CN114744110A - Compound doped Ge-Sb-Te phase-change material based on lattice matching and phase-change memory - Google Patents
Compound doped Ge-Sb-Te phase-change material based on lattice matching and phase-change memory Download PDFInfo
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Abstract
The invention provides a lattice matching based compound doped Ge-Sb-Te phase-change material and a phase-change memory, belonging to the technical field of micro-nano electronics and having a chemical formula of (MA)x(Ge‑Sb‑Te)1‑xWherein, MA is a high-melting-point compound with a face-centered cubic structure, the melting point of the high-melting-point compound is more than 900K, the high-melting-point compound MA with the face-centered cubic structure is matched with the crystal lattice of a Ge-Sb-Te system, x represents the percentage of the number of molecules of the compound with the face-centered cubic structure in the total number of molecules, and 0<x<10% of the MA comprises one or more of SrS, CaSe, CaS, ScN, ScBi, TiN and HfN. The invention also provides a phase change memory comprising the phase change material. The phase-change material can simultaneously improve the erasing speed and the cycle performance of the phase-change memory, improve the stability of the device and finally realize the improvement of the comprehensive performance of the device in all directions.
Description
Technical Field
The invention belongs to the technical field of micro-nano electronics, and particularly relates to a compound doped Ge-Sb-Te phase-change material based on lattice matching and a phase-change memory.
Background
In the age of rapid development of electronic technology and information industry, along with the explosive growth of data, the performance requirements of people on nonvolatile memories are higher and higher. Phase Change Memories (PCMs) are considered by the international semiconductor industry association as the most likely future mainstream memories to replace flash and dynamic memories by virtue of their advantages of high integration, fast response speed, long cycle life, and low power consumption.
The basic principle of the phase change memory is that an electric pulse signal is applied to a memory cell to enable the phase change material to generate reversible phase change between an amorphous state and a crystalline state so as to realize the storage of '0' and '1'. An electric pulse with narrow pulse width and high amplitude is applied to the unit to carry out RESET operation on the unit, and the crystalline phase change memory material is melted and quickly cooled to be converted into an amorphous disordered state, so that quick resistance change from a low resistance state '0' to a high resistance state '1' is realized. On the contrary, an electric pulse with wide pulse width and low amplitude is applied to the phase change unit to carry out SET operation on the phase change unit, the amorphous phase change memory material is crystallized through a similar annealing process and returns to a low resistance state, and the 1 erasing and writing back 0 is realized.
The optimization of the performance of the phase-change material is the key for improving the performance of the phase-change memory, and the microstructure of the phase-change material determines the macroscopic characteristics of the phase-change memory. Researches find that the reliability and the cyclic erasing and writing characteristics of the phase change memory are mainly related to an internal atom migration mechanism of the phase change material in the repeated heating and cooling processes. The data retention time of a phase change memory is mainly determined by the amorphous stability of the phase change material. The erasing speed of the phase change memory is mainly determined by the crystallization speed of the phase change material.
The phase-change material is mainly a chalcogenide compound material, wherein a compound consisting of three elements of Ge, Sb and Te is the most common. The Ge-Sb-Te system is a phase change material that has attracted much attention in recent years, and combines the advantages of the Sb-Te system and the Ge-Te system, but the phase change memory device based on the Ge-Sb-Te system has poor cycle performance and the phase change speed cannot meet the application in the memory level memory, and the like, and therefore, the cycle performance and the erase/write speed of the phase change memory device based on the Ge-Sb-Te system need to be further improved.
At present, the main performance optimization means for the Ge-Sb-Te system phase-change material is doping. Other elements are introduced into the Ge-Sb-Te system phase-change material to form different microstructures, and the local characteristics of the phase-change material are changed, so that the performance of the phase-change memory device is improved. The existing Ge-Sb-Te system doping mechanism for improving the performance of the Ge-Sb-Te system mainly comprises that doping single elements (such as N, Sc, Al, Ti and the like) form bonds with one or more elements in the Ge-Sb-Te system, the crystallization process of the Ge-Sb-Te system is locally regulated and controlled, and the amorphous stability of the Ge-Sb-Te system material and the performance of a device are improved. The doping mode has simple process, but the doped single element is generally combined with a certain element in the substrate phase-change material to form a bond, so that the original component of the phase-change material is changed, the lattice structure of the phase-change material is damaged, the crystallization speed is sacrificed to a certain extent while the high resistance stability of the device is improved, and the comprehensive improvement of the performance of the device is difficult to realize.
