WO2021082808A1 - Doped ge-sb-based phase change material, phase change memory and preparation method therefor - Google Patents

Doped ge-sb-based phase change material, phase change memory and preparation method therefor Download PDF

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WO2021082808A1
WO2021082808A1 PCT/CN2020/116619 CN2020116619W WO2021082808A1 WO 2021082808 A1 WO2021082808 A1 WO 2021082808A1 CN 2020116619 W CN2020116619 W CN 2020116619W WO 2021082808 A1 WO2021082808 A1 WO 2021082808A1
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phase change
sputtering
doped
target
change material
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Chinese (zh)
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徐�明
李博文
缪向水
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华中科技大学
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10N70/041—Modification of switching materials after formation, e.g. doping
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect

Definitions

  • the invention belongs to the technical field of microelectronics, and particularly relates to a doped Ge-Sb-based phase change material, a preparation method of the material, and a phase change memory (PCM) containing the material.
  • PCM phase change memory
  • PCM Phase change memory
  • the above-mentioned excellent storage performance is determined by its storage mechanism: after applying electric pulses of different amplitudes and widths to phase change storage materials, Joule heating can be used to achieve rapid transition between amorphous and crystalline states (nanosecond level), And corresponding to the huge difference in resistance level to store "0" and "1". At the same time, the information can be read by reading the size of the resistance by applying a small pulse.
  • the storage mechanism of PCM is closely related to the Joule heating effect, the commercialization process of PCM has been limited by large operating current and power consumption, and it is difficult to further increase storage density and reduce device cost.
  • the RESET process in which a certain volume of phase change material needs to be heated to a higher melting point or higher to achieve amorphization through melting-quenching, determines the overall power consumption level of the PCM.
  • the existing main ways to improve power consumption on the one hand, such as reducing the area of the heating electrode, are facing problems such as a sharp increase in cost after further reduction in size, and difficulty in integrating the gate tube with a larger current density; on the other hand, from From the perspective of traditional phase change materials and thermal insulation layers, the current density and power consumption reduction achieved by improving the thermal conductivity of phase change materials and insulation materials is limited.
  • the main purpose of the present invention is to provide a new type of doped Ge-Sb-based phase change material and a phase change memory (PCM) of said material.
  • the doping element M in the Ge-Sb-based phase change material exists in the Ge-Sb grain boundary, which hinders the crystallization of the Ge-Sb-based material, thereby refining the crystal grains; making the phase change material have amplitude modulation decomposition The effect is non-homogeneous phase structure.
  • the degree of phase separation in the system is controlled by doping, electric pulse, laser, etc., to realize the transformation of the phase change material between different resistance states, and the local heating effect can be used to effectively improve the heating efficiency and dissipation degree of PCM , which greatly reduces the power consumption of RESET, and is used to solve the problems of large density changes and high operation energy consumption during the reading and writing process of phase change materials in the prior art.
  • the first aspect of the present invention provides a phase change material comprising a doped Ge-Sb-based material, characterized in that the general chemical formula of the doped Ge-Sb-based material is M x (Ge i Sb j ) 100-x ;
  • M is a doping element, and the M is at least one of C, N, O, and Sn;
  • the M atoms are present in the Ge-Sb grain boundary, thereby hindering the crystallization of Ge-Sb-based materials to form a heterogeneous phase structure inside; preferably, the amorphous structure in the doped Ge-Sb-based material system can be controlled.
  • the composition ratio of the phase and the crystal phase is used to realize the transformation of the phase change material between different resistance states.
  • the preferred range of X is 10 ⁇ x ⁇ 20.
  • the method for adjusting the ratio of the amorphous phase and the crystal phase composition is at least one of pulse excitation or laser excitation.
  • the doped Ge-Sb-based material can switch between a metastable high-resistance state and a metastable low-resistance state; wherein the metastable high-resistance resistance is at least 100% of the metastable low-resistance resistance. Times.
  • the doped Ge-Sb-based material is prepared by magnetron sputtering method, chemical vapor deposition method, atomic layer deposition method, electroplating method or electron beam evaporation method.
  • phase change material is prepared by a magnetron sputtering method, including: when the M is C or Sn element,
  • a GeiSbj alloy target and an M elemental target are used for co-sputtering.
  • phase change material is prepared by a magnetron sputtering method, including: when the M is O or N element,
  • a Ge i Sb j alloy target is used for sputtering.
  • a phase change memory cell comprising: a bottom electrode, an isolation layer, a phase change film, and a top electrode sequentially arranged on a substrate, the top electrode being in contact with the phase change film;
  • the material of the phase change film is the aforementioned phase change material.
  • the thickness of the phase change film is 20-150 nm.
  • the doped Ge-Sb-based phase change material, the preparation method of the material, and the phase change memory (PCM) containing the material provided by the present invention have the following beneficial effects:
  • the present invention provides a novel doped Ge-Sb-based phase change material, which can be used to prepare a phase change memory.
  • the doping element M in the Ge-Sb-based phase change material exists in the Ge-Sb grain boundary, which hinders the crystallization of the Ge-Sb-based material so that the phase change material has a heterogeneous phase structure with an amplitude modulation decomposition effect.
  • the degree of phase separation in the system is controlled by means of doping, electric pulse, laser, etc., to realize the transformation of the phase change material between different resistance states, where the resistance between the metastable high resistance state and the metastable low resistance state
  • the magnitude of the change is more than two orders of magnitude. Therefore, the phase change memory prepared by using this material can store data by using the difference in conductivity that appears when the crystalline state and the amorphous state of this special material are transformed into each other.
  • the M x (Ge i Sb j ) 100-x phase change compared with the prior art Ge-Sb-Te based phase change material (GST material, commonly known as Ge 2 Sb 2 Te 5 ), the M x (Ge i Sb j ) 100-x phase change.
  • GST material commonly known as Ge 2 Sb 2 Te 5
  • the heterogeneous phase change material system M x (Ge i Sb j ) 100-x phase change memory material has a smaller phase change area, so that its density change is smaller, so that the stress generated after the phase change is reduced, and the cycle of the device is reduced.
  • the non-uniform phase architecture makes the resistance values of the high and low resistance states of M x (Ge i Sb j ) 100-x very large, which greatly reduces the operating power consumption of the device and has the potential to be further scalable Sex.
  • FIG. 1 is a schematic diagram of the structure of a phase change memory cell prepared from an M-doped Ge-Sb-based phase change material according to the present invention
  • FIG. 2 is a TEM characterization diagram of an M-doped Ge-Sb-based phase change material network crystal-amorphous structure realized according to the present invention
  • Fig. 3 is a schematic diagram of pulse width pulses of a specific erase operation/RESET and a specific write operation/SET implemented in accordance with the present invention.
  • Embodiment 4 is a test result of applying a specific write operation/SET continuous pulse to the phase change memory in Embodiment 1 implemented according to the present invention
  • FIG. 5 is a test result of applying a specific erase operation/RESET continuous pulse to the phase change memory in Embodiment 1 implemented according to the present invention.
  • the phase change material system M x (Ge i Sb j ) 100-x has an amplitude modulation decomposition effect, that is, when the amorphous phase change material is in a state of different crystallinity, there are different resistance states in the corresponding metastable state. Thereby, the transformation of the phase change material between different resistance states can be realized by controlling the composition ratio of the amorphous phase and the crystalline phase in the phase change material system.
  • the preferred range of X is 10 ⁇ x ⁇ 20, and M is more preferably 10.
  • the doping amount of M will affect the heterogeneous phase structure of the phase change material.
  • the proportion of M atoms is less than 10%, the content of M is too low to completely inhibit the crystallization of Ge i Sb j , and the crystal grains are too large.
  • the resistance ratio between the states does not change much, and the amplitude modulation decomposition effect cannot be produced; on the contrary, when the proportion of M atoms is greater than 20%, chemical chains are easily formed, which makes the material resistance uneven.
  • Ge i Sb j crystal has good chemical stability, and at the same time, the content of Sb element is higher, so that it has a faster crystallization speed, which makes the phase change material change faster between different resistance states. More preferably, the Ge i Sb j crystal can be selected from at least one of Ge 10 Sb 90 , Ge 15 Sb 85 , Ge 20 Sb 80 , and Ge 25 Sb 75.
  • the composition ratio of the amorphous phase and the crystalline phase is adjusted by at least one of pulse excitation or laser excitation.
  • the specific phase change process of the material is a phase change formed by the conversion between a stable crystal structure and an amorphous state.
  • the M x (Ge i Sb j ) 100-x system material can be reversibly crystalline/amorphous.
  • the adjustment method is preferably an electric pulse; specifically, by applying a pulse voltage or a pulse current to the phase change material.
  • the phase change material can switch between a metastable high resistance state and a metastable low resistance state; wherein the metastable high resistance state is at least 100 times the metastable low resistance state.
  • the degree of phase separation in the M x (Ge i Sb j ) 100- system can be controlled by means of doping, electric pulse or laser, even if the phase change material has at least two metastable resistance states, specifically referring to The material can produce at least two metastable structures with different resistance values.
  • the phase change material has an amplitude modulation decomposition effect, the resistance change range between its different metastable states can reach more than two orders of magnitude.
  • the phase change memory requires that the phase change material has a larger amorphous/crystalline resistance ratio and better chemical stability.
  • a method for preparing the phase change material includes: magnetron sputtering, chemical vapor deposition, atomic layer deposition, electroplating, or electron beam evaporation. At least one.
  • the method is a magnetron sputtering method, preferably a DC magnetron sputtering method, when the M is C or Sn element,
  • the three elemental targets of Ge, Sb, and M are sputtered onto the substrate by the sputtering method; further, high-purity argon gas is introduced as the sputtering gas during sputtering, and the sputtering pressure It is 0.5 Pa, the background vacuum requirement is 10 -4 Pa or less, and the sputtering power is 25W.
  • the Ge i Sb j alloy target and the M elemental target are sputtered onto the substrate by the sputtering method; further, high-purity argon gas is introduced as the sputtering gas during sputtering, and the sputtering pressure is 0.5 Pa, the background vacuum requirement is 10 -4 Pa or less, and the sputtering power is 40W.
