the chemical formula structure of which is Zr x (Ge 2 Sb 2 Te 5 ) 100- x , where 0<x<20, the crystallization temperature of the film is 165~200℃, and the highest temperature of the data stored for 10 years is 84.4~120.9℃; the test results show that with the increase of Zr doping content, the crystallization temperature of the sample The resistance is also increased, which helps reduce the power consumption of the PRAM. The invention has strong process controllability, low production cost and good repeatability. The prepared Zr-doped GST thin film material not only has the advantages of small component deviation, high adhesion strength, uniform and dense film quality, but also has high crystallization Temperature, fast crystallization speed, large amorphous/crystalline resistance ratio and good thermal stability can be used to prepare large-area phase-change thin films on an industrial scale, so as to meet the application requirements of future phase-change memory materials .
附图说明 Description of drawings
图1为不同组分的Zrx(GST)100-x薄膜方块电阻随温度变化关系曲线； Fig. 1 is the Zr x (GST) 100-x film sheet resistance curve of different components as a function of temperature;
图2为不同组分的Zrx(GST)100-x薄膜的数据保持力计算结果图； Fig. 2 is the data retention calculation result figure of the Zr x (GST) 100-x film of different components;
图3为组分Zr9(GST)91的薄膜样品在不同温度下退火后的X射线衍射图谱； Fig. 3 is the X-ray diffraction pattern of the film sample of component Zr 9 (GST) 91 after annealing at different temperatures;
图4为不同组分的Zrx(GST)100-x薄膜在250℃下退火后的X射线衍射图谱； Fig. 4 is the X-ray diffraction pattern of the Zr x (GST) 100-x film of different components after annealing at 250 ℃;
图5为不同组分的Zrx(GST)100-x薄膜在300℃下退火后的X射线衍射图谱； Fig. 5 is the X-ray diffraction pattern of the Zr x (GST) 100-x film of different components after annealing at 300 ℃;
图6为不同组分的Zrx(GST)100-x薄膜在350℃下退火后的X射线衍射图谱。 Fig. 6 is the X-ray diffraction patterns of Zr x (GST) 100-x films with different components after annealing at 350°C.
具体实施方式 detailed description
以下结合附图实施例对本发明作进一步详细描述。 The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.
一、具体实施例 1. Specific examples
一种用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料，其化学结构式为Zrx(Ge2Sb2Te5)100-x，其中0<x<20，该薄膜材料的结晶温度为150-300℃，非晶电阻在106~108Ω，晶态电阻103~104Ω。其制备方法如下：采用高纯度圆块状Zr单质与Ge2Sb2Te5作为靶材，采用磁控溅射装置，采用双靶共溅射方法，以高纯氩气作为工作气体，采用石英片或硅片为衬底材料进行表面沉积，具体步骤如下： A Zr-doped Ge 2 Sb 2 Te 5 thin film material for phase change memory, its chemical structural formula is Zr x (Ge 2 Sb 2 Te 5 ) 100-x , where 0<x<20, the crystallization of the thin film material The temperature is 150-300°C, the amorphous resistance is 10 6 ~10 8 Ω, and the crystalline resistance is 10 3 ~10 4 Ω. Its preparation method is as follows: using high-purity round Zr simple substance and Ge 2 Sb 2 Te 5 as target materials, using a magnetron sputtering device, using a double-target co-sputtering method, using high-purity argon as a working gas, and using quartz Chips or silicon wafers are used as substrate materials for surface deposition, and the specific steps are as follows:
（1）将Ge2Sb2Te5圆块状玻璃靶材和Zr单质靶材背面，完全贴合一块与玻璃靶材直径相同，厚度为1mm的铜片，制得磁控溅射镀膜靶材；将Zr单质靶材安装在磁控直流直流溅射靶中，将Ge2Sb2Te5靶材安装在磁控射频溅射靶中； (1) The Ge 2 Sb 2 Te 5 round bulk glass target and the back of the Zr simple target are completely attached to a copper sheet with the same diameter as the glass target and a thickness of 1mm to obtain a magnetron sputtering coating target ; The Zr single target is installed in the magnetron DC sputtering target, and the Ge 2 Sb 2 Te 5 target is installed in the magnetron RF sputtering target;
（2）将石英片或硅片衬底材料放入去离子水中，超声清洗20分钟，然后放入无水乙醇中超声清洗20分钟，取出后用高纯氮气吹干，放入溅射腔室； (2) Put the quartz wafer or silicon wafer substrate material into deionized water, ultrasonically clean it for 20 minutes, then put it into anhydrous ethanol and ultrasonically clean it for 20 minutes, take it out and dry it with high-purity nitrogen, and put it into the sputtering chamber ;
（3）将磁控溅射室进行抽真空，直至溅射室内真空度达到2×10-4Pa时，向室内通入高纯氩气，氩气流量为50ml/min，直至溅射腔室内气压达到溅射所需的起辉气压0.3Pa； (3) Vacuumize the magnetron sputtering chamber until the vacuum degree in the sputtering chamber reaches 2×10 -4 Pa, then introduce high-purity argon gas into the chamber at a flow rate of 50ml/min until the sputtering chamber The pressure reaches the starting pressure of 0.3Pa required for sputtering;
（4）开启射频电源，待辉光稳定后，将Zr单质靶的直流溅射功率调整为3~9W，Ge2Sb2Te5靶的射频溅射功率调整为60W，于室温下进行溅射镀膜，共溅射15min后，得到用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料。 (4) Turn on the RF power supply, and after the glow is stable, adjust the DC sputtering power of the Zr single target to 3~9W, and adjust the RF sputtering power of the Ge 2 Sb 2 Te 5 target to 60W, and perform sputtering at room temperature Coating and co-sputtering for 15 minutes, a Zr-doped Ge 2 Sb 2 Te 5 thin film material for phase change memory is obtained.
上述得到的沉积态的Zr掺杂Ge2Sb2Te5薄膜材料放入快速退火炉中，在高纯氩气氛围保护下，迅速升温至200~350℃下进行退火，即得到热处理后的Zr掺杂GST相变存储薄膜材料。 The deposited Zr-doped Ge 2 Sb 2 Te 5 thin film material obtained above is placed in a rapid annealing furnace, and under the protection of a high-purity argon atmosphere, the temperature is rapidly raised to 200~350°C for annealing, and the heat-treated Zr Doped GST phase change memory thin film material.
上述所用的磁控溅射装置由中国科学院沈阳科学仪器研制中心有限公司制造的JGP-450磁控溅射沉积***。采用的溅射靶材均为纯度99.99%，尺寸Φ50×3mm。在圆块状Ge2Sb2Te5与Zr单质背面粘贴1mm厚的直径相同的铜片，以解决玻璃靶材在溅射过程中散热问题。 The magnetron sputtering device used above is a JGP-450 magnetron sputtering deposition system manufactured by Shenyang Scientific Instrument Development Center Co., Ltd., Chinese Academy of Sciences. The sputtering targets used are all 99.99% pure and have a size of Φ50×3mm. A 1mm-thick copper sheet with the same diameter is pasted on the back of the round Ge 2 Sb 2 Te 5 and Zr simple substance to solve the heat dissipation problem of the glass target during the sputtering process.