Therefore, a novel method for modifying a Ge-Sb-Te system is required to be developed to realize precise, sensitive and simple regulation and control of the microstructure of the device, so that the performance of the device is comprehensively improved, and the device can be applied as a commercial phase-change storage material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a Ge-Sb-Te phase change material doped compound based on lattice matching and a phase change memory, and through the doping of a stable face-centered cubic structure compound based on lattice matching, crystallization is accelerated, and the integrity of the lattice structure of the phase change material is ensured, so that the cycle performance of the device is improved, the grain size is reduced, the atom migration of phase change elements is prevented, the stability of the device is improved, and finally the comprehensive performance of the device is improved in all directions.
In order to achieve the aim, the invention provides a compound doped Ge-Sb-Te phase-change material based on lattice matching, which has the chemical formula (MA)x(Ge-Sb-Te)1-xWherein, MA is a high melting point compound with a face-centered cubic structure, the melting point of the high melting point compound is higher than that of the Ge-Sb-Te phase-change material, the melting point is higher than 900K, the high melting point compound MA with the face-centered cubic structure is in lattice matching with a Ge-Sb-Te system, x represents the percentage of the number of molecules of the compound with the face-centered cubic structure in the total number of molecules, and 0<x<10% of the MA comprises one or more of SrS, CaSe, CaS, ScN, ScBi, TiN and HfN.
Furthermore, the high-melting-point compound MA with the face-centered cubic structure forms a stable nucleation point on the Ge-Sb-Te system phase change layer, and is used as a crystallization template of a Ge-Sb-Te system in the crystallization process, so that the crystallization of the Ge-Sb-Te system can be accelerated.
Furthermore, the M element and the A element in the high-melting-point compound MA with the face-centered cubic structure and the elements in the Ge-Sb-Te system phase-change material are independent of each other, and are not bonded, substituted or gap-doped, so that the lattice structure of the phase-change material can be ensured to be complete, and the cycle performance of the device can be improved finally.
Furthermore, the high-melting-point compound MA with the face-centered cubic structure is uniformly distributed at the crystal boundary of the crystalline Ge-Sb-Te system phase-change material in an amorphous form, and can be used for reducing the grain size of the Ge-Sb-Te system phase-change material, hindering the atomic migration of phase-change elements and finally improving the reliability of devices.
Further, the Ge-Sb-Te system phase-change material comprises Ge2Sb2Te5、Ge1Sb2Te4And Ge1Sb4Te7One or more of.
Further, the material is prepared by a magnetron sputtering method, a chemical vapor deposition method, an atomic layer deposition method, an electroplating method or/and an electron beam evaporation method.
And further, the material is prepared by adopting a Ge-Sb-Te system target and MA target co-sputtering mode.
According to the second aspect of the present invention, there is also provided a phase change memory of a phase change material, which comprises a bottom electrode, an isolation layer, a phase change memory material thin film layer and a top electrode, which are sequentially stacked, wherein the phase change memory material thin film layer is doped with a Ge-Sb-Te phase change material based on a lattice matching compound as described above.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
in the phase-change material doped with the stable face-centered cubic structure compound based on lattice matching, the compound MA forms stable nucleation points on a phase-change layer of a Ge-Sb-Te system, so that a template is provided for crystallization of an amorphous Ge-Sb-Te system, and crystallization of the amorphous Ge-Sb-Te system is accelerated; the chemical bond energy of the compound MA is large, the compound MA hardly forms bonds with elements in the Ge-Sb-Te system material in the thin film material, only M-A, M-M and A-A bonds are formed, displacement or gap doping is not generated, the completeness of the lattice structure of the Ge-Sb-Te system phase change material is ensured, and the cycle performance of the device is improved; in addition, the compound MA is uniformly distributed at the grain boundary of the Ge-Sb-Te system in an amorphous form, so that the grain size is effectively reduced, the atomic migration of phase change elements is hindered, and the reliability of the device is improved, thereby comprehensively improving the comprehensive performance of the device.