  • the method is a magnetron sputtering method, preferably a DC magnetron sputtering method, when the M is O or N element,
  • the two elemental targets of Ge and Sb are sputtered onto the substrate by the sputtering method; further, high-purity O 2 or N 2 gas is introduced as the sputtering gas during sputtering, and the sputtering
  • the injection pressure is 0.5Pa
  • the background vacuum requirement is 10 -4 or less
  • the sputtering power is 25W.
  • the Ge i Sb j alloy target is sputtered onto the substrate by a sputtering method; further, high-purity O 2 or N 2 gas is introduced as the sputtering gas during sputtering, and the sputtering gas pressure is 0.5 Pa, the background vacuum requirement is 10 -4 or less, and the sputtering power is 40W.
  • a phase change memory cell with a structure as shown in FIG. 1, comprising: a bottom electrode 2, an isolation layer 3, a phase change film 4, and a top electrode 5 which are sequentially arranged on a substrate 1.
  • the top electrode 5 is in contact with the phase change film 4; wherein the material of the phase change film 4 is the aforementioned phase change material.
  • the thickness of the phase change film 4 is 20-150 nm, more preferably 100 nm.
  • the thickness of the phase change film is determined by the sputtering time of the target, and the sputtering time is 86-646s, more preferably 431s.
  • the material of the substrate 1 is SiO 2 /p-Si; specifically, a sputtering method is used to deposit silicon-rich silicon dioxide on the p-Si crystalline material.
  • the material of the bottom electrode 2 and the top electrode 5 is Pt. More preferably, the bottom electrode is made by a DC magnetron sputtering method and has a thickness of 100 nm.
  • the Pt target material was sputtered onto the SiO 2 /Si (100) substrate by a sputtering method; further, high-purity argon was introduced as the sputtering gas during sputtering, the sputtering pressure was 0.5 Pa, and the background vacuum The requirement is 10 -4 or less; when using DC source sputtering, the sputtering power is 35W.
  • the material of the isolation layer 3 is SiO 2 . More preferably, the SiO 2 isolation layer is prepared by plasma enhanced chemical vapor deposition (PECVD).
  • PECVD plasma enhanced chemical vapor deposition
  • EBL ultraviolet lithography or electron blocking layer
  • ICP inductively coupled plasma
  • a phase change memory including the aforementioned phase change memory cell.
  • the phase change memory utilizes the conductivity difference shown by the M x (Ge i Sb j ) 100-x phase change material when the crystalline state and the amorphous state are transformed into each other to store data.
  • a method for operating a phase change memory includes: applying pre-operation to the aforementioned phase change memory to obtain a phase change memory in a metastable high resistance state; A specific write operation is applied to the memory to obtain a phase change memory in a metastable low resistance state; a specific erase operation is applied to the phase change memory in a metastable low resistance state to obtain a phase change memory in a metastable high resistance state; The transition of variable memory between different metastable resistance states.
  • the pre-operation includes at least one of annealing or pulse application.
  • the voltage pulse amplitude of the write operation is 1.5V-2.5V, and the pulse width is 1-20 ⁇ s; the voltage pulse amplitude of the erase operation is 1V-3V, and the pulse width is 30ns-100ns.
  • the phase change film in the phase change memory is affected by annealing or pulse application, even if the phase change film forms an amorphous layer, a metastable high resistance phase change memory is obtained, and a specific write operation /SET is applied to set logic 1.
  • the sputtering substrate rotates to the target position to turn on the radio frequency power of the target position, and the phase change film is sputtered.
  • the sputtering thickness is 100nm.
  • Pt film bottom electrode Put the Pt target and SiO 2 /Si(100) substrate into the corresponding position in the sputtering chamber, the purity of the target is 99.99% (atomic percentage), and the vacuum in the chamber is evacuated to below 10 -4 ; Pass high-purity Ar gas into the sputtering chamber as the sputtering gas, the Ar gas flow is stable at 10sccm, the sputtering pressure is set to 0.5Pa, the distance between the target and the substrate is set to 150mm, the support position is turned on, and the speed is 135r /min; Turn on the magnetron sputtering DC source and adjust the sputtering power to 35w.
  • SiO 2 isolation layer use ultraviolet lithography or EBL to prepare feature patterns on the SiO 2 layer; ICP etching removes the SiO 2 isolation layer at the feature pattern to make it communicate with the bottom electrode; then remove the photoresist; finally use MJB4 ultraviolet
  • the electrode pattern is engraved on the photoetching machine with a thickness of 100nm.
  • phase change memory is prepared.
  • the phase change memory cell of the phase change memory is schematically shown in FIG.
  • the bottom electrode 2, the isolation layer 3, the phase change film 4, and the top electrode 5 are in contact with the phase change film 4.
  • the material of the top electrode and the bottom electrode is Pt, the thickness is 100nm, and the material of the isolation layer is SiO 2 , a thickness of 100nm, the phase change memory material of the functional layer is made of O x (Ge 15 Sb 85) 1-x, the thickness of 100nm.
  • Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
  • the target sputtering substrate is rotated to the target position to turn on the target position's radio frequency power supply to start sputtering the phase change film, and the sputtering thickness is 100 nm.
  • Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
  • Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
  • the target sputtering substrate rotates to the target position to turn on the RF power supply of the target position, and start sputtering the target material to clean the surface of the target material; after the surface of the target material is cleaned, turn off the DC power applied on the target, and sputter the C target on the base.
  • the film rotates to the target position to turn on the target position's radio frequency power supply, and the phase change film is sputtered.
  • the sputtering thickness is 100 nm.
  • Step (2) (3) replace (2) (3) in Example 1 with the corresponding phase change film prepared
  • Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
  • the sputtering substrate is rotated to the target position, and the RF power supply is turned on at the target position, and the target material is sputtered to clean the surface of the target material; after the surface of the target material is cleaned, the DC power supply applied to the target is turned off, and the Sn sputtering substrate is rotated Go to the target position and turn on the target position's RF power supply to start sputtering the phase change film, and the sputtering thickness is 100nm.
  • Step (2) (3) replace (2) (3) in Example 1 with the corresponding phase change film prepared
  • Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
  • the Ge-Sb-based phase change memory material O 10 (Ge 10 Sb 90 ) 90 prepared in embodiment 1 is subjected to TEM characterization to obtain a meshed non
  • the crystal structure diagram is shown in Figure 2.
  • different dashed lines are used to mark the amorphous and crystalline regions in the material.
  • the Ge-Sb-based phase change memory material doped with M has an obvious phase separation process.
  • the ratio of the two phase components can be adjusted to realize the phase change memory material in different resistance states. Between the changes.
  • the resistance value of the phase change memory based on M x (Ge i Sb j ) 100-x varies with the applied pulse size, as shown in Fig. 3 and Fig. 4 .
  • the pulse range is 0-3V
  • the pulse width of the Set process is 10 ⁇ s
  • the pulse width of the Reset process is 50ns.
  • phase change memory material when voltage pulses of different sizes are applied, there will be an amplitude modulation decomposition process inside the phase change memory material, which changes the material
  • the composition ratio of the crystalline phase and the crystalline phase is electrically characterized as a continuous change in the resistance value, and, due to the presence of the amorphous phase in the material, the low-resistance state and high-resistance state of the material are more than 100 times that of traditional phase change memory materials ,

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Abstract

The present invention provides a new doped Ge-Sb-based phase change material, a phase change memory (PCM) for the material, and a specific method for operating the PCM. The chemical general formula of the doped Ge-Sb-based material is Mx(Ge i Sb j) 100-x; M is a doping element, and M is at least one of C, N, O and Sn; x represents the percentage of the number of atoms of M, 0<x≤30, i and j represent the percentages of the number of atoms of elements Ge and Sb, 0<i≤50, i+j=100; the doping element M in the Ge-Sb-based phase change material exists in a Ge-Sb grain boundary, and hinders crystallization of the Ge-Sb-based material so that the phase change material forms a non-uniform phase structure. The degree of intra-system phase separation is then controlled by means of doping, electrical pulse, laser, etc., so as to realize the transition of different resistance states of the phase change material. The local heating effect can be used to effectively improve the heating efficiency and dissipation degree of the PCM, greatly reducing the power consumption of the RESET, for solving the problems in the prior art that the density of the phase change material changes greatly during the reading and writing process, and the operation energy consumption is high, etc.

Description

一种掺杂的Ge-Sb相变材料、相变存储器及其制备方法Doped Ge-Sb phase change material, phase change memory and preparation method thereof 【技术领域】【Technical Field】
本发明属于微电子技术领域，特别涉及一种掺杂的Ge-Sb基相变材料、该材料的制备方法以及含有该材料的相变存储器(PCM)。The invention belongs to the technical field of microelectronics, and particularly relates to a doped Ge-Sb-based phase change material, a preparation method of the material, and a phase change memory (PCM) containing the material.
【背景技术】【Background technique】
相变存储器(PCM)凭借其优异的读写性能、可微缩以及与CMOS的良好兼容性而被认为可破除由DRAM和闪存间巨大的速度和容量差异造成的存储层级壁垒，从而有效改善现有计算架构的性能。甚至在其速度和成本的不断优化下，PCM很有可能取代闪存成为下一代主流非易失存储器产品，具有广阔的市场前景。其中，上述优异的存储性能决定于其存储机理：相变存储材料在外加不同幅值和宽度的电脉冲后，可利用焦耳加热实现非晶和晶态两者间快速转变(纳秒级别)，并对应巨大的电阻高低差异来存储“0”和“1”。同时只需外加小脉冲即可通过读取电阻大小来读取信息。Phase change memory (PCM) is considered to be able to break the storage-level barriers caused by the huge speed and capacity difference between DRAM and flash memory due to its excellent read and write performance, scalability, and good compatibility with CMOS, thereby effectively improving the existing Calculate the performance of the architecture. Even with the continuous optimization of its speed and cost, PCM is likely to replace flash memory and become the next-generation mainstream non-volatile memory product, which has a broad market prospect. Among them, the above-mentioned excellent storage performance is determined by its storage mechanism: after applying electric pulses of different amplitudes and widths to phase change storage materials, Joule heating can be used to achieve rapid transition between amorphous and crystalline states (nanosecond level), And corresponding to the huge difference in resistance level to store "0" and "1". At the same time, the information can be read by reading the size of the resistance by applying a small pulse.