实施例1 Example 1
一种用于相变存储器的Zr掺杂Ge2Sb2Te5薄膜材料，其制备方法如下： A Zr-doped Ge 2 Sb 2 Te 5 thin film material for phase change memory, the preparation method of which is as follows:
（1）采用Ge2Sb2Te5和Zr单质双靶共溅射镀膜：将Zr单质靶材安装在磁控直流直流溅射靶中，将Ge2Sb2Te5靶材安装在磁控射频溅射靶中；对溅射腔室进行抽真空处理，当溅射腔室内真空度达到2×10---4Pa时，向室内充入高纯氩气，氩气流量为50.0ml/min，直至腔室内达到溅射所需的起辉气压0.3Pa；开启射频电源，待辉光稳定后，调节Zr单质所在的直流溅射靶功率为3W，Ge2Sb2Te5靶材所在磁控射频溅射功率为60W，待功率稳定后，开启衬底转盘自转并将自转速率设定为5rpm，打开衬底下方的挡板，溅射15分钟后得到沉积态的Zr掺杂GST薄膜； (1) Using Ge 2 Sb 2 Te 5 and Zr simple substance double-target co-sputtering coating: the Zr single substance target is installed in the magnetron DC DC sputtering target, and the Ge 2 Sb 2 Te 5 target is installed in the magnetron radio frequency In the sputtering target; vacuumize the sputtering chamber. When the vacuum degree in the sputtering chamber reaches 2×10 - - -4 Pa, fill the chamber with high-purity argon gas, and the flow rate of argon gas is 50.0ml/min , until the ignition pressure required for sputtering is 0.3Pa in the chamber; turn on the RF power supply, and after the glow is stable, adjust the power of the DC sputtering target where the Zr element is located to 3W, and the magnetron where the Ge 2 Sb 2 Te 5 target is located The RF sputtering power is 60W. After the power is stabilized, turn on the substrate turntable and set the rotation rate to 5rpm, open the baffle under the substrate, and obtain a deposited Zr-doped GST film after 15 minutes of sputtering;
（2）将步骤（1）得到的沉积态的相变存储薄膜样品放入快速退火炉中，在高纯氮气氛围的保护下，迅速升温到200~350℃下进行退火，得到热处理后的Zr掺杂Ge2Sb2Te5薄膜材料。退火期间通入高纯氮气的作用是为避免薄膜在高温下发生氧化。 (2) Put the as-deposited phase-change memory film sample obtained in step (1) into a rapid annealing furnace, and under the protection of a high-purity nitrogen atmosphere, rapidly raise the temperature to 200-350°C for annealing, and obtain the heat-treated Zr Doped Ge 2 Sb 2 Te 5 thin film material. The function of feeding high-purity nitrogen gas during annealing is to avoid oxidation of the film at high temperature.
上述实施例1制备得到的Zr掺杂Ge2Sb2Te5薄膜组分由X射线能谱分析法（EDS）测得，薄膜厚度由台阶仪测得，测试结果为：薄膜组分为Zr4(GST)96，薄膜厚度为210nm。 The composition of the Zr-doped Ge 2 Sb 2 Te 5 thin film prepared in the above example 1 was measured by X-ray energy spectroscopy (EDS), and the thickness of the film was measured by a step meter. The test results are: the thin film composition is Zr 4 (GST) 96 , and the film thickness is 210nm.
实施例2 Example 2
同实施例1，其区别点在于，调节Zr单质所在的直流溅射靶功率为5W，Ge2Sb2Te5靶材所在磁控射频溅射功率为60W。 Same as Example 1, the difference is that the power of the DC sputtering target where the Zr element is located is adjusted to 5W, and the magnetron radio frequency sputtering power where the Ge 2 Sb 2 Te 5 target is located is 60W.
上述实施例1制备得到的Zr掺杂Ge2Sb2Te5薄膜组分由X射线能谱分析法（EDS）测得，薄膜厚度由台阶仪测得，测试结果为：薄膜组分为Zr6(GST)94，薄膜厚度为235nm。 The composition of the Zr-doped Ge 2 Sb 2 Te 5 thin film prepared in the above example 1 was measured by X-ray energy spectroscopy (EDS), and the thickness of the film was measured by a step meter. The test results are: the thin film composition is Zr 6 (GST) 94 , and the film thickness is 235nm.
实施例3 Example 3
同实施例1，其区别点在于，调节Zr单质所在的直流溅射靶功率为7W，Ge2Sb2Te5靶材所在磁控射频溅射功率为60W。 Same as Example 1, the difference lies in that the power of the direct current sputtering target where the Zr simple substance is located is adjusted to 7W, and the power of the magnetron radio frequency sputtering target where the Ge 2 Sb 2 Te 5 target is located is 60W.
上述实施例1制备得到的Zr掺杂Ge2Sb2Te5薄膜组分由X射线能谱分析法（EDS）测得，薄膜厚度由台阶仪测得，测试结果为：薄膜组分为Zr9(GST)91，薄膜厚度为260nm。 The composition of the Zr-doped Ge 2 Sb 2 Te 5 film prepared in Example 1 above was measured by X-ray energy spectroscopy (EDS), and the thickness of the film was measured by a procedural instrument. The test results are: the film composition is Zr 9 (GST) 91 , and the film thickness is 260 nm.