Drawings
FIG. 1 is a schematic atomic structure diagram of a doped cubic compound of the present invention stably existing in a Ge-Sb-Te matrix material.
Fig. 2 is a flow chart of a phase change memory preparation method of a lattice-matching-based stable face-centered cubic compound doped Ge-Sb-Te system phase change material according to embodiment 2 of the present invention.
Fig. 3 is a graph of R-V measurements at a fixed pulse width of 8ns for two different devices in example 4 and comparative example 1.
FIG. 4 is a graph based on TiN-Ge in example 41Sb4Te7A cycle characteristic test chart of the phase-change memory device of (1) at a fixed pulse width of 20 ns.
FIG. 5 is a graph based on pure Ge in comparative example 11Sb4Te7A cycle characteristic test chart of the phase-change memory device of (1) at a fixed pulse width of 20 ns.
FIG. 6 is a schematic structural position diagram after atoms in a phase-change material model of a stable face-centered cubic structure compound doped Ge-Sb-Te system based on lattice matching move for 60ps at a temperature of 600K by utilizing a first principle.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention relates to an information memory, in particular to a novel Ge-Sb-Te system phase-change material doped with a stable face-centered cubic structure compound based on lattice matching and having high rapid cycle performance and a phase-change memory. The method relates to a doping process of a stable face-centered cubic structure compound with lattice matching, wherein a Ge-Sb-Te system phase change material is regulated and controlled by utilizing a compound structure, stable nucleation points are formed on a Ge-Sb-Te system phase change layer by doping the stable face-centered cubic structure compound with lattice matching, and a reliable crystallization template is provided by the face-centered cubic structure matched with the Ge-Sb-Te system lattice, so that the crystallization of Ge-Sb-Te is accelerated; elements in the stable face-centered cubic structure compound hardly form bonds with elements in the Ge-Sb-Te system phase-change material, so that displacement or gap doping is avoided, the lattice structure of the phase-change material is ensured to be complete, and the cycle performance of a device is improved; in addition, the stable face-centered cubic structure compound is easy to be uniformly distributed at the crystal boundary of the crystalline phase change material in an amorphous form, so that the grain size is reduced, the atom migration of phase change elements is prevented, the stability of the device is improved, and finally the comprehensive performance of the device is improved in an all-round manner.
FIG. 1 is a schematic diagram of the atomic structure of the doped cubic compound in the Ge-Sb-Te matrix material, and it can be known that the cubic compound forms stable nucleation points, and the face-centered cubic structure matched with the Ge-Sb-Te system provides a reliable crystallization template to accelerate the crystallization of Ge-Sb-Te. The invention relates to a phase-change material obtained by introducing a lattice-matched stable face-centered cubic structure compound MA into a Ge-Sb-Te system phase-change material, and the general formula of the chemical composition of the phase-change material is (MA)x(Ge-Sb-Te)1-xWherein MA is a stable face-centered cubic structure compound with lattice matching, x represents the percentage of high-melting-point compound molecules in the total molecules, and the preferable value range of x is 0<x<More preferably, x is 5%. The value of x can be regulated and controlled by adjusting the sputtering power of MA during preparation. Preferably, (MA)x(Ge-Sb-Te)1-xThe thickness of the phase-change film material is 10 nm-300 nm.
In one embodiment of the invention, the phase change memory unit sequentially comprises a bottom electrode, an isolation layer, a phase change material film layer and a top electrode. The phase change material thin film layer is made of the Ge-Sb-Te phase change material doped with the stable face-centered cubic structure compound based on lattice matching, and is filled in small holes with the diameter of 250nm and the depth of 100 nm. The bottom electrode is made of TiN. The isolation layer is made of SiO2. The top electrode is made of metal Pt.
The invention also provides a preparation method of the Ge-Sb-Te system phase-change material doped with the lattice-matched stable face-centered cubic structure compound for the phase-change memory, and the preparation method comprises a magnetron sputtering method, a chemical vapor deposition method, an atomic layer deposition method, an electroplating method, an electron beam evaporation method and the like. The preparation of the magnetron sputtering method is most flexible, the Ge-Sb-Te system target and the MA target can be adopted for co-sputtering, and the method can prepare the Ge-Sb-Te system phase-change material doped with the lattice-matched stable face-centered cubic structure compound according to the proportion of the chemical general formula.
