CN114744109A - Sb-Te phase change material doped with tetrahedral structure compound and phase change memory - Google Patents

Sb-Te phase change material doped with tetrahedral structure compound and phase change memory Download PDF

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CN114744109A
CN114744109A CN202210326791.1A CN202210326791A CN114744109A CN 114744109 A CN114744109 A CN 114744109A CN 202210326791 A CN202210326791 A CN 202210326791A CN 114744109 A CN114744109 A CN 114744109A
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phase change
change material
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程晓敏
曾运韬
李凯
缪向水
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Huazhong University of Science and Technology
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    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of the switching material, e.g. layer deposition
    • H10N70/026—Formation of the switching material, e.g. layer deposition by physical vapor deposition, e.g. sputtering
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/305—Sulfides, selenides, or tellurides

Abstract

The invention provides a tetrahedral-structure compound-doped Sb-Te phase-change material and a phase-change memory, belonging to the technical field of micro-nano electronicsx(Sb‑Te)1‑xMA is a compound having a tetrahedral structure, x represents the percentage of the number of molecules of the compound having a tetrahedral structure to the total number of molecules, 0<x<10% of tetrahedral structure compound is selected from one or more of SiC, SiN and GeC. The invention also provides a phase change memory comprising the Sb-Te phase change material. Sb-T doped with tetrahedral structure compoundThe e phase-change material has better amorphous stability and data retention capacity, does not form a bond with elements in the Sb-Te system phase-change material, can ensure the complete crystal lattice structure of the Sb-Te system phase-change material, can also reduce the grain size, prevents the atom migration of the phase-change elements, and finally realizes the improvement of the comprehensive performance of the device in all directions.

Description

Sb-Te phase change material doped with tetrahedral structure compound and phase change memory
Technical Field
The invention belongs to the technical field of micro-nano electronics, and particularly relates to a stable tetrahedral compound doped Sb-Te phase change material 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 demand of people for nonvolatile memory is 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 memories 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 cell is that an electric pulse signal acts on a device unit to enable the phase change material to generate reversible phase change between an amorphous state and a polycrystalline 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 storage 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 storage material is crystallized through a similar annealing process and returns to a low resistance state, and the 1 erasing and writing back to 0 is realized.
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 Sb-Te system is a phase-change material which is widely concerned in recent years, the crystallization temperature is low, the growth-dominated crystallization process is realized, and the crystallization speed is high, so that the phase-change memory device based on the Sb-Te system has the characteristic of high SET speed. However, the amorphous stability is poor, and the data retention stability of the device needs to be further improved.
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. At present, the main optimization means for improving the stability of the Sb-Te system phase-change material is to introduce a tetrahedral structure by doping, such as doping of fourth main group elements. In an amorphous state, the structure (octahedron) difference between the strongly bonded tetrahedral cluster and the Sb-Te crystal is large, and spontaneous crystallization of the phase-change material is hindered, so that the amorphous stability and the data retention capacity of the phase-change material are improved. However, the incorporation of the single element generally combines with a certain element in the substrate phase-change material to form a bond, so as to change the original composition of the phase-change material and destroy the lattice structure of the phase-change material, thereby sacrificing the crystallization speed to a certain extent while improving the stability of the device, and hardly realizing the overall improvement of the device performance.
Therefore, there is a need to develop a new method and product for modifying Sb-Te material system to achieve precise, sensitive and simple control of its microstructure, so that it can be applied as a commercial phase change memory material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the Sb-Te phase change material and the phase change memory doped with the stable tetrahedral structure compound, and the stable tetrahedral structure compound is doped to form a tetrahedral cluster with larger difference with the octahedral crystal structure in the Sb-Te system phase change layer so as to block spontaneous crystallization of the Sb-Te system phase change material, thereby improving the amorphous stability and the data retention capacity of the Sb-Te system phase change material, not forming bonds with elements in the Sb-Te system phase change material, ensuring the integrity of the lattice structure of the Sb-Te system phase change material, reducing the grain size, preventing atom migration of the phase change element, and finally realizing the improvement of the comprehensive performance of the device in an all-round way.