由于PCM的存储机制与焦耳热效应密切相关，致使PCM的商业化进程一直受限于较大的操作电流和功耗，难以进一步增加存储密度、降低器件成本。尤其是需要将特定体积的相变材料温度加热至更高的熔点以上才能通过熔融-淬火实现非晶化的RESET过程，决定了PCM的整体功耗水平。而现有用于改善功耗的主要途径，一方面，如减小加热电极面积，面临尺寸进一步微缩后的成本激增、较大的电流密度难以与选通管有效集成等难题；另一方面，从传统相变材料和热绝缘层角度出发，通过改善相变材料和绝缘材料热导率而达到的电流密度和功耗减小程度有限。Because the storage mechanism of PCM is closely related to the Joule heating effect, the commercialization process of PCM has been limited by large operating current and power consumption, and it is difficult to further increase storage density and reduce device cost. In particular, the RESET process, in which a certain volume of phase change material needs to be heated to a higher melting point or higher to achieve amorphization through melting-quenching, determines the overall power consumption level of the PCM. The existing main ways to improve power consumption, on the one hand, such as reducing the area of the heating electrode, are facing problems such as a sharp increase in cost after further reduction in size, and difficulty in integrating the gate tube with a larger current density; on the other hand, from From the perspective of traditional phase change materials and thermal insulation layers, the current density and power consumption reduction achieved by improving the thermal conductivity of phase change materials and insulation materials is limited.
【发明内容】[Summary of the invention]
有鉴于此，本发明的主要目的在于提供一种新型的掺杂的Ge-Sb基相变材料、所述材料的相变存储器(PCM)。其中，所述Ge-Sb基相变材料中的掺杂元素M存在于Ge-Sb晶界中，阻碍Ge-Sb基材料结晶，从而细化晶粒；使得所述相变材料成为具有调幅分解效应非均一相结构。再通过掺杂、电脉冲、激光等方式控制体系内分相程度，来实现所述相变材料在不同阻态之间的转变，可利用局域加热效应有效改善PCM的加热效率和耗散程度，极大的减小RESET功耗，用于解决现有技术中相变材料读写过程中密度变化大，操作能耗高等问题。In view of this, the main purpose of the present invention is to provide a new type of doped Ge-Sb-based phase change material and a phase change memory (PCM) of said material. Wherein, the doping element M in the Ge-Sb-based phase change material exists in the Ge-Sb grain boundary, which hinders the crystallization of the Ge-Sb-based material, thereby refining the crystal grains; making the phase change material have amplitude modulation decomposition The effect is non-homogeneous phase structure. Then the degree of phase separation in the system is controlled by doping, electric pulse, laser, etc., to realize the transformation of the phase change material between different resistance states, and the local heating effect can be used to effectively improve the heating efficiency and dissipation degree of PCM , Which greatly reduces the power consumption of RESET, and is used to solve the problems of large density changes and high operation energy consumption during the reading and writing process of phase change materials in the prior art.
因此，本发明第一方面，提供一种相变材料，其包括掺杂的Ge-Sb基材料，其特征在于，所述掺杂的Ge-Sb基材料的化学通式为M x(Ge iSb j) 100-x； Therefore, the first aspect of the present invention provides a phase change material comprising a doped Ge-Sb-based material, characterized in that the general chemical formula of the doped Ge-Sb-based material is M x (Ge i Sb j ) 100-x ;
其中，M为掺杂元素，所述M为C、N、O、Sn中的至少一种；Wherein, M is a doping element, and the M is at least one of C, N, O, and Sn;
其中，x代表M的原子个数百分比，0＜x≤30，i、j代表Ge、Sb元素的原子个数百分比，0＜i≤50，i+j＝100；Among them, x represents the atomic percentage of M, 0<x≤30, i and j represent the atomic percentage of Ge and Sb elements, 0<i≤50, i+j=100;
其中，所述M原子存在于Ge-Sb晶界中，从而阻碍Ge-Sb基材料结晶使其内部形成非均一相结构；优选可通过控制所述掺杂的Ge-Sb基材料体系内非晶相和晶相的成分比例，来实现所述相变材料在不同阻态之间的转变。Wherein, the M atoms are present in the Ge-Sb grain boundary, thereby hindering the crystallization of Ge-Sb-based materials to form a heterogeneous phase structure inside; preferably, the amorphous structure in the doped Ge-Sb-based material system can be controlled. The composition ratio of the phase and the crystal phase is used to realize the transformation of the phase change material between different resistance states.
进一步地，所述掺杂的Ge-Sb基材料的Mx(Ge iSb j) 100-x化学通式中，X的优选范围为10＜x≤20。 Further, in the general chemical formula of Mx(Ge i Sb j ) 100-x of the doped Ge-Sb-based material, the preferred range of X is 10<x≦20.
进一步地，所述掺杂的Ge-Sb基材料的M x(Ge iSb j) 100-x化学通式中，i与j的优选范围为10＜i≤20,70≤j＜95，i+j＝100。 Further, in the general chemical formula of M x (Ge i Sb j ) 100-x of the doped Ge-Sb-based material, the preferred range of i and j is 10<i≤20, 70≤j<95, i +j=100.
进一步地，所述掺杂的Ge-Sb基材料内部形成的非均一相结构中，非晶相和晶相成分比例的调节方式为脉冲激励或激光激励中至少一种。Further, in the heterogeneous phase structure formed inside the doped Ge-Sb-based material, the method for adjusting the ratio of the amorphous phase and the crystal phase composition is at least one of pulse excitation or laser excitation.
进一步地，所述掺杂的Ge-Sb基材料可在亚稳高阻态和亚稳低阻态之间转换；其中，所述亚稳高阻态电阻至少是亚稳低阻态电阻的100倍。Further, the doped Ge-Sb-based material can switch between a metastable high-resistance state and a metastable low-resistance state; wherein the metastable high-resistance resistance is at least 100% of the metastable low-resistance resistance. Times.
进一步地，所述掺杂的Ge-Sb基材料采用磁控溅射法、化学气相沉积法、原子层沉积法、电镀法或电子束蒸发法中的方法制备得到。Further, the doped Ge-Sb-based material is prepared by magnetron sputtering method, chemical vapor deposition method, atomic layer deposition method, electroplating method or electron beam evaporation method.
进一步地，所述相变材料采用磁控溅射法制备得到，包括：当所述M为C或Sn元素时，Further, the phase change material is prepared by a magnetron sputtering method, including: when the M is C or Sn element,
在惰性气体的氛围下，采用Ge、Sb和M三个单质靶共溅射；或In an inert gas atmosphere, three elemental targets of Ge, Sb and M are used for co-sputtering; or
在惰性气体的氛围下，采用GeiSbj合金靶与M单质靶共溅射。In an inert gas atmosphere, a GeiSbj alloy target and an M elemental target are used for co-sputtering.
进一步地，所述相变材料采用磁控溅射法制备得到，包括：当所述M为O或N元素时，Further, the phase change material is prepared by a magnetron sputtering method, including: when the M is O or N element,
在O 2或N 2气体的氛围下，采用Ge、Sb两个单质靶共溅射；或 In an atmosphere of O 2 or N 2 gas, two elemental targets of Ge and Sb are used for co-sputtering; or
在O 2或N 2气体的氛围下，采用Ge iSb j合金靶溅射。 In an atmosphere of O 2 or N 2 gas, a Ge i Sb j alloy target is used for sputtering.
本发明的第二方面，提供一种相变存储单元，包括：依次设置于衬底上的底电极、隔离层、相变薄膜以及顶电极，所述顶电极与所述相变薄膜接触；In a second aspect of the present invention, there is provided a phase change memory cell, comprising: a bottom electrode, an isolation layer, a phase change film, and a top electrode sequentially arranged on a substrate, the top electrode being in contact with the phase change film;
其中，所述相变薄膜的材质为前述的相变材料。Wherein, the material of the phase change film is the aforementioned phase change material.
进一步地，所述相变薄膜的厚度为20-150nm。Further, the thickness of the phase change film is 20-150 nm.
本发明提供的掺杂的Ge-Sb基相变材料、该材料的制备方法、含有该材料的相变存储器(PCM)，具有以下有益效果：The doped Ge-Sb-based phase change material, the preparation method of the material, and the phase change memory (PCM) containing the material provided by the present invention have the following beneficial effects:
一方面，本发明提供了一种新型的掺杂的Ge-Sb基相变材料，可用于制备相变存储器。其中，所述Ge-Sb基相变材料中的掺杂元素M存在于Ge-Sb晶界中，阻碍Ge-Sb基材料结晶使得所述相变材料成为具有调幅分解效应非均一相结构。再通过掺杂、电脉冲、激光等方式控制体系内分相程度，来实现所述相变材料在不同阻态之间的转变，其中亚稳高阻态与亚稳低阻态之间的电阻变化幅度在两个数量级以上。因此，使用该材料制备的相变存储器可以利用这种特殊材料的晶态和非晶态之间相互转化时所表现出来的导电性差异来存储数据。On the one hand, the present invention provides a novel doped Ge-Sb-based phase change material, which can be used to prepare a phase change memory. Wherein, the doping element M in the Ge-Sb-based phase change material exists in the Ge-Sb grain boundary, which hinders the crystallization of the Ge-Sb-based material so that the phase change material has a heterogeneous phase structure with an amplitude modulation decomposition effect. Then the degree of phase separation in the system is controlled by means of doping, electric pulse, laser, etc., to realize the transformation of the phase change material between different resistance states, where the resistance between the metastable high resistance state and the metastable low resistance state The magnitude of the change is more than two orders of magnitude. Therefore, the phase change memory prepared by using this material can store data by using the difference in conductivity that appears when the crystalline state and the amorphous state of this special material are transformed into each other.