The lattice-matched Ge-Sb-Te system phase-change storage material doped with the compound with the stable face-centered cubic structure and the device have mature preparation process and are easy to realize the compatibility with the prior microelectronic process technology. The phase change material of the Ge-Sb-Te system is regulated and controlled by using a doped compound with a stable face-centered cubic structure matched with the crystal lattice, stable nucleation points are formed on the phase change layer of the Ge-Sb-Te system, and a reliable crystallization template is provided by the face-centered cubic structure matched with the crystal lattice of the Ge-Sb-Te system, so that the crystallization of the Ge-Sb-Te is accelerated; the elements in the stable face-centered cubic structure compound hardly form bonds with the elements in the Ge-Sb-Te system phase-change material, so that displacement or gap doping is avoided, the lattice structure of the phase-change material is ensured to be complete, and the cycle performance of the device can be improved. In addition, the stable face-centered cubic structure compound is easily and uniformly distributed at the crystal boundary of the crystalline phase change material in an amorphous form, the grain size is reduced, the atom migration of phase change elements is prevented, and the stability of the device is improved, so that the comprehensive performance of the Ge-Sb-Te system phase change memory is improved.
To illustrate the methods and materials of the present invention in more detail, further details are provided below in conjunction with more specific examples.
Example 1
Lattice-matched stable face-centered cubic structure compound-doped Ge for phase-change memory device prepared in the present example2Sb2Te5The chemical formula of the phase-change film material is (MA) x (GST)1-x, wherein MA represents SrS, GST represents Ge2Sb2Te5In this embodiment, x is 0.05.
SrS-Ge2Sb2Te5The phase change storage film material is prepared by adopting a magnetron sputtering method. During preparation, high-purity argon is introduced as sputtering gas, the sputtering pressure is 0.5Pa, and Ge is2Sb2Te5The target adopts a direct current power supply, and the power supply power is 30W; the SrS target adopts an alternating current power supply, and the power supply power is 60W. The specific preparation process comprises the following steps:
1. selecting SiO with the size of 1cm multiplied by 1cm2The crystal lattice orientation of the/Si substrate is 100 directions, and the surface and the back are cleaned to remove dust particles, organic impurities and inorganic impurities.
a) Mixing SiO2the/Si (100-direction lattice orientation) substrate was placed in an acetone solution and rinsed with deionized water with ultrasonic vibration at 40W power for 10 minutes.
b) Ultrasonic vibration of the substrate treated by acetone in ethanol solution at 40W power for 10 minutes, washing with deionized water and obtaining high-purity N2And air-drying the surface and the back to obtain the substrate to be sputtered.
2. SrS-Ge is prepared by adopting a direct-current and alternating-current power co-sputtering method2Sb2Te5And (3) phase change storage thin film material.
a) Placing SrS target and Ge2Sb2Te5The alloy target material has a purity of 99.99% (atomic percent), and the background of the alloy target material is vacuumized to 10%-4Pa。
b) High-purity Ar gas is used as sputtering gas, the sputtering pressure is adjusted to 0.5Pa, and the distance between the target and the substrate is 120 mm.
c) The DC power supply was set to 30W and the AC power supply was set to 60W.
d) For SrS target and Ge2Sb2Te5And (5) pre-sputtering the target for 10min, and cleaning the surface of the target.
e) After the pre-sputtering is finished, the baffle is opened, and the thickness of the prepared film is about 100nm when the sputtering time is 6 min.
Example 2
In this embodiment, SrS doped Ge is used2Sb2Te5Phase change film material as phase change layer material for preparing memory device, wherein SrS doped Ge2Sb2Te5The phase change layer is prepared by a magnetron sputtering method. During preparation, high-purity argon is introduced as sputtering gas, the sputtering pressure is 0.5Pa, and Ge is2Sb2Te5The target adopts a direct current power supply, and the power supply power is 30W; the SrS target adopts an alternating current power supply, and the power supply power is 60W. Fig. 2 is a flow chart of a phase change memory manufacturing process of a Ge-Sb-Te system phase change material doped with a stable face-centered cubic compound based on lattice matching according to embodiment 2 of the present invention, and it can be seen that the specific manufacturing process includes the following steps:
1. selecting SiO with the size of 1cm multiplied by 1cm2the/Si (100) substrate is cleaned on the surface and the back surface to remove dust particles, organic and inorganic impurities.