To achieve the above object, according to one aspect of the present invention, there is also provided a tetrahedral compound doped Sb-Te phase change material having a chemical formula of MAx(Sb-Te)1-xWherein MA is a compound having a tetrahedral structure, x represents the percentage of the number of molecules of the compound having a tetrahedral structure to the total number of molecules, and 0<x<10% of tetrahedral structure compound is selected from one or more of SiC, SiN, GeC, GeN, BN, GaN and the like.
Furthermore, the tetrahedral compound MA has stable structure in the Sb-Te system phase change layer, and the structure is completely different from the structure of the Sb-Te system octahedral crystal, so that the spontaneous crystallization of the Sb-Te system phase change material can be hindered, and the amorphous stability and the data retention capability of the Sb-Te system phase change material are improved.
Furthermore, the MA element of the tetrahedral structure compound and the element in the Sb-Te system phase-change material are mutually independent without bonding and displacement or gap doping phenomenon, thereby ensuring the integrity of the lattice structure of the Sb-Te system phase-change material and keeping the performance of rapid crystallization.
Further, only the following chemical bonds are present, including M-A bonds, M-M bonds, A-A bonds, and Sb-Te bonds.
Furthermore, the tetrahedral structure compound MA is uniformly distributed at the crystal boundary of the crystalline phase change material in an amorphous form, so as to reduce the grain size, hinder the atom migration of the phase change element, and finally improve the reliability of the device.
Further, the material is prepared by a magnetron sputtering method, a chemical vapor deposition method, an atomic layer deposition method, an electroplating method or an electron beam evaporation method.
Furthermore, the Sb-Te system phase-change material comprises SbTe and Sb2Te1、Sb2Te3And Sb4Te1。
Further, the material is obtained by co-sputtering an Sb-Te system target and an MA target.
According to the second aspect of the invention, the phase change memory of the Sb-Te system phase change material 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 made of the Sb-Te phase change material doped with the tetrahedral structure compound.
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 based on the stable tetrahedral structure compound, the stable tetrahedral structure compound MA forms a stable tetrahedral structure in the Sb-Te system phase-change layer, and the difference between the stable tetrahedral structure compound MA and the Sb-Te system octahedral crystal structure is larger, so that the spontaneous crystallization of the Sb-Te system phase-change material is hindered, and the amorphous stability and the data retention capability of the Sb-Te system phase-change material are improved. In addition, the stable chemical bond energy of the tetrahedral compound MA is large, the chemical bond energy hardly forms bonds with elements in the Sb-Te system material in the film material, only M-A, M-M and A-A bonds are formed, displacement or gap doping is not generated, and the completeness of the lattice structure of the Sb-Te system phase-change material can be ensured, so that the performance characteristic of rapid crystallization of the Sb-Te system phase-change material is not influenced. In addition, the stable tetrahedral structure compound MA is easily uniformly distributed at the grain boundary of the crystalline phase change material in an amorphous form, is used for reducing the grain size, hindering the atom migration of phase change elements, improving the reliability of the device and finally improving the comprehensive performance of the device in an all-round way.
Drawings
FIG. 1 is a schematic structural diagram of a tetrahedral compound doped Sb-Te phase change material.
Fig. 2 is a flow chart of a phase change memory based on a stable face-centered cubic compound doped Sb-Te system phase change material according to embodiment 2 of the present invention.