另一方面，本发明与现有技术的Ge-Sb-Te基相变材料(GST材料，常见的有Ge 2Sb 2Te 5)相比，M x(Ge iSb j) 100-x相变材料体系中Sb元素含量很高，使其具有更快的晶化速度，并且在相转变的过程中，可进行调幅分相。同时，非均一相变材料体系M x(Ge iSb j) 100-x相变存储材料由于相变区域更小，使其密度变化更小，使得相变后产生的应力减小，器件的循环耐久性能提高；同时，非均一相体系结构使M x(Ge iSb j) 100-x高低阻态的阻值都很大，极大地降低了器件的操作功耗，并具有潜在的进一步可微缩性。 On the other hand, compared with the prior art Ge-Sb-Te based phase change material (GST material, commonly known as Ge 2 Sb 2 Te 5 ), the M x (Ge i Sb j ) 100-x phase change The high content of Sb in the material system allows it to have a faster crystallization rate, and during the phase transition, amplitude modulation and phase separation can be carried out. At the same time, the heterogeneous phase change material system M x (Ge i Sb j ) 100-x phase change memory material has a smaller phase change area, so that its density change is smaller, so that the stress generated after the phase change is reduced, and the cycle of the device is reduced. The endurance performance is improved; at the same time, the non-uniform phase architecture makes the resistance values of the high and low resistance states of M x (Ge i Sb j ) 100-x very large, which greatly reduces the operating power consumption of the device and has the potential to be further scalable Sex.
【附图说明】【Explanation of the drawings】
为了更清楚地说明本发明实施例或现有技术中的技术方案，以下将对实施例或现有技术描述中所需要使用的附图作简单地介绍。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art.
图1为按照本发明实现的M掺杂的Ge-Sb基相变材料制备的相变存储器单元结构示意图；FIG. 1 is a schematic diagram of the structure of a phase change memory cell prepared from an M-doped Ge-Sb-based phase change material according to the present invention;
图2为按照本发明实现的M掺杂的Ge-Sb基相变材料网状晶体-非晶结构TEM表征图；FIG. 2 is a TEM characterization diagram of an M-doped Ge-Sb-based phase change material network crystal-amorphous structure realized according to the present invention;
图3为按照本发明实现的特定擦操作/RESET和特定写操作/SET脉宽脉冲示意图。Fig. 3 is a schematic diagram of pulse width pulses of a specific erase operation/RESET and a specific write operation/SET implemented in accordance with the present invention.
图4为按照本发明实现的实施例1中对相变存储器施加特定写操作/SET连续脉冲测试结果；4 is a test result of applying a specific write operation/SET continuous pulse to the phase change memory in Embodiment 1 implemented according to the present invention;
图5为按照本发明实现的实施例1中对相变存储器施加特定擦操作/RESET 连续脉冲测试结果。FIG. 5 is a test result of applying a specific erase operation/RESET continuous pulse to the phase change memory in Embodiment 1 implemented according to the present invention.
附图标记：1-衬底，2-底电极，3-隔离层，4-相变薄膜，5-顶电极Reference signs: 1-substrate, 2-bottom electrode, 3-separation layer, 4-phase change film, 5-top electrode
【具体实施方式】【Detailed ways】
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。The embodiments of the present invention will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. If no specific conditions are indicated in the examples, it shall be carried out in accordance with the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used without the manufacturer's indication are all conventional products that can be purchased on the market.
在整个说明书中，除非另有特别说明，本文使用的术语应理解为如本领域中通常所使用的含义。因此，除非另有定义，本文使用的所有技术和科学术语具有与本发明所属领域技术人员的一般理解相同的含义。若存在矛盾，本说明书优先。Throughout the specification, unless otherwise specified, the terms used herein should be understood as the meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs. If there is a conflict, this manual takes precedence.
本发明提供一种相变材料，其包括掺杂的Ge-Sb基材料，所述掺杂的Ge-Sb基材料的化学通式为M x(Ge iSb j) 100-x；其中，M为掺杂元素，所述M为C、N、O、Sn中的至少一种；x代表M的原子个数百分比，0＜x≤30，i、j代表Ge、Sb元素的原子个数百分比，0＜i≤50，i+j＝100； The present invention provides a phase change material, which includes a doped Ge-Sb-based material, and the general chemical formula of the doped Ge-Sb-based material is M x (Ge i Sb j ) 100-x ; where M It is a doping element, the M is at least one of C, N, O, and Sn; x represents the atomic percentage of M, 0<x≤30, and i and j represent the atomic percentage of Ge and Sb elements , 0＜i≤50, i+j=100;
具体地，所述M原子存在于Ge-Sb晶界中，从而阻碍Ge-Sb基材料结晶，细化晶粒，使其内部形成非均一相结构。使相变材料体系M x(Ge iSb j) 100-x具有调幅分解效应，即非晶态的相变材料在不同结晶程度的状态时，对应亚稳态中存在不同电阻态。从而可通过控制所述相变材料体系内非晶相和晶相的成分比例，来实现所述相变材料在不同阻态之间的转变。 Specifically, the M atoms exist in the Ge-Sb grain boundary, thereby hindering the crystallization of the Ge-Sb-based material, refining the crystal grains, and forming a heterogeneous phase structure inside. The phase change material system M x (Ge i Sb j ) 100-x has an amplitude modulation decomposition effect, that is, when the amorphous phase change material is in a state of different crystallinity, there are different resistance states in the corresponding metastable state. Thereby, the transformation of the phase change material between different resistance states can be realized by controlling the composition ratio of the amorphous phase and the crystalline phase in the phase change material system.
优选地，所述掺杂的Ge-Sb基材料的Mx(GeiSbj) 100-x化学通式中，X的优选范围为10＜x≤20，M更优选为10。M的掺杂量会影响相变材料的非均一相结构，当M原子占比小于10％时，由于含量太低，无法完全抑制Ge iSb j的结晶，晶粒过大，晶体与非晶态之间的电阻比变化不大，无法产生调幅分解效应；相反，当M原子占比大于20％时，易形成化学链，使得材料电阻不均。 Preferably, in the general chemical formula of Mx(GeiSbj) 100-x of the doped Ge-Sb-based material, the preferred range of X is 10<x≦20, and M is more preferably 10. The doping amount of M will affect the heterogeneous phase structure of the phase change material. When the proportion of M atoms is less than 10%, the content of M is too low to completely inhibit the crystallization of Ge i Sb j , and the crystal grains are too large. The resistance ratio between the states does not change much, and the amplitude modulation decomposition effect cannot be produced; on the contrary, when the proportion of M atoms is greater than 20%, chemical chains are easily formed, which makes the material resistance uneven.
优选地，所述掺杂的Ge-Sb基材料的M x(Ge iSb j) 100-x化学通式中，i与j的优选范围为10＜i≤20,70≤j＜95，i+j＝100。Ge iSb j晶体具有较好的化学稳定性，同时Sb元素含量较高，使其具有更快的晶化速度，使相变材料在不同阻态之间的转变更快。更优地，Ge iSb j晶体可选自Ge 10Sb 90、Ge 15Sb 85、Ge 20Sb 80、Ge 25Sb 75中至少一种。 Preferably, in the general chemical formula of M x (Ge i Sb j ) 100-x of the doped Ge-Sb-based material, the preferred range of i and j is 10<i≤20, 70≤j<95, i +j=100. Ge i Sb j crystal has good chemical stability, and at the same time, the content of Sb element is higher, so that it has a faster crystallization speed, which makes the phase change material change faster between different resistance states. More preferably, the Ge i Sb j crystal can be selected from at least one of Ge 10 Sb 90 , Ge 15 Sb 85 , Ge 20 Sb 80 , and Ge 25 Sb 75.
根据一种实施方式，所述掺杂的Ge-Sb基材料内部形成的非均一相结构中，非晶相和晶相的成分比例的调节方式为脉冲激励或激光激励中至少一种。所述材料具体相变过程是由稳定的晶体结构与非晶态之间转化形成的相变，通过上述方式可使M x(Ge iSb j) 100-x体系材料进行晶体/非晶体的可逆相变。所述调节方式优选为电脉冲；具体地，通过给所述相变材料施加脉冲电压或脉冲电流。 According to one embodiment, in the heterogeneous phase structure formed inside the doped Ge-Sb-based material, the composition ratio of the amorphous phase and the crystalline phase is adjusted by at least one of pulse excitation or laser excitation. The specific phase change process of the material is a phase change formed by the conversion between a stable crystal structure and an amorphous state. Through the above method, the M x (Ge i Sb j ) 100-x system material can be reversibly crystalline/amorphous. Phase change. The adjustment method is preferably an electric pulse; specifically, by applying a pulse voltage or a pulse current to the phase change material.
根据一种实施方式，所述相变材料可在亚稳高阻态和亚稳低阻态之间转换；其中，所述亚稳高阻态电阻至少是亚稳低阻态电阻的100倍。如上所述，通过掺杂、电脉冲或激光等方式可控制M x(Ge iSb j) 100-体系内分相程度，即使所述相变材料具有至少两种亚稳阻态，具体是指所述材料可至少产生两种不同电阻值的亚稳态结构。同时，由于所述相变材料具有调幅分解效应，其不同亚稳态之间的电阻变化幅度可达到两个数量级以上。 According to an embodiment, the phase change material can switch between a metastable high resistance state and a metastable low resistance state; wherein the metastable high resistance state is at least 100 times the metastable low resistance state. As mentioned above, the degree of phase separation in the M x (Ge i Sb j ) 100- system can be controlled by means of doping, electric pulse or laser, even if the phase change material has at least two metastable resistance states, specifically referring to The material can produce at least two metastable structures with different resistance values. At the same time, because the phase change material has an amplitude modulation decomposition effect, the resistance change range between its different metastable states can reach more than two orders of magnitude.
这里值得说明的是，相变存储器要求相变材料同时有较大的非晶态/晶态电阻比和较好的化学稳定性，根据上述可知，本发明提供的M x(Ge iSb j) 100-x相变材料，优选范围在0＜x≤30，0＜i≤50，i+j＝100条件下；更优范围在10＜x≤20，10＜i≤20,70≤j＜95，i+j＝100条件下，具有最优良性能。 It is worth noting here that the phase change memory requires that the phase change material has a larger amorphous/crystalline resistance ratio and better chemical stability. According to the above, the M x (Ge i Sb j ) provided by the present invention 100-x phase change material, the preferred range is 0＜x≤30, 0＜i≤50, i+j=100; the more preferred range is 10＜x≤20, 10＜i≤20, 70≤j＜ 95, under the condition of i+j=100, it has the best performance.
根据一种实施方式，提供了一种所述的相变材料的制备方法，所述制备方法包括：磁控溅射法、化学气相沉积法、原子层沉积法、电镀法或电子束蒸发法中至少一种。According to one embodiment, there is provided a method for preparing the phase change material. The preparation method includes: magnetron sputtering, chemical vapor deposition, atomic layer deposition, electroplating, or electron beam evaporation. At least one.