a) Mixing SiO2the/Si (100) substrate was placed in an acetone solution and rinsed with deionized water with ultrasonic vibration at 40W power for 10 minutes.
b) Ultrasonic vibration of the substrate treated by acetone in ethanol solution at 40W power for 10 minutes, washing with deionized water and obtaining high-purity N2And air-drying the surface and the back to obtain the substrate to be sputtered.
2. Preparing a 100nm TiN bottom electrode by a direct-current power sputtering method.
3. By chemical vapour depositionMethod for depositing 100nm SiO on TiN bottom electrode2An insulating layer.
4. SiO by electron beam lithography and the like2The insulating layer formed a via hole having a depth of 100nm and a diameter of 250 nm.
5. The memory array is formed by a photolithography process.
6. Filling SrS-Ge in the through hole by adopting an alternating current power supply sputtering method2Sb2Te5Phase change storage thin film material
a) Placing SrS target and Ge2Sb2Te5The alloy target material has a purity of 99.99% (atomic percent), and the background of the alloy target material is vacuumized to 10%-4Pa。
b) High-purity Ar gas is used as sputtering gas, the sputtering pressure is adjusted to 0.5Pa, and the distance between the target and the substrate is 120 mm.
c) The DC power supply was set to 30W and the AC power supply was set to 60W.
d) For SrS target and Ge2Sb2Te5And (5) pre-sputtering the target for 10min, and cleaning the surface of the target.
e) After the pre-sputtering is finished, the baffle is opened, and the thickness of the prepared phase change layer is about 100nm when the sputtering time is 6 min.
7. Preparing 100nm Pt top electrode by using a direct-current power supply sputtering method to obtain a complete SrS-Ge-based Pt top electrode2Sb2Te5A phase change memory device array of a phase change layer.
Example 3
Lattice-matched stable face-centered cubic structure compound-doped Ge for phase-change memory device prepared in the present example1Sb4Te7The general chemical formula of the phase-change film material is (MA)x(GST)1-xWherein MA represents TiN, GST represents Ge1Sb4Te7In this embodiment, x is 0.05.
TiN-Ge1Sb4Te7The phase change storage film material is prepared by adopting a magnetron sputtering method. During preparation, high-purity argon is introduced as sputtering gas, the sputtering pressure is 0.5Pa, and Ge is1Sb4Te7The target is provided with a direct current power supply,the power of the power supply is 30W. The TiN target adopts a direct current power supply, and the power supply power is 20W. The specific preparation process comprises the following steps:
1. selecting SiO with the size of 1cm multiplied by 1cm2the/Si (100) substrate is cleaned on the surface and the back surface to remove dust particles, organic and inorganic impurities.
a) Mixing SiO2the/Si (100) substrate was placed in an acetone solution and rinsed with deionized water with ultrasonic vibration at 40W power for 10 minutes.
b) Ultrasonic vibration of the substrate treated by acetone in ethanol solution at 40W power for 10 minutes, washing with deionized water and obtaining high-purity N2And (5) air-drying the surface and the back to obtain the substrate to be sputtered.
2. Method for preparing TiN-Ge by adopting direct current and alternating current power supply co-sputtering method1Sb4Te7And (3) phase change storage thin film material.
a) Placing TiN target material and Ge1Sb4Te7The alloy target material has a purity of 99.99% (atomic percent), and the background of the alloy target material is vacuumized to 10%-4Pa。
b) High-purity Ar gas is used as sputtering gas, the sputtering pressure is adjusted to 0.5Pa, and the distance between the target and the substrate is 120 mm.
c) Set Ge1Sb4Te7The power of the direct current power supply of the target material is 30W, and the power of the direct current power supply of the TiN target material is 20W.
d) And carrying out presputtering on the TiN target and the Ge1Sb4Te7 target for 10min, and cleaning the surfaces of the targets.
e) After the pre-sputtering is finished, the baffle is opened, and the thickness of the prepared film is about 100nm when the sputtering time is 6 min.