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 Sb-Te system phase-change material based on stable tetrahedron structure compound doping and high thermal stability and a phase-change memory. The stable tetrahedron structure compound doping process is adopted, the Sb-Te system phase-change material is regulated and controlled by utilizing the compound organization, and stable tetrahedron clusters which are different from octahedron crystal structures of the Sb-Te system phase-change materials greatly are formed in the Sb-Te system phase-change layers through the stable tetrahedron structure compound doping, so that the spontaneous crystallization of the Sb-Te system phase-change materials is hindered, and the amorphous stability and the data retention capacity of the Sb-Te system phase-change materials are improved. Elements in the stable tetrahedral structure compound hardly form bonds with elements in the Sb-Te system phase-change material, so that displacement or gap doping is avoided, and the completeness of the lattice structure of the Sb-Te system phase-change material is ensured, so that the performance characteristic of quick crystallization of the Sb-Te system phase-change material is not influenced. In addition, the stable tetrahedral structure compound is easy to be uniformly distributed at the crystal boundary of the crystalline Sb-Te system phase change material in an amorphous form, the grain size is reduced, the atom migration of phase change elements is prevented, the reliability 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 structural diagram of a Sb-Te phase change material doped with a tetrahedral compound, and it can be known from the diagram that the doped tetrahedral compound exists stably in a matrix material, and a stable tetrahedral structure with a larger difference from an octahedral structure of a Sb-Te system crystal can hinder spontaneous crystallization of the Sb-Te system phase change material, thereby improving amorphous stability and data retention capability thereof. The invention introduces stable tetrahedron structure compound MA into Sb-Te system phase-change material to obtain the phase-change material, the general formula of the chemical composition of the phase-change material is MAx(Sb-Te)1-xWherein MA is a stable tetrahedral compound, 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 isx(Sb-Te)1-xThe thickness of the phase-change film material is 50 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 Sb-Te system phase-change material doped based on the stable tetrahedral structure compound, the Sb-Te system phase-change material is filled in small holes with the diameter of 250nm and the depth of 100nm, the bottom electrode is made of TiN, and the isolation layer is made of SiO2The top electrode is made of metal Pt.
The invention provides a stable Sb-Te system phase-change material doped with a tetrahedral structure compound for a phase-change memory, which 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 stable Sb-Te system phase-change material doped with the tetrahedral compound can be prepared according to the proportion of a chemical general formula by the method.
The stable Sb-Te system phase-change storage material doped with the tetrahedral compound and the device have mature preparation process and are easy to realize the compatibility with the prior microelectronic process technology.
In order to illustrate the process of the invention in more detail, further details are given below with reference to more specific examples.
Example 1
The chemical general formula of the Sb-Te system phase-change thin-film material doped with the stable tetrahedral structure compound for the phase-change memory device prepared in the embodiment is MAx(ST)1-xWherein MA represents SiN and ST represents Sb2Te3In this embodiment, x is 0.05.
SiN-Sb2Te3The system 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, the SiN target adopts an alternating current power supply, and the power supply power is 40W; sb2Te3The 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/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. SiN-Sb prepared by adopting direct current and alternating current power co-sputtering method2Te3And (3) phase change storage thin film material.
Placing the SiN target material and Sb2Te3The purity of the target material reaches 99.99 percent (atomic percent), and the background of the target material is vacuumized to 10 percent-5Pa。
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.
Setting the power of an alternating current power supply of the SiN target material to 40W, Sb2Te3The power of the alternating current power supply of the target material is 60W.
For SiN target material and Sb2Te3And (5) pre-sputtering the target for 10min, and cleaning the surface of the target.
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 8 min.
Example 2
Sb doped with SiN in this example2Te3The phase change thin film material is used as a phase change layer material for preparing a memory device, wherein Sb is doped with SiN2Te3The 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, the SiN target adopts an alternating current power supply, the power supply power is 40W, and Sb is2Te3The 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 based on a stable face-centered cubic compound doped Sb-Te system phase change material according to embodiment 2 of the present invention, and it can be seen that a specific preparation 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. 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 SiN-Sb in the through hole by adopting an alternating current power supply sputtering method2Te3Phase change storage thin film material
Placing the SiN target material and Sb2Te3The purity of the target material reaches 99.99 percent (atomic percent), and the background of the target material is vacuumized to 10 percent-5Pa。
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.
Setting the power of an alternating current power supply of the SiN target material to 80W, Sb2Te3The power of the alternating current power supply of the target material is 60W.
For SiN target material and Sb2Te3And (5) pre-sputtering the target for 10min, and cleaning the surface of the target.
And after the pre-sputtering is finished, opening the baffle, and when the sputtering time is 8min, the thickness of the prepared phase change layer is about 100 nm.
7. Preparing 100nm Pt top electrode by using a direct-current power supply sputtering method to obtain complete Pt top electrode based on SiN-Sb2Te3A phase change memory device array includes a system phase change layer.
Example 3
The chemical general formula of the Sb-Te system phase-change thin-film material doped with the stable tetrahedral structure compound for the phase-change memory device prepared in the embodiment is MAx(ST)1-xWherein MA represents GeC, ST represents Sb2Te3In this embodiment, x is 0.04.