根据一种具体的实施方式，所述方法为磁控溅射法，优选为采用直流磁控溅射法，当所述M为C或Sn元素时，According to a specific embodiment, the method is a magnetron sputtering method, preferably a DC magnetron sputtering method, when the M is C or Sn element,
(1)在惰性气体的氛围下，采用Ge、Sb和M三个单质靶共溅射；(1) In an inert gas atmosphere, three elemental targets of Ge, Sb and M are used for co-sputtering;
(2)在惰性气体的氛围下，采用Ge iSb j合金靶与M单质靶共溅射； (2) Co-sputtering with Ge i Sb j alloy target and M elemental target in an inert gas atmosphere;
可采用以上两种方法中的任意一种。Either of the above two methods can be used.
具体地，采用方法(1)时，将Ge、Sb和M三个单质靶采用溅射方法溅射至基片上；进一步地，溅射时通入高纯氩气作为溅射气体，溅射气压为0.5Pa，背景真空要求为10 -4Pa以下，溅射功率为25W。采用方法(2)时，将Ge iSb j合金靶与M单质靶采用溅射方法溅射至基片上；进一步地，溅射时通入高纯氩气作为溅射气体，溅射气压为0.5Pa，背景真空要求为10 -4Pa以下，溅射功率为40W。 Specifically, when the method (1) is used, the three elemental targets of Ge, Sb, and M are sputtered onto the substrate by the sputtering method; further, high-purity argon gas is introduced as the sputtering gas during sputtering, and the sputtering pressure It is 0.5 Pa, the background vacuum requirement is 10 -4 Pa or less, and the sputtering power is 25W. When using method (2), the Ge i Sb j alloy target and the M elemental target are sputtered onto the substrate by the sputtering method; further, high-purity argon gas is introduced as the sputtering gas during sputtering, and the sputtering pressure is 0.5 Pa, the background vacuum requirement is 10 -4 Pa or less, and the sputtering power is 40W.
根据一种具体的实施方式，所述方法为磁控溅射法，优选为采用直流磁控溅 射法，当所述M为O或N元素时，According to a specific embodiment, the method is a magnetron sputtering method, preferably a DC magnetron sputtering method, when the M is O or N element,
(1)在O 2或N 2气体的氛围下，采用Ge、Sb两个单质靶共溅射； (1) In an atmosphere of O 2 or N 2 gas, two elemental targets of Ge and Sb are used for co-sputtering;
(2)在O 2或N 2气体的氛围下，采用Ge iSb j合金靶溅射； (2) Sputtering with Ge i Sb j alloy target in an atmosphere of O 2 or N 2 gas;
可采用以上两种方法中的任意一种。Either of the above two methods can be used.
具体地，采用方法(1)时，将Ge和Sb两个单质靶采用溅射方法溅射至基片上；进一步地，溅射时通入高纯O 2或N 2气体作为溅射气体，溅射气压为0.5Pa，背景真空要求为10 -4以下，溅射功率为25W。采用方法(2)时，将Ge iSb j合金靶采用溅射方法溅射至基片上；进一步地，溅射时通入高纯O 2或N 2气体作为溅射气体，溅射气压为0.5Pa，背景真空要求为10 -4以下，溅射功率为40W。 Specifically, when the method (1) is used, the two elemental targets of Ge and Sb are sputtered onto the substrate by the sputtering method; further, high-purity O 2 or N 2 gas is introduced as the sputtering gas during sputtering, and the sputtering The injection pressure is 0.5Pa, the background vacuum requirement is 10 -4 or less, and the sputtering power is 25W. When using method (2), the Ge i Sb j alloy target is sputtered onto the substrate by a sputtering method; further, high-purity O 2 or N 2 gas is introduced as the sputtering gas during sputtering, and the sputtering gas pressure is 0.5 Pa, the background vacuum requirement is 10 -4 or less, and the sputtering power is 40W.
根据一种实施方式，提供一种相变存储单元，结构如图1所示，包括：依次设置于衬底1上的底电极2、隔离层3、相变薄膜4以及顶电极5，所述顶电极5与所述相变薄膜4接触；其中，所述相变薄膜4的材质为前述的相变材料。According to one embodiment, there is provided a phase change memory cell with a structure as shown in FIG. 1, comprising: a bottom electrode 2, an isolation layer 3, a phase change film 4, and a top electrode 5 which are sequentially arranged on a substrate 1. The top electrode 5 is in contact with the phase change film 4; wherein the material of the phase change film 4 is the aforementioned phase change material.
优选地，所述相变薄膜4的厚度为20-150nm，更优选为100nm。相变薄膜的厚度由靶材溅射时间决定，溅射时间为86-646s，更优为431s。Preferably, the thickness of the phase change film 4 is 20-150 nm, more preferably 100 nm. The thickness of the phase change film is determined by the sputtering time of the target, and the sputtering time is 86-646s, more preferably 431s.
优选地，所述衬底1的材质为SiO 2/p-Si；具体地，使用溅射方法在p-Si结晶材料上淀积富硅二氧化硅。 Preferably, the material of the substrate 1 is SiO 2 /p-Si; specifically, a sputtering method is used to deposit silicon-rich silicon dioxide on the p-Si crystalline material.
优选地，所述底电极2和顶电极5的材质为Pt。更优地，底电极采用直流磁控溅射法制得，厚度为100nm。Preferably, the material of the bottom electrode 2 and the top electrode 5 is Pt. More preferably, the bottom electrode is made by a DC magnetron sputtering method and has a thickness of 100 nm.
具体地，将Pt靶材采用溅射方法溅射至SiO 2/Si(100)基片上；进一步地，溅射时通入高纯氩气作为溅射气体，溅射气压为0.5Pa，背景真空要求为10 -4以下；当采用直流源溅射，溅射功率为35W。 Specifically, the Pt target material was sputtered onto the SiO 2 /Si (100) substrate by a sputtering method; further, high-purity argon was introduced as the sputtering gas during sputtering, the sputtering pressure was 0.5 Pa, and the background vacuum The requirement is 10 -4 or less; when using DC source sputtering, the sputtering power is 35W.
优选地，所述隔离层3的材质为SiO 2。更优地，所述SiO 2隔离层采用等离子体增强化学的气相沉积法(PECVD)制备。 Preferably, the material of the isolation layer 3 is SiO 2 . More preferably, the SiO 2 isolation layer is prepared by plasma enhanced chemical vapor deposition (PECVD).
具体地，在SiO 2层上采用紫外光刻或电子阻挡层(EBL)制备特征图案，再使用电感耦合等离子体(ICP)刻蚀除去特征图形处的SiO 2隔离层，使其与底电极连通；再去光刻胶；再使用MJB4紫外光刻机套刻上电极图案，厚度为100nm。 Specifically, ultraviolet lithography or electron blocking layer (EBL) is used to prepare a feature pattern on the SiO 2 layer, and then an inductively coupled plasma (ICP) etching is used to remove the SiO 2 isolation layer at the feature pattern to make it communicate with the bottom electrode ; Then go to the photoresist; then use the MJB4 UV lithography machine to engrave the electrode pattern, the thickness is 100nm.
根据一种实施方式，提供一种相变存储器，包括前述的相变存储单元。本发明中，所述相变存储器是利用M x(Ge iSb j) 100-x相变材料在晶态和非晶态之间相互转化时所表现出来的导电性差异来存储数据的。 According to an embodiment, a phase change memory is provided, including the aforementioned phase change memory cell. In the present invention, the phase change memory utilizes the conductivity difference shown by the M x (Ge i Sb j ) 100-x phase change material when the crystalline state and the amorphous state are transformed into each other to store data.
根据一种实施方式，提供一种相变存储器的操作方法，包括：对前述的相变存储器施加预操作，得到亚稳高阻态的相变存储器；对所述亚稳高阻态的相变存储器施加特定写操作，得到亚稳低阻态的相变存储器；对所述亚稳低阻态的相变存储器施加特定擦操作，得到亚稳高阻态的相变存储器；从而实现所述相变存储器在不同亚稳阻态之间的转变。According to an embodiment, a method for operating a phase change memory is provided, which includes: applying pre-operation to the aforementioned phase change memory to obtain a phase change memory in a metastable high resistance state; A specific write operation is applied to the memory to obtain a phase change memory in a metastable low resistance state; a specific erase operation is applied to the phase change memory in a metastable low resistance state to obtain a phase change memory in a metastable high resistance state; The transition of variable memory between different metastable resistance states.
优选地，所述预操作包括退火或施加脉冲中至少一种。Preferably, the pre-operation includes at least one of annealing or pulse application.
优选地，所述写操作的电压脉冲幅值为1.5V-2.5V，脉宽1-20μs；所述擦操作的电压脉冲幅值为1V-3V，脉宽30ns-100ns。Preferably, the voltage pulse amplitude of the write operation is 1.5V-2.5V, and the pulse width is 1-20 μs; the voltage pulse amplitude of the erase operation is 1V-3V, and the pulse width is 30ns-100ns.
本发明中，通过退火或施加脉影响相变存储器中相变薄膜，即使相变薄膜形成非晶层，得到亚稳高阻态的相变存储器，施加特定写操作/SET用于设置逻辑1，使相变薄膜非晶层再结晶回到结晶态，即使相变存储器由亚稳高阻态向亚稳低阻态转变；施加特定擦操作/RESET脉冲即逻辑0，使相变薄膜再产生非晶层，即使相变存储器由亚稳低阻态向亚稳高阻态转变；如图3所示特定擦操作/RESET脉冲比特定写操作/SET脉宽要窄。In the present invention, the phase change film in the phase change memory is affected by annealing or pulse application, even if the phase change film forms an amorphous layer, a metastable high resistance phase change memory is obtained, and a specific write operation /SET is applied to set logic 1. Recrystallize the amorphous layer of the phase change film back to the crystalline state, even if the phase change memory changes from a metastable high-resistance state to a metastable low-resistance state; apply a specific erase operation/RESET pulse, which is logic 0, to make the phase change film regenerate non-crystalline Crystal layer, even if the phase change memory changes from a metastable low resistance state to a metastable high resistance state; as shown in Figure 3, the specific erase operation/RESET pulse is narrower than the specific write operation/SET pulse width.