Example 4
In this example, Ge doped with TiN was used1Sb4Te7The phase change film material is used as a phase change layer material for preparing a memory device, wherein TiN is doped with Ge1Sb4Te7The phase change layer is prepared by a magnetron sputtering method. During preparation, high-purity argon is introduced as sputtering gas, the sputtering pressure is 0.5Pa, and Ge is1Sb4Te7The target adopts a direct current power supply, and the power supply power is 30W; the TiN target adopts a direct current power supply and electricityThe source power was 20W. The specific preparation process comprises the following steps:
1. selecting SiO with the size of 1cm multiplied by 1cm2the/Si (100) substrate is cleaned on the surface and the back surface to remove dust particles, organic and inorganic impurities.
a) Mixing SiO2the/Si (100) substrate was placed in an acetone solution and rinsed with deionized water with ultrasonic vibration at 40W power for 10 minutes.
b) Ultrasonic vibration of the substrate treated by acetone in ethanol solution at 40W power for 10 minutes, washing with deionized water and obtaining high-purity N2And air-drying the surface and the back to obtain the substrate to be sputtered.
2. Preparing a 100nm TiN bottom electrode by a direct-current power sputtering method.
3. Depositing 100nm SiO on TiN bottom electrode by chemical vapor deposition2An insulating layer.
4. On SiO by processes such as electron beam lithography2The insulating layer formed a via hole having a depth of 100nm and a diameter of 250 nm.
5. The memory array is formed by a photolithography process.
6. Filling TiN-Ge in the through hole by adopting an alternating current power supply sputtering method1Sb4Te7Phase change storage thin film material
a) Placing TiN target material and Ge1Sb4Te7The alloy target material has a purity of 99.99% (atomic percent), and the background of the alloy target material is vacuumized to 10%-4Pa。
b) High-purity Ar gas is used as sputtering gas, the sputtering pressure is adjusted to 0.5Pa, and the distance between the target and the substrate is 120 mm.
c) Set Ge1Sb4Te7The power of the direct current power supply of the target material is 30W, and the power of the direct current power supply of the TiN target material is 20W.
d) For TiN target material and Ge1Sb4Te7And (5) pre-sputtering the target for 10min, and cleaning the surface of the target.
e) After the pre-sputtering is finished, the baffle is opened, and the thickness of the prepared phase change layer is about 100nm when the sputtering time is 6 min.
7. Preparation 1 by direct-current power sputtering method00nm Pt top electrode to obtain complete TiN-Ge-based1Sb4Te7A phase change memory device array of a phase change layer.
Comparative example 1
Pure Ge was used in this comparative example1Sb4Te7The phase change film material is used as a phase change layer material to prepare a storage device, wherein pure Ge is adopted1Sb4Te7The phase change layer is prepared by a magnetron sputtering method. During preparation, high-purity argon is introduced as sputtering gas, the sputtering pressure is 0.5Pa, and Ge is1Sb4Te7The target adopts a direct current power supply, and the power supply power is 30W. The specific preparation process comprises the following steps:
1. selecting SiO with the size of 1cm multiplied by 1cm2the/Si (100) substrate is cleaned on the surface and the back surface to remove dust particles, organic and inorganic impurities.
a) Mixing SiO2the/Si (100) substrate was placed in an acetone solution and rinsed with deionized water with ultrasonic vibration at 40W power for 10 minutes.
b) Ultrasonic vibration of the substrate treated by acetone in ethanol solution at 40W power for 10 minutes, washing with deionized water and obtaining high-purity N2And air-drying the surface and the back to obtain the substrate to be sputtered.
2. Preparing a 100nm TiN bottom electrode by a direct-current power sputtering method.
3. Depositing 100nm SiO on TiN bottom electrode by chemical vapor deposition2An insulating layer.
4. On SiO by processes such as electron beam lithography2The insulating layer formed a via hole having a depth of 100nm and a diameter of 250 nm.