实施例4 Example 4
同实施例1，其区别点在于，调节Zr单质所在的直流溅射靶功率为9W，Ge2Sb2Te5靶材所在磁控射频溅射功率为60W。 Same as Example 1, the difference lies in that the power of the DC sputtering target where the Zr simple substance is located is adjusted to 9W, and the power of the magnetron radio frequency sputtering target where the Ge 2 Sb 2 Te 5 target is located is 60W.
上述实施例1制备得到的Zr掺杂Ge2Sb2Te5薄膜组分由X射线能谱分析法（EDS）测得，薄膜厚度由台阶仪测得，测试结果为：薄膜组分为Zr12(GST)88，薄膜厚度为290nm。 The composition of the Zr-doped Ge 2 Sb 2 Te 5 thin film prepared in the above example 1 was measured by X-ray energy spectroscopy (EDS), and the thickness of the film was measured by a step meter. The test results are: the thin film composition is Zr 12 (GST) 88 , and the film thickness is 290nm.
二、实验结果分析 2. Analysis of experimental results
对上述实施例制备的Zrx(GST)100-x薄膜进行性能测试，图1和图2为原位电阻性能测试结果。图1为不同组分的薄膜在10℃/min升温速率下方块电阻与温度的关系。由于薄膜的电阻在结晶温度（Tc）处急剧下降，从图1中可以看出，组分为Zr4(GST)96的薄膜具有两次结晶现象，随着Zr含量的增加，两次结晶现象被抑制，材料的结晶温度也明显升高，材料的热稳定性得到提高，进而可以提高相变存储器的数据保持力，这也在图2中得到证实。由图2可知，随着Zr含量的增加，材料10年数据保持力也不断提高。 Performance tests were performed on the Zr x (GST) 100-x films prepared in the above examples, and Figures 1 and 2 show the results of the in-situ resistance performance tests. Figure 1 shows the relationship between sheet resistance and temperature for films with different components at a heating rate of 10 °C / min. Because the resistance of the film drops sharply at the crystallization temperature (Tc), it can be seen from Figure 1 that the film with the composition of Zr 4 (GST) 96 has a double crystallization phenomenon, and with the increase of the Zr content, the double crystallization phenomenon is suppressed, the crystallization temperature of the material is also significantly increased, and the thermal stability of the material is improved, which in turn can improve the data retention of the phase change memory, which is also confirmed in Figure 2. It can be seen from Figure 2 that with the increase of Zr content, the 10-year data retention of the material is also continuously improved.
图3为组分Zr9(GST)91的薄膜样品在不同温度下退火后的X射线衍射图。由图可知，在150℃退火后的X射线衍射图呈现宽的大包络，没出现析晶峰，说明分Zr9(GST)91薄膜样品在该温度下为非晶态；当温度高于200℃时，出现了明显的析晶峰，这表明该组分的薄膜样品的析晶温度在150℃到200℃之间，该结果与图1相符。 Fig. 3 is the X-ray diffraction pattern of the thin film samples of the composition Zr 9 (GST) 91 after annealing at different temperatures. It can be seen from the figure that the X-ray diffraction pattern after annealing at 150°C presents a wide and large envelope, and no devitrification peak appears, indicating that the Zr 9 (GST) 91 thin film sample is amorphous at this temperature; when the temperature is higher than At 200°C, an obvious crystallization peak appeared, which indicated that the crystallization temperature of the film sample of this component was between 150°C and 200°C, and the result was consistent with Figure 1.