实施例Example
以下参考附图所示的示意性的示例，进一步说明本发明。通过以下说明，本发明的各方面优点将更加明显。附图中相同的附图标记指代相同的部件。示意性附图中各部件的形状和尺寸仅用于示意，并不能被认为体现了实际的形状、尺寸和绝对的位置。Hereinafter, the present invention will be further explained with reference to the schematic examples shown in the drawings. Through the following description, the advantages of various aspects of the present invention will be more obvious. The same reference numerals in the drawings refer to the same parts. The shape and size of each component in the schematic drawings are for illustration only, and cannot be considered to reflect the actual shape, size and absolute position.
实施例1Example 1
本实施例提供了一种O掺杂的Ge-Sb基相变存储器，其中x＝10，i＝10，j＝90，即结构式为：O 10(Ge 10Sb 90) 90，其制作方法如下： This embodiment provides an O-doped Ge-Sb-based phase change memory, where x=10, i=10, and j=90, that is, the structural formula is: O 10 (Ge 10 Sb 90 ) 90 , and the manufacturing method is as follows :
(1)掺杂O的Ge-Sb基相变薄膜制备(1) Preparation of O-doped Ge-Sb-based phase change film
装好Ge和Sb溅射单质靶材(分别设为A/B靶)，靶材的纯度均达到99.999％(原子百分比)，并将本底充入高纯O 2；设定溅射功率为25W；使用高纯O 2作为溅射气体(体积百分比达到99.999％)，设定O 2气流量为10sccm，并将溅射气压调节至0.5Pa。 Install Ge and Sb sputtering elementary target materials (set as A/B targets respectively), the purity of the target materials reaches 99.999% (atomic percentage), and fill the background with high-purity O 2 ; set the sputtering power as 25W; Use high-purity O 2 as the sputtering gas (volume percentage reaches 99.999%), set the O 2 gas flow rate to 10 sccm, and adjust the sputtering gas pressure to 0.5 Pa.
将空基托旋转到靶位，打开Ge靶上所施加的射频电源，开始对靶材进行溅 射，清洁靶材表面；靶材表面清洁完成后，关闭靶上所施加的直流电源，将Sb靶(溅射基片旋转到靶位开启靶位射频电源，开始溅射相变薄膜，溅射的厚度为100nm。Rotate the empty base to the target position, turn on the RF power applied on the Ge target, start sputtering on the target, and clean the surface of the target; after the surface of the target is cleaned, turn off the DC power applied on the target, and set the Sb Target (The sputtering substrate rotates to the target position to turn on the radio frequency power of the target position, and the phase change film is sputtered. The sputtering thickness is 100nm.
(2)掺杂O的Ge-Sb基相变存储器制备前准备(2) Preparation before preparation of O-doped Ge-Sb-based phase change memory
Pt膜底电极：将Pt靶材和SiO 2/Si(100)基片放入溅射腔中对应位置，靶材纯度为99.99％(原子百分比)，并将腔内真空抽至10 -4以下；向溅射腔内通入高纯度Ar气作为溅射气体，Ar气流稳定为10sccm，溅射气压设定为0.5Pa，靶材和基片距离设置为150mm，开启托位自转，转速为135r/min；开启磁控溅射直流源，溅射功率调节为35w。待辉光稳定后，将空托旋转到Pt靶材正上方，打开Pt靶位处的挡板，预溅射5-10min，清洁靶材表面；预溅射完成之后，先关闭Pt靶位处的挡板，将放有待溅射基片的托位旋转至Pt靶材正上方，Pt在该溅射条件下的溅射速率为0.143nm/s，根据溅射速率设定相应的溅射时间，制备厚度为100nm的Pt底电极。 Pt film bottom electrode: Put the Pt target and SiO 2 /Si(100) substrate into the corresponding position in the sputtering chamber, the purity of the target is 99.99% (atomic percentage), and the vacuum in the chamber is evacuated to below 10 -4 ; Pass high-purity Ar gas into the sputtering chamber as the sputtering gas, the Ar gas flow is stable at 10sccm, the sputtering pressure is set to 0.5Pa, the distance between the target and the substrate is set to 150mm, the support position is turned on, and the speed is 135r /min; Turn on the magnetron sputtering DC source and adjust the sputtering power to 35w. After the glow stabilizes, rotate the empty tray directly above the Pt target, open the baffle at the Pt target, and pre-sputter for 5-10 minutes to clean the surface of the target; after the pre-sputter is completed, first close the Pt target Rotate the support position where the substrate to be sputtered is placed directly above the Pt target. The sputtering rate of Pt under this sputtering condition is 0.143nm/s, and the corresponding sputtering time is set according to the sputtering rate , A Pt bottom electrode with a thickness of 100 nm was prepared.
SiO 2隔离层：在SiO 2层上采用紫外光刻或EBL制备特征图案；ICP刻蚀除去特征图形处的SiO 2隔离层，使其与底电极连通；再去光刻胶；最后使用MJB4紫外光刻机套刻上电极图案，厚度为100nm。 SiO 2 isolation layer: use ultraviolet lithography or EBL to prepare feature patterns on the SiO 2 layer; ICP etching removes the SiO 2 isolation layer at the feature pattern to make it communicate with the bottom electrode; then remove the photoresist; finally use MJB4 ultraviolet The electrode pattern is engraved on the photoetching machine with a thickness of 100nm.
(3)掺杂O的Ge-Sb基相变存储器制备(3) Preparation of O-doped Ge-Sb-based phase change memory
将O 10(Ge 10Sb 90) 90作为相变存储材料功能层材质，制备得到相变存储器，该相变存储器的相变存储单元，示意图如图1所示，包括依次设置在衬底上1的底电极2、隔离层3、相变薄膜4、顶电极5，顶电极5与相变薄膜4接触，顶电极和底电极的材质为Pt，厚度为100nm，隔离层的材质为SiO 2，厚度为100nm，相变存储材料功能层的材质为O x(Ge 15Sb 85) 1-x，厚度也为100nm。 Using O 10 (Ge 10 Sb 90 ) 90 as the material of the functional layer of the phase change memory material, a phase change memory is prepared. The phase change memory cell of the phase change memory is schematically shown in FIG. The bottom electrode 2, the isolation layer 3, the phase change film 4, and the top electrode 5 are in contact with the phase change film 4. The material of the top electrode and the bottom electrode is Pt, the thickness is 100nm, and the material of the isolation layer is SiO 2 , a thickness of 100nm, the phase change memory material of the functional layer is made of O x (Ge 15 Sb 85) 1-x, the thickness of 100nm.
实施例2Example 2
本实施例提供一种O掺杂的Ge-Sb基相变存储器，其中x＝10，i＝15，j＝85，即结构式为：O 10(Ge 10Sb 90) 90，其制作方法如下： This embodiment provides an O-doped Ge-Sb-based phase change memory, where x=10, i=15, and j=85, that is, the structural formula is: O 10 (Ge 10 Sb 90 ) 90 , and the manufacturing method is as follows:
(1)掺杂O的Ge-Sb基相变薄膜制备(1) Preparation of O-doped Ge-Sb-based phase change film
装好Ge 15Sb 85溅射合金靶材(设为A靶)，靶材的纯度均达到99.999％(原子百分比)，并将本底充入高纯；设定溅射功率为40W；使用高纯O 2作为溅射气体(体积百分比达到99.999％)，设定O 2气流量为10sccm，并将溅射气压调节 至0.5Pa。 Install the Ge 15 Sb 85 sputtering alloy target material (set as target A), the purity of the target material reaches 99.999% (atomic percentage), and the background is filled with high purity; set the sputtering power to 40W; use high Pure O 2 is used as the sputtering gas (volume percentage reaches 99.999%), the O 2 gas flow is set to 10 sccm, and the sputtering gas pressure is adjusted to 0.5 Pa.
将空基托旋转到靶位，打开Ge 15Sb 85靶上所施加的射频电源，开始溅射相变薄膜，溅射的厚度为100nm。 Rotate the empty base to the target position, turn on the radio frequency power applied on the Ge 15 Sb 85 target, and start sputtering the phase change film with a thickness of 100 nm.
步骤(2)(3)将实施例1中(2)(3)换为对应制备的相变薄膜。Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
实施例3～9Examples 3-9
采用同实施例1或2相同的方法，选取不同的Ge-Sb基材料和掺杂元素，使用相应的磁控直流溅射工艺制备相变薄膜，从而制备相变存储器。各Ge-Sb基材料、掺杂元素和使用溅射方法参数总结于表1。Using the same method as in Embodiment 1 or 2, different Ge-Sb-based materials and doping elements are selected, and the corresponding magnetron DC sputtering process is used to prepare the phase change film, thereby preparing the phase change memory. The parameters of the Ge-Sb-based materials, doping elements and sputtering methods used are summarized in Table 1.
实施例10Example 10
本实施例提供了一种N掺杂的Ge-Sb基相变存储器，其中x＝10，i＝10，j＝90，即结构式为：N 10(Ge 10Sb 90) 90，其制作方法如下： This embodiment provides an N-doped Ge-Sb-based phase change memory, where x=10, i=10, j=90, that is, the structural formula is: N 10 (Ge 10 Sb 90 ) 90 , and the manufacturing method is as follows :
(1)掺杂N的Ge-Sb基相变薄膜制备(1) Preparation of N-doped Ge-Sb-based phase change film
装好Ge和Sb溅射单质靶材(分别设为A/B靶)，靶材的纯度均达到99.999％(原子百分比)，并将本底充入高纯N 2；设定溅射功率为25W；使用高纯N 2作为溅射气体(体积百分比达到99.999％)，设定N 2气流量为10sccm，并将溅射气压调节至0.4Pa。 Install Ge and Sb sputtering elementary target materials (set as A/B targets respectively), the purity of the target materials reaches 99.999% (atomic percentage), and fill the background with high-purity N 2 ; set the sputtering power as 25W; Use high-purity N 2 as the sputtering gas (volume percentage reaches 99.999%), set the N 2 gas flow rate to 10 sccm, and adjust the sputtering gas pressure to 0.4 Pa.