5. The memory array is formed by a photolithography process.
6. Filling Ge in the through hole by adopting an alternating current power sputtering method1Sb4Te7And (3) phase change storage thin film material.
a) Well placed Ge1Sb4Te7The alloy target material has a purity of 99.99% (atomic percent), and the background of the alloy target material is vacuumized to 10%-4Pa。
b) High-purity Ar gas is used as sputtering gas, the sputtering pressure is adjusted to 0.5Pa, and the distance between the target and the substrate is 120 mm.
c) Set Ge1Sb4Te7The power of the direct current power supply of the target material is 30W.
d) To Ge1Sb4Te7And (5) pre-sputtering the target for 10min, and cleaning the surface of the target.
e) After the pre-sputtering is finished, the baffle is opened, and the thickness of the prepared phase change layer is about 100nm when the sputtering time is 6 min.
7. The 100nm Pt top electrode is prepared by a direct-current power sputtering method to obtain a complete Ge-based Pt top electrode1Sb4Te7A phase change memory device array of a phase change layer.
The TiN-Ge-based samples of example 4 and comparative example 1 were prepared1Sb4Te7Phase change memory device and pure Ge1Sb4Te7The phase change memory devices are respectively subjected to electrical characteristic tests.
FIG. 3 is a plot of R-V measurements at a fixed pulse width of 8ns for two different devices in example 4 and comparative example 1, reflecting the SET speed performance of the devices, as is evident from the plots based on TiN-Ge1Sb4Te7The phase change memory can be successfully changed from a high resistance value state SET to a low resistance value state under the pulse width of 8 ns; based on pure Ge1Sb4Te7The pulse amplitude of the phase change memory device increased to 2.4V failed the SET device. Illustrating TiN-Ge based on lattice-matched compound doping1Sb4Te7The operation speed of the phase change memory device is greatly improved.
Fig. 4 and 5 are graphs of cycle characteristics of two different devices in example 4 and comparative example 1 at a fixed pulse width of 20 ns. Based on TiN-Ge in FIG. 41Sb4Te7The maximum cycle number of the phase-change memory device is close to E9, while fig. 5 is based on pure Ge1Sb4Te7The maximum cycle number of the phase-change memory device of (2) is 3.5E 6. The stable face-centered cubic structure compound doping is verified to improve the cycle performance of the Ge-Sb-Te system phase-change memory device.
Lattice matching based on Materials Studio softwareCompound doped TiN-Ge1Sb4Te7The phase change storage thin film material is modeled, and the motion condition of atoms in a model at the temperature of 600K is simulated by utilizing a first nature principle. FIG. 6 is a schematic diagram of structural positions of atoms in a phase-change material model of a Ge-Sb-Te system doped with a stable face-centered cubic structure compound based on lattice matching after 60ps of movement at a temperature of 600K by utilizing a first principle, and doped TiN can be found in Ge1Sb4Te7The system still keeps the stable existence of the combination state, and provides a stable structure-matched nucleation point for the system.
In the above examples, SrS and TiN were selected for the high melting point compound MA with a face centered cubic structure, and Ge was selected for the Ge-Sb-Te system phase change material2Sb2Te5And Ge1Sb4Te7In fact, Ge-Sb-Te system phase-change material can also be selected1Sb2Te4The face-centered cubic high-melting-point compound MA can also be one or more of CaSe, CaS, ScN, ScBi and HfN, such as CaSe-Ge1Sb2Te4，CaS-Ge2Sb2Te5，ScN-Ge1Sb4Te7，ScBi-Ge2Sb2Te5And HfN-Ge2Sb2Te5And the like.