GeC-Sb2Te3The system 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, the GeC target adopts an alternating current power supply, and the power supply power is 30W; sb2Te3The 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 1cm2Cleaning the surface and back of a/Si (100) substrate to remove dust particles and organic substancesAnd 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. GeC-Sb prepared by adopting direct-current and alternating-current power co-sputtering method2Te3And (3) phase change storage thin film material.
a) Placing GeC target material and Sb2Te3The purity of the target material reaches 99.99 percent (atomic percent), and the background of the target material is vacuumized to 10 percent-5Pa。
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) Setting the power of an alternating current power supply of the GeC target material to be 30W, Sb2Te3The power of the alternating current power supply of the target material is 60W.
d) For GeC target material and Sb2Te3And (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 8 min.
Example 4
In this example, GeC-doped Sb is used2Te3The phase change thin film material is used as a phase change layer material for preparing a storage device, wherein the GeC is doped with Sb2Te3The 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, the GeC target adopts an alternating current power supply, the power supply power is 30W, and Sb is2Te3The 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/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 is placed in an acetone solution and treated with 40W workUltrasonic vibration at a rate of 10 minutes, rinsing with deionized water.
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. Preparing a 100nm TiN bottom electrode by a direct-current power supply sputtering method.
3. Depositing 100nm SiO on TiN bottom electrode by chemical vapor deposition2An insulating layer.
4. On SiO by electron beam lithography and other processes2The 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 GeC-Sb in the through hole by adopting an alternating current power supply sputtering method2Te3Phase change storage thin film material
a) Placing GeC target material and Sb2Te3The purity of the target material reaches 99.99 percent (atomic percent), and the background of the target material is vacuumized to 10 percent-5Pa。
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) Setting the power of an alternating current power supply of the GeC target material to be 30W, Sb2Te3The power of the alternating current power supply of the target material is 60W.
d) For GeC target material and Sb2Te3And (5) pre-sputtering the target for 10min, and cleaning the surface of the target.
e) And after the pre-sputtering is finished, opening the baffle, and when the sputtering time is 8min, the thickness of the prepared phase change layer is about 100 nm.
7. Preparing a 100nm Pt top electrode by adopting a direct-current power sputtering method to obtain a complete GeC-Sb-based Pt top electrode2Te3A phase change memory device array includes a system phase change layer.
Example 5
The chemical general formula of the Sb-Te system phase-change thin-film material doped with the stable tetrahedral structure compound and prepared in the embodiment is MAx(ST)1-xWherein MA representsGaN, ST stands for Sb4Te1In this embodiment, x is 0.04.
GaN-Sb4Te1The system 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, the GaN target adopts an alternating current power supply, and the power supply power is 32W; sb4Te1The 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/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. GaN-Sb prepared by adopting direct current and alternating current power co-sputtering method4Te1And (3) phase change storage thin film material.
a) Placing the GaN target material and the Sb4Te1The purity of the target material reaches 99.99 percent (atomic percent), and the background of the target material is vacuumized to 10 percent-5Pa。
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) Setting the power of an alternating current power supply of the GaN target material to be 32W, Sb4Te1The power of the alternating current power supply of the target material is 60W.
d) For GaN target material and Sb4Te1And (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 8 min.
Example 6
In this example, Sb doped with GaN was used4Te1The phase-change thin film material is used as a phase-change layer material to prepare a memory device, wherein,GaN-doped Sb4Te1The 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, the GaN target adopts an alternating current power supply, the power supply power is 32W, and Sb is4Te1The 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/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 GeC-Sb in the through hole by adopting an alternating current power supply sputtering method2Te3Phase change storage thin film material
a) Placing the GaN target material and Sb4Te1The purity of the target material reaches 99.99 percent (atomic percent), and the background of the target material is vacuumized to 10 percent-5Pa。
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) Setting the power of an alternating current power supply of the GaN target material as 32W and Sb4Te1The power of the alternating current power supply of the target material is 60W.
d) For GaN target material and Sb4Te1And (5) pre-sputtering the target for 10min, and cleaning the surface of the target.
e) And after the pre-sputtering is finished, opening the baffle, and when the sputtering time is 8min, the thickness of the prepared phase change layer is about 100 nm.