将空基托旋转到靶位，打开Ge靶上所施加的射频电源，开始对靶材进行溅射，清洁靶材表面；靶材表面清洁完成后，关闭靶上所施加的直流电源，将Sb靶溅射基片旋转到靶位开启靶位射频电源，开始溅射相变薄膜，溅射的厚度为100nm。Rotate the empty base to the target position, turn on the RF power applied on the Ge target, start sputtering on the target, and clean the surface of the target; after the surface of the target is cleaned, turn off the DC power applied on the target, and set the Sb The target sputtering substrate is rotated to the target position to turn on the target position's radio frequency power supply to start sputtering the phase change film, and the sputtering thickness is 100 nm.
步骤(2)(3)将实施例1中(2)(3)换为对应制备的相变薄膜。Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
实施例11Example 11
本实施例提供了一种N掺杂的Ge-Sb基相变存储器，其中x＝10，i＝15，j＝85，即结构式为：N 10(Ge 15Sb 85) 90，其制作方法如下： This embodiment provides an N-doped Ge-Sb-based phase change memory, where x=10, i=15, j=85, that is, the structural formula is: N 10 (Ge 15 Sb 85 ) 90 , and the manufacturing method is as follows :
(1)掺杂N的Ge-Sb基相变薄膜制备(1) Preparation of N-doped Ge-Sb-based phase change film
装好Ge 15Sb 85溅射合金靶材(设为A靶)，靶材的纯度均达到99.999％(原子百分比)，并将本底充入高纯N 2；设定溅射功率为40W；使用高纯N 2作为溅射气体(体积百分比达到99.999％)，设定N 2气流量为10sccm，并将溅射气压调节至0.4Pa。 Install the Ge 15 Sb 85 sputtering alloy target material (set as target A), the purity of the target material reaches 99.999% (atomic percentage), and fill the background with high-purity N 2 ; set the sputtering power to 40W; Use high-purity N 2 as the sputtering gas (volume percentage reaches 99.999%), set the N 2 gas flow rate to 10 sccm, and adjust the sputtering gas pressure to 0.4 Pa.
将空基托旋转到靶位，打开Ge 15Sb 85靶上所施加的射频电源，开始溅射相变薄膜，溅射的厚度为100nm。 Rotate the empty base to the target position, turn on the radio frequency power applied on the Ge 15 Sb 85 target, and start sputtering the phase change film with a thickness of 100 nm.
步骤(2)(3)将实施例1中(2)(3)换为对应制备的相变薄膜。Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
实施例12Example 12
本实施例提供了一种C掺杂的Ge-Sb基相变存储器，其中x＝10，i＝10，j＝90，即结构式为：C 10(Ge 10Sb 90) 90，其制作方法如下： This embodiment provides a C-doped Ge-Sb-based phase change memory, where x=10, i=10, and j=90, that is, the structural formula is: C 10 (Ge 10 Sb 90 ) 90 , and the manufacturing method is as follows :
(1)掺杂C的Ge-Sb基相变薄膜制备(1) Preparation of C-doped Ge-Sb-based phase change film
装好Ge、Sb和C溅射单质靶材(分别设为A/B/C靶)，靶材的纯度均达到99.999％(原子百分比)，并将本底充入高纯Ar；设定溅射功率为25W；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10sccm，并将溅射气压调节至0.5Pa。Install Ge, Sb and C sputtering elemental targets (set as A/B/C targets respectively), the purity of the target materials reaches 99.999% (atomic percentage), and fill the background with high-purity Ar; set the sputtering The firing power is 25W; high-purity Ar is used as the sputtering gas (volume percentage reaches 99.999%), the Ar gas flow is set to 10sccm, and the sputtering gas pressure is adjusted to 0.5Pa.
将空基托旋转到靶位，打开Ge靶上所施加的射频电源，开始对靶材进行溅射，清洁靶材表面；靶材表面清洁完成后，关闭靶上所施加的直流电源，将Sb靶溅射基片旋转到靶位开启靶位射频电源，开始对靶材进行溅射，清洁靶材表面；靶材表面清洁完成后，关闭靶上所施加的直流电源，将C靶溅射基片旋转到靶位开启靶位射频电源，开始溅射相变薄膜，溅射的厚度为100nm。Rotate the empty base to the target position, turn on the RF power applied on the Ge target, start sputtering on the target, and clean the surface of the target; after the surface of the target is cleaned, turn off the DC power applied on the target, and set the Sb The target sputtering substrate rotates to the target position to turn on the RF power supply of the target position, and start sputtering the target material to clean the surface of the target material; after the surface of the target material is cleaned, turn off the DC power applied on the target, and sputter the C target on the base. The film rotates to the target position to turn on the target position's radio frequency power supply, and the phase change film is sputtered. The sputtering thickness is 100 nm.
步骤(2)(3)将实施例1中(2)(3)换为对应制备的相变薄膜Step (2) (3) replace (2) (3) in Example 1 with the corresponding phase change film prepared
实施例13Example 13
本实施例提供了一种C掺杂的Ge-Sb基相变存储器，其中x＝10，i＝15，j＝85，即结构式为：C 10(Ge 15Sb 85) 90，其制作方法如下： This embodiment provides a C-doped Ge-Sb-based phase change memory, where x=10, i=15, j=85, that is, the structural formula is: C 10 (Ge 15 Sb 85 ) 90 , and the manufacturing method is as follows :
(1)掺杂C的Ge-Sb基相变薄膜制备(1) Preparation of C-doped Ge-Sb-based phase change film
装好Ge 15Sb 85溅射合金和C溅射单质靶材(分别设为A/B靶)，靶材的纯度均达到99.999％(原子百分比)，并将本底充入高纯Ar；设定溅射功率为40W；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10sccm，并将溅射气压调节至0.5a。 Install Ge 15 Sb 85 sputtering alloy and C sputtering elemental targets (set as A/B targets respectively), and the purity of the target materials reaches 99.999% (atomic percentage), and the background is filled with high-purity Ar; Set the sputtering power to 40W; use high-purity Ar as the sputtering gas (volume percentage reaches 99.999%), set the Ar gas flow rate to 10sccm, and adjust the sputtering gas pressure to 0.5a.
将空基托旋转到靶位，打开Ge 15Sb 85靶上所施加的射频电源，开始对靶材进行溅射，清洁靶材表面；靶材表面清洁完成后，关闭靶上所施加的直流电源，将C靶溅射基片旋转到靶位开启靶位射频电源，开始溅射相变薄膜，溅射的厚度为100nm。 Rotate the empty base to the target position, turn on the RF power applied on the Ge 15 Sb 85 target, start sputtering on the target, and clean the surface of the target; after the surface of the target is cleaned, turn off the DC power applied on the target , Rotate the C target sputtering substrate to the target position and turn on the target position's radio frequency power supply to start sputtering the phase change film, and the sputtering thickness is 100nm.
步骤(2)(3)将实施例1中(2)(3)换为对应制备的相变薄膜。Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
实施例14Example 14
本实施例提供了一种Sn掺杂的Ge-Sb基相变存储器，其中x＝10，i＝10，j＝90，即结构式为：Sn 10(Ge 10Sb 90) 90，其制作方法如下： This embodiment provides a Sn-doped Ge-Sb-based phase change memory, where x=10, i=10, and j=90, that is, the structural formula is: Sn 10 (Ge 10 Sb 90 ) 90 , and the manufacturing method is as follows :
(1)掺杂Sn的Ge-Sb基相变薄膜制备(1) Preparation of Sn-doped Ge-Sb-based phase change film
装好Ge、Sb和Sn溅射单质靶材(分别设为A/B/C靶)，靶材的纯度均达到99.999％(原子百分比)，并将本底充入高纯Ar；设定溅射功率为25W；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10sccm，并将溅射气压调节至0.5Pa。Install Ge, Sb and Sn sputtering elemental targets (set as A/B/C targets respectively), the purity of the target materials all reach 99.999% (atomic percentage), and fill the background with high-purity Ar; set the sputtering The firing power is 25W; high-purity Ar is used as the sputtering gas (volume percentage reaches 99.999%), the Ar gas flow is set to 10sccm, and the sputtering gas pressure is adjusted to 0.5Pa.
将空基托旋转到靶位，打开Ge靶上所施加的射频电源，开始对靶材进行溅射，清洁靶材表面；靶材表面清洁完成后，关闭靶上所施加的直流电源，将Sb溅射基片旋转到靶位开启靶位射频电源，开始对靶材进行溅射，清洁靶材表面；靶材表面清洁完成后，关闭靶上所施加的直流电源，将Sn溅射基片旋转到靶位开启靶位射频电源，开始溅射相变薄膜，溅射的厚度为100nm。Rotate the empty base to the target position, turn on the RF power applied on the Ge target, start sputtering on the target, and clean the surface of the target; after the surface of the target is cleaned, turn off the DC power applied on the target, and set the Sb The sputtering substrate is rotated to the target position, and the RF power supply is turned on at the target position, and the target material is sputtered to clean the surface of the target material; after the surface of the target material is cleaned, the DC power supply applied to the target is turned off, and the Sn sputtering substrate is rotated Go to the target position and turn on the target position's RF power supply to start sputtering the phase change film, and the sputtering thickness is 100nm.
步骤(2)(3)将实施例1中(2)(3)换为对应制备的相变薄膜Step (2) (3) replace (2) (3) in Example 1 with the corresponding phase change film prepared
实施例15Example 15
本实施例提供了一种Sn掺杂的Ge-Sb基相变存储器，其中x＝10，i＝15，j＝85，即结构式为：Sn 10(Ge 15Sb 85) 90，其制作方法如下： This embodiment provides a Sn-doped Ge-Sb-based phase change memory, where x=10, i=15, j=85, that is, the structural formula is: Sn 10 (Ge 15 Sb 85 ) 90 , and the manufacturing method is as follows :
(1)掺杂Sn的Ge-Sb基相变薄膜制备(1) Preparation of Sn-doped Ge-Sb-based phase change film
装好Ge 15Sb 85溅射合金靶材(设为A靶)，靶材的纯度均达到99.999％(原子百分比)，并将本底充入高纯Ar；设定溅射功率为40W；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10sccm，并将溅射气压调节至0.5Pa。 Install the Ge 15 Sb 85 sputtering alloy target material (set as target A), the purity of the target material reaches 99.999% (atomic percentage), and the background is filled with high-purity Ar; set the sputtering power to 40W; use High-purity Ar is used as the sputtering gas (volume percentage reaches 99.999%), the Ar gas flow is set to 10 sccm, and the sputtering gas pressure is adjusted to 0.5 Pa.