图4，图5和图6是不同组分的Zrx(GST)100-x薄膜分别在250℃，300℃和350℃下退火后的X射线衍射图谱。实施例1制备的薄膜从非晶态到多晶态的相变是一个两步的结晶过程，即首先从非晶态变化到亚稳态面心立方结构(fcc)，然后从fcc继续变化到六方密堆结构(hex)。从图6中可以看到，在350℃温度下退火3min后，Zrx(GST)100-x薄膜各个组分都有晶体析出。并且随着Zr含量的增加，析晶峰的强度有明显的减弱，这说明Zr的掺杂抑制了GST的析晶，从而提高了Zrx(GST)100-x薄膜的结晶温度，使得材料的热稳定性大大改善。 Fig. 4, Fig. 5 and Fig. 6 are the X-ray diffraction patterns of Zr x (GST) 100-x films with different components annealed at 250°C, 300°C and 350°C respectively. The phase transition of the film prepared in Example 1 from the amorphous state to the polycrystalline state is a two-step crystallization process, that is, it first changes from the amorphous state to the metastable face-centered cubic structure (fcc), and then continues to change from fcc to Hexagonal close-packed structure (hex). It can be seen from Figure 6 that after annealing at 350°C for 3 minutes, each component of the Zr x (GST) 100-x film has crystals precipitated. And with the increase of Zr content, the intensity of the devitrification peak is obviously weakened, which shows that the doping of Zr inhibits the devitrification of GST, thereby increasing the crystallization temperature of the Zr x (GST) 100-x film, making the material's Thermal stability is greatly improved.
上述说明并非对本发明的限制，本发明也并不限于上述举例。本技术领域的普通技术人员在本发明的实质范围内，作出的变化、改型、添加或替换，也应属于本发明的保护范围，本发明的保护范围以权利要求书为准。 The above description does not limit the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by those skilled in the art within the essential scope of the present invention shall also belong to the protection scope of the present invention, and the protection scope of the present invention shall be determined by the claims.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106374043A (en) * | 2016-09-26 | 2017-02-01 | 江苏理工学院 | A kind of Si-Sb-Se nano phase change film material and its preparation method and application |
| CN106960907A (en) * | 2017-02-28 | 2017-07-18 | 宁波大学 | A kind of rare earth Er doping Ge2Sb2Te5Phase transiting storing thin-film material and preparation method thereof |
| CN110176536A (en) * | 2019-04-18 | 2019-08-27 | 宁波大学 | A kind of vanadium dioxide-Sb thin-film material and preparation method thereof having both high speed and high data retention |
| WO2024255478A1 (en) * | 2023-06-16 | 2024-12-19 | 华为技术有限公司 | Phase change material, storage chip, and device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817009A (en) * | 2011-06-09 | 2012-12-12 | 气体产品与化学公司 | Binary and ternary metal chalcogenide materials and method of making and using the same |
| CN104831235A (en) * | 2015-03-26 | 2015-08-12 | 中国科学院上海微***与信息技术研究所 | Zr-Sb-Te series phase-change materials used for phase-change memories and preparing method thereof |
-
2016
- 2016-03-03 CN CN201610119008.9A patent/CN105742489B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817009A (en) * | 2011-06-09 | 2012-12-12 | 气体产品与化学公司 | Binary and ternary metal chalcogenide materials and method of making and using the same |
| CN104831235A (en) * | 2015-03-26 | 2015-08-12 | 中国科学院上海微***与信息技术研究所 | Zr-Sb-Te series phase-change materials used for phase-change memories and preparing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| E.M. VINOD等: ""Temperature dependent optical constants of amorphous Ge2Sb2Te5 thin films"", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106374043A (en) * | 2016-09-26 | 2017-02-01 | 江苏理工学院 | A kind of Si-Sb-Se nano phase change film material and its preparation method and application |
| CN106960907A (en) * | 2017-02-28 | 2017-07-18 | 宁波大学 | A kind of rare earth Er doping Ge2Sb2Te5Phase transiting storing thin-film material and preparation method thereof |
| CN106960907B (en) * | 2017-02-28 | 2019-03-15 | 宁波大学 | A kind of rare earth Er doping Ge2Sb2Te5Phase transiting storing thin-film material and preparation method thereof |
| CN110176536A (en) * | 2019-04-18 | 2019-08-27 | 宁波大学 | A kind of vanadium dioxide-Sb thin-film material and preparation method thereof having both high speed and high data retention |
| CN110176536B (en) * | 2019-04-18 | 2023-04-18 | 宁波大学 | Vanadium dioxide-Sb thin film material and preparation method thereof |
| WO2024255478A1 (en) * | 2023-06-16 | 2024-12-19 | 华为技术有限公司 | Phase change material, storage chip, and device |
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