7. Preparing a 100nm Pt top electrode by adopting a direct-current power sputtering method to obtain a complete GaN-Sb-based Pt top electrode4Te1A phase change memory device array includes a system phase change layer.
The chemical formula of the Sb-Te phase-change material doped with the tetrahedral structure compound is MAx(Sb-Te)1-xThe MA can be selected from one or two of SiC and GeN, and the Sb-Te system phase-change material can also be selected from SbTe and Sb2Te1And Sb4Te1. The value range of x can be determined according to the structures of the Sb-Te system phase-change material and the tetrahedral structure compound, 0<x<10％。
In the Sb-Te system phase-change material doped based on the stable tetrahedral structure compound, the Sb-Te system phase-change material is regulated and controlled by using the doped stable tetrahedral structure compound, a stable tetrahedral cluster which has a larger difference with an octahedral crystal structure is formed in the Sb-Te system phase-change layer, and spontaneous crystallization of the Sb-Te system phase-change material is hindered, so that the amorphous stability and the data retention capacity of the Sb-Te system phase-change material are improved; elements in the stable tetrahedral structure compound hardly form bonds with elements in the Sb-Te system phase-change material, so that displacement or gap doping is avoided, and the completeness of the lattice structure of the Sb-Te system phase-change material is ensured, so that the performance characteristic of quick crystallization of the Sb-Te system phase-change material is not influenced; in addition, the stable tetrahedral structure compound is easy to be distributed at the crystal boundary of the crystalline Sb-Te system phase change material in an amorphous form, so that the grain size is reduced, the atom migration of phase change elements is prevented, the reliability 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 (9)

1. Four-layerThe Sb-Te phase-change material doped with the compound with the surface structure is characterized in that the chemical formula is MAx(Sb-Te)1-xWherein MA is a compound having a tetrahedral structure, x represents the percentage of the number of molecules of the compound having a tetrahedral structure to the total number of molecules, and 0<x<10% of tetrahedral structure compound is selected from one or more of SiC, SiN and GeC.
2. The tetrahedron structured compound-doped Sb-Te phase change material as claimed in claim 1, wherein the tetrahedron structured compound MA is in a Sb-Te system phase change layer, has a stable structure, and has a structure different from that of Sb-Te system octahedron crystal, so that spontaneous crystallization of the Sb-Te system phase change material can be inhibited, and thus the amorphous stability and data retention capability of the Sb-Te system phase change material can be improved.
3. The tetrahedron structured compound doped Sb-Te phase change material of claim 1, wherein the MA element of the tetrahedron structured compound and the element of the Sb-Te system phase change material are independent from each other without bonding, displacement or gap doping, thereby ensuring the integrity of the lattice structure of the Sb-Te system phase change material and maintaining the rapid crystallization property.
4. A tetrahedral compound doped Sb-Te phase change material according to claim 3 wherein only the following chemical bonds are present, including M-a bonds, M-M bonds, a-a bonds and Sb-Te bonds.
5. The tetrahedron structured compound doped Sb-Te phase change material of claim 3, wherein the tetrahedron structured compound MA is uniformly distributed in an amorphous form at the grain boundary of the crystalline phase change material for reducing the grain size, hindering the atomic migration of the phase change element, and finally improving the reliability of the device.
6. The tetrahedral structure compound doped Sb-Te phase change material of claim 3, characterized in that it is prepared by magnetron sputtering, chemical vapor deposition, atomic layer deposition, electroplating or electron beam evaporation.
7. A tetrahedral compound doped Sb-Te phase change material according to any one of claims 1 to 6, characterized in that the Sb-Te system phase change material comprises SbTe, Sb2Te1、Sb2Te3And Sb4Te1。
8. The tetrahedral structure compound doped Sb-Te phase change material of claim 7, obtained by co-sputtering a Sb-Te system target and a MA target.
9. A phase change memory of Sb-Te system phase change material, characterized in that it comprises a bottom electrode, an isolation layer, a phase change memory material thin film layer and a top electrode, which are stacked in sequence, the phase change memory material thin film layer is made of Sb-Te phase change material doped with tetrahedral structure compound according to any one of claims 1 to 8.
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