将空基托旋转到靶位，打开Ge 15Sb 85靶上所施加的射频电源，开始对靶材进行溅射，清洁靶材表面；靶材表面清洁完成后，关闭靶上所施加的直流电源，将Sn溅射基片旋转到靶位开启靶位射频电源，开始溅射相变薄膜，溅射的厚度为100nm。 Rotate the empty base to the target position, turn on the RF power applied on the Ge 15 Sb 85 target, start sputtering on the target, and clean the surface of the target; after the surface of the target is cleaned, turn off the DC power applied on the target , Rotate the Sn sputtering substrate to the target position and turn on the target position's radio frequency power supply to start sputtering the phase change film, and the sputtering thickness is 100nm.
步骤(2)(3)将实施例1中(2)(3)换为对应制备的相变薄膜。Steps (2) and (3) replace (2) and (3) in Example 1 with the correspondingly prepared phase change film.
表1实施例1～15中掺杂的Ge-Sb基材料样品成分和磁控直流溅射法工艺Table 1 Sample composition and magnetron DC sputtering process of the doped Ge-Sb-based materials in Examples 1-15
Figure PCTCN2020116619-appb-000001
Figure PCTCN2020116619-appb-000001
根据实施例1～15说明，M x(Ge iSb j) 100-x体系的相变薄膜，其中，M为C、N、O、Sn，且0＜x≤30，0＜i≤50，i+j＝100；是可以通过设置溅射法工艺参数进行制备的。 According to the description of Examples 1-15, M x (Ge i Sb j ) 100-x system phase change film, where M is C, N, O, Sn, and 0<x≤30, 0<i≤50, i+j=100; can be prepared by setting sputtering process parameters.
下面将详细描述本发明实施例1的相变存储器应用及特殊操作：将实施例1制得的Ge-Sb基相变存储材料O 10(Ge 10Sb 90) 90做TEM表征得到的网状非晶结构图，如图2所示。图中用不同的虚线分别标出材料中的非晶区域和晶态区域。可以看出，掺杂M之后的Ge-Sb基相变存储材料存在明显的分相过程，通过使用特定的电学操作，可以调节两种相成分的比例，实现相变存储材料在不同阻态之间的转变。 The application and special operation of the phase change memory of embodiment 1 of the present invention will be described in detail below: the Ge-Sb-based phase change memory material O 10 (Ge 10 Sb 90 ) 90 prepared in embodiment 1 is subjected to TEM characterization to obtain a meshed non The crystal structure diagram is shown in Figure 2. In the figure, different dashed lines are used to mark the amorphous and crystalline regions in the material. It can be seen that the Ge-Sb-based phase change memory material doped with M has an obvious phase separation process. By using specific electrical operations, the ratio of the two phase components can be adjusted to realize the phase change memory material in different resistance states. Between the changes.
在对相变存储器施加连续Set、Reset脉冲时，得到基于M x(Ge iSb j) 100-x的相变存储器阻值随着施加脉冲大小的变化曲线图，如图3，图4所示。脉冲范围为0-3V，Set过程脉冲宽度为10μs，Reset过程脉冲宽度为50ns，可以看到，当 施加不同大小的电压脉冲时，相变存储材料内部会存在调幅分解过程，改变了材料中非晶相和晶相的成分比例，在电学上表征为电阻值的连续变化，并且，由于材料中非晶相的存在，材料的低阻态和高阻态为传统相变存储材料的100倍以上，这使得基于M x(Ge iSb j) 100-x的相变存储器的操作功耗只有传统相变存储器的1/100，大大减小了存储器件的热损耗，同时降低了单元之间的热串扰，有利于存储阵列的进一步尺寸微缩。 When applying continuous Set and Reset pulses to the phase change memory, the resistance value of the phase change memory based on M x (Ge i Sb j ) 100-x varies with the applied pulse size, as shown in Fig. 3 and Fig. 4 . The pulse range is 0-3V, the pulse width of the Set process is 10μs, and the pulse width of the Reset process is 50ns. It can be seen that when voltage pulses of different sizes are applied, there will be an amplitude modulation decomposition process inside the phase change memory material, which changes the material The composition ratio of the crystalline phase and the crystalline phase is electrically characterized as a continuous change in the resistance value, and, due to the presence of the amorphous phase in the material, the low-resistance state and high-resistance state of the material are more than 100 times that of traditional phase change memory materials , This makes the operating power consumption of the phase change memory based on M x (Ge i Sb j ) 100-x only 1/100 of that of the traditional phase change memory, which greatly reduces the heat loss of the storage device and reduces the inter-unit Thermal crosstalk is conducive to the further downsizing of the storage array.
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。Those skilled in the art can easily understand that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement and improvement, etc. made within the spirit and principle of the present invention, All should be included in the protection scope of the present invention.

Claims (10)

  1. 一种相变材料，其包括掺杂的Ge-Sb基材料，其特征在于，所述掺杂的Ge-Sb基材料的化学通式为M x(Ge iSb j) 100-x； A phase change material comprising a doped Ge-Sb-based material, characterized in that the general chemical formula of the doped Ge-Sb-based material is M x (Ge i Sb j ) 100-x ;
    其中，M为掺杂元素，所述M为C、N、O、Sn中的至少一种；Wherein, M is a doping element, and the M is at least one of C, N, O, and Sn;
    其中，x代表M的原子个数百分比，0＜x≤30，i、j代表Ge、Sb元素的原子个数百分比，0＜i≤50，i+j＝100；Among them, x represents the atomic percentage of M, 0<x≤30, i and j represent the atomic percentage of Ge and Sb elements, 0<i≤50, i+j=100;
    其中，所述M原子存在于Ge-Sb晶界中，从而阻碍Ge-Sb基材料结晶使其内部形成非均一相结构。Wherein, the M atoms exist in the Ge-Sb grain boundary, thereby hindering the crystallization of the Ge-Sb-based material to form a heterogeneous phase structure inside.
  2. 根据权利要求1所述的相变材料，其特征在于，所述掺杂的Ge-Sb基材料的M x(Ge iSb j) 100-x化学通式中，X的优选范围为10＜x≤20。 The phase change material according to claim 1, wherein in the general chemical formula of M x (Ge i Sb j ) 100-x of the doped Ge-Sb-based material, the preferred range of X is 10<x ≤20.
  3. 根据权利要求1所述的相变材料，其特征在于，所述掺杂的Ge-Sb基材料的M x(Ge iSb j) 100-x化学通式中，i与j的优选范围为10＜i≤20，70≤j＜95，i+j＝100。 The phase change material according to claim 1, wherein in the general chemical formula of M x (Ge i Sb j ) 100-x of the doped Ge-Sb-based material, the preferred range of i and j is 10 <i≤20, 70≤j<95, i+j=100.
  4. 根据权利要求1所述的相变材料，其特征在于，所述掺杂的Ge-Sb基材料内部形成的非均一相结构中，非晶相和晶相成分比例的调节方式为脉冲激励或激光激励中至少一种。The phase change material according to claim 1, characterized in that, in the heterogeneous phase structure formed inside the doped Ge-Sb-based material, the composition ratio of the amorphous phase and the crystal phase is adjusted by pulse excitation or laser At least one of the incentives.
  5. 根据权利要求1所述的相变材料，其特征在于，所述掺杂的Ge-Sb基材料可在亚稳高阻态和亚稳低阻态之间转换；其中，所述亚稳高阻态电阻至少是亚稳低阻态电阻的100倍。The phase change material according to claim 1, wherein the doped Ge-Sb-based material can switch between a metastable high resistance state and a metastable low resistance state; wherein the metastable high resistance The state resistance is at least 100 times the metastable low resistance state resistance.
  6. 根据权利要求1所述的相变材料，其特征在于，所述掺杂的Ge-Sb基材料采用磁控溅射法、化学气相沉积法、原子层沉积法、电镀法或电子束蒸发法中的方法制备得到。The phase change material according to claim 1, wherein the doped Ge-Sb-based material adopts magnetron sputtering, chemical vapor deposition, atomic layer deposition, electroplating, or electron beam evaporation. The method is prepared.
  7. 根据权利要求6所述的相变材料，其特征在于，其采用磁控溅射法制备得到，包括：当所述M为C或Sn元素时，The phase change material according to claim 6, characterized in that it is prepared by magnetron sputtering method, comprising: when the M is C or Sn element,
    在惰性气体的氛围下，采用Ge、Sb和M三个单质靶共溅射；或In an inert gas atmosphere, three elemental targets of Ge, Sb and M are used for co-sputtering; or
    在惰性气体的氛围下，采用Ge iSb j合金靶与M单质靶共溅射。 In an inert gas atmosphere, a Ge i Sb j alloy target and an M elemental target are used for co-sputtering.
  8. 根据权利要求6所述的相变材料，其特征在于，其采用磁控溅射法制备得到，包括：当所述M为O或N元素时，The phase change material according to claim 6, characterized in that it is prepared by magnetron sputtering method, comprising: when the M is O or N element,
    在O 2或N 2气体的氛围下，采用Ge、Sb两个单质靶共溅射；或 In an atmosphere of O 2 or N 2 gas, two elemental targets of Ge and Sb are used for co-sputtering; or
    在O 2或N 2气体的氛围下，采用Ge iSb j合金靶溅射。 In an atmosphere of O 2 or N 2 gas, a Ge i Sb j alloy target is used for sputtering.
  9. 一种相变存储单元，其特征在于，包括：依次设置于衬底上的底电极、隔离层、相变薄膜以及顶电极，所述顶电极与所述相变薄膜接触；A phase change memory cell, characterized by comprising: a bottom electrode, an isolation layer, a phase change film and a top electrode which are sequentially arranged on a substrate, the top electrode being in contact with the phase change film;
    其中，所述相变薄膜的材质为权利要求1-8任一项所述的相变材料。Wherein, the material of the phase change film is the phase change material according to any one of claims 1-8.
  10. 根据权利要求9所述的相变存储单元，其特征在于，所述相变薄膜的厚度为20-150nm。9. The phase change memory cell of claim 9, wherein the thickness of the phase change film is 20-150 nm.
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