Compared with the Ge-Sb-Te system phase-change storage material which is not regulated by the stable face-centered cubic structure compound tissue matched with the crystal lattice in the prior art, in the Ge-Sb-Te system phase-change material doped with the stable face-centered cubic structure compound based on the crystal lattice matching, the Ge-Sb-Te system phase-change material is regulated by utilizing the doped stable face-centered cubic structure compound tissue matched with the crystal lattice, a stable nucleation point is formed on a Ge-Sb-Te system phase-change layer, and the face-centered cubic structure matched with the crystal lattice of the Ge-Sb-Te system provides a reliable template to accelerate crystallization; elements in the stable face-centered cubic structure compound hardly form bonds with elements in the Ge-Sb-Te system phase-change material, so that displacement or gap doping is avoided, the lattice structure of the phase-change material is ensured to be complete, and the cycle performance of a device is improved; in addition, the stable face-centered cubic structure compound is easy to be uniformly distributed at the crystal boundary of the crystalline phase change material in an amorphous form, so that the grain size is reduced, the atom migration of phase change elements is prevented, the stability of the device is improved, and finally the comprehensive performance of the device is improved in an all-round manner.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A compound doped Ge-Sb-Te phase-change material based on lattice matching is characterized in that the chemical formula is (MA)x(Ge-Sb-Te)1-xWherein, MA is a high melting point compound with a face-centered cubic structure, the melting point of the high melting point compound is higher than 900K, the high melting point compound MA with the face-centered cubic structure is in lattice matching with a Ge-Sb-Te system, x represents the percentage of the number of molecules of the high melting point compound with the face-centered cubic structure in the total number of molecules, and 0<x<10% of the MA comprises one or more of SrS, CaSe, CaS, ScN, ScBi, TiN and HfN.
2. The lattice matching based compound doped Ge-Sb-Te phase change material as claimed in claim 1, wherein the high melting point compound MA with a face-centered cubic structure is doped in the Ge-Sb-Te system phase change layer to form a stable nucleation point, and is used as a crystallization template of the Ge-Sb-Te system during crystallization to accelerate the crystallization of the Ge-Sb-Te system.
3. The Ge-Sb-Te phase-change material doped with the compound based on the lattice matching as claimed in claim 1, wherein M element and A element in the high-melting-point compound MA with the face-centered cubic structure are independent of elements in the Ge-Sb-Te system phase-change material, and are free from bonding, displacement and gap doping, so that the complete lattice structure of the phase-change material during crystallization can be ensured, and the cycle performance of the device can be improved finally.
4. The lattice matching based compound doped Ge-Sb-Te phase change material as claimed in one of claims 1 to 3, wherein the high melting point compound MA with a face-centered cubic structure is uniformly distributed in an amorphous form at the grain boundary of the crystalline Ge-Sb-Te system phase change material, and can be used for reducing the grain size of the Ge-Sb-Te system phase change material, hindering the atomic migration of phase change elements and finally improving the reliability of the device.
5. The lattice matching based compound doped Ge-Sb-Te phase change material of claim 4, wherein the Ge-Sb-Te system phase change material is selected from Ge-Sb-Te2Sb2Te5、Ge1Sb2Te4And Ge1Sb4Te7One or more of.
6. The phase-change material doped with Ge-Sb-Te according to claim 5, wherein the phase-change material is prepared by a magnetron sputtering method, a chemical vapor deposition method, an atomic layer deposition method, an electroplating method or/and an electron beam evaporation method.
7. The lattice matching based compound doped Ge-Sb-Te phase change material as claimed in claim 5, wherein the material is prepared by co-sputtering a Ge-Sb-Te system target and an MA target.
8. A phase change memory of a phase change material, which is characterized by comprising a bottom electrode, an isolation layer, a phase change memory material thin film layer and a top electrode which are sequentially stacked, wherein the phase change memory material thin film layer is formed by doping Ge-Sb-Te phase change material based on a lattice matching compound according to any one of claims 1 to 7.
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| PCT/CN2022/093092 WO2023184668A1 (en) | 2022-03-31 | 2022-05-16 | Lattice matching-based compound-doped ge-sb-te phase change material and phase change memory |
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| US5596522A (en) * | 1991-01-18 | 1997-01-21 | Energy Conversion Devices, Inc. | Homogeneous compositions of microcrystalline semiconductor material, semiconductor devices and directly overwritable memory elements fabricated therefrom, and arrays fabricated from the memory elements |
| US5825046A (en) * | 1996-10-28 | 1998-10-20 | Energy Conversion Devices, Inc. | Composite memory material comprising a mixture of phase-change memory material and dielectric material |
| US7501648B2 (en) * | 2006-08-16 | 2009-03-10 | International Business Machines Corporation | Phase change materials and associated memory devices |
| US7491573B1 (en) * | 2008-03-13 | 2009-02-17 | International Business Machines Corporation | Phase change materials for applications that require fast switching and high endurance |
| US8097871B2 (en) * | 2009-04-30 | 2012-01-17 | Macronix International Co., Ltd. | Low operational current phase change memory structures |
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