CN108823530B - Composite phase-change film material (Si/Ge)2Sb2Te5/Si）nPreparation method of (1) - Google Patents
Composite phase-change film material (Si/Ge)2Sb2Te5/Si）nPreparation method of (1) Download PDFInfo
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- 238000013329 compounding Methods 0.000 claims description 3
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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
- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a composite phase change film material (Si/Ge)2Sb2Te5/Si）nThe film material is prepared by 10 groups of Si/Ge by a magnetron sputtering method2Sb2Te5Each group of composite film units comprises two layers of Si nano films and one layer of Ge2Sb2Te5And (3) a nano film. The composite phase change film material utilizes Si-Ge2Sb2Te5The interface effect and the stress regulate and control the phase change characteristic, the used Si nano film has relatively high thermal expansion coefficient, and the Si nano film can be used for regulating Ge in the temperature rise process2Sb2Te5Providing a tensile stress in Ge2Sb2Te5The contraction of the structure is hindered during phase change, so that the Ge can be obviously regulated2Sb2Te5The phase transition temperature and the phase transition rate can realize the regulation and control of crystallization temperature, crystallization rate, thermal stability and data retention, and can regulate and control crystalline resistance.
Description
The invention provides a composite phase change thin film material (Si/Ge) with the name of 201510923584.4 as application number and 2015, 12 and 14 as application date2Sb2Te5/Si）nAnd process for its preparationThe divisional application of (1).
Technical Field
The invention relates to a phase-change film material in the technical field of microelectronics, in particular to a composite phase-change film material (Si/Ge)2Sb2Te5/Si）nThe preparation method of (1).
Background
With the global extension and popularization of multimedia computer networks, the development and research of storage media are receiving more and more attention. Ge (germanium) oxide2Sb2Te5GST is the most well-studied and mature phase change material, and is very suitable for commercial memories. However, Ge2Sb2Te5There are still many defects or deficiencies to be solved, and their low crystallization temperature and poor thermal stability make GST data retention unsatisfactory, and there are many places to be improved and improved (Loke, d. et al, Science, 2012,336 (6088): 1566). For example, Ge2Sb2Te5The crystallization temperature of the film is only about 160 ℃, the data can be maintained for 10 years only at the ambient temperature of 85 ℃, and secondly, Ge2Sb2Te5The crystallization mechanism of the film mainly based on nucleation leads the phase change speed of the film to be slower, and can not meet the information storage requirement of the future high-speed and big data era. These problems hinder further industrialization thereof.
People to Ge2Sb2Te5Various optimization methods are proposed, for example by doping other elements or in two Ge layers2Sb2Te5Other thin film layers are inserted between the two layers for modification.
Regarding the way of doping other elements, chinese patent document CN 101109056B (application No. 200710042918.2) discloses an Al-doped phase-change thin film material Alx（Ge2Sb2Te5）100-xWherein x is more than 0 and less than or equal to 5, and a magnetron sputtering coating system is used for preparing the metal aluminum target material and Ge2Sb2Te5The target material is respectively arranged in a magnetic control direct current sputtering target and a magnetic control radio frequency sputtering targetAnd (4) annealing to realize the phase change of the film in each temperature zone.
With regard to Ge in two layers2Sb2Te5Chinese patent document CN 102832340B (application number 201210335211.1) discloses a phase change memory unit, which comprises a Ge-Sb-Te phase change material layer, wherein a plurality of antimony thin films which are crystallized from the phase change material layer to the phase change material layer are inserted in the Ge-Sb-Te phase change material layer; the preparation method comprises the steps of 1) depositing a Ge-Sb-Te phase-change material layer on a prepared heating electrode substrate; 2) depositing an antimony film on the Ge-Sb-Te phase-change material layer; 3) depositing another Ge-Sb-Te phase-change material layer on the antimony thin film; 4) repeating the steps 2) to 3) n times, wherein n is an integer.
Disclosure of Invention
The invention aims to solve the technical problem of providing a composite phase change film material (Si/Ge) with controllable phase change rate and thermal stability for a phase change memory2Sb2Te5/Si）nThe preparation method of (1).
The technical scheme for realizing the aim of the invention is a composite phase change film material (Si/Ge)2Sb2Te5/Si）nThe composite phase-change film material is prepared from 10 groups of Si/Ge2Sb2Te5Each group of composite film units comprises two layers of Si nano films and one layer of Ge2Sb2Te5Nano thin film of Ge2Sb2Te5The surfaces of the two sides of the film are completely coated by the Si film; two adjacent groups of Si/Ge2Sb2Te5the/Si composite film unit shares one layer of Si film.
The composite phase-change film material (Si/Ge) with the composition2Sb2Te5/Si）nThe thickness of the Si nano-film is 5nm, Ge2Sb2Te5The thickness of the nano film is 5 nm.
The preparation method comprises the following steps:
preparing a substrate, and cleaning and drying the substrate for later use.
Preparing the magnetron sputtering, namely preparing the magnetron sputtering,putting the substrate to be sputtered cleaned in the step I on a base, and putting Si and Ge2Sb2Te5The sputtering target materials are respectively arranged in a magnetron radio frequency sputtering target, a sputtering chamber of a magnetron sputtering coating system is vacuumized, and high-purity argon is used as a sputtering gas.
(iii) preparation of [ Si (x)/Ge by magnetron sputtering2Sb2Te5（x）/Si（x）] nCleaning the Si target and Ge in the multilayer composite film2Sb2Te5After the surface of the target material is cleaned, the substrate to be sputtered is rotated to a Si target position, and a Si thin film layer is obtained after sputtering is finished; after the Si film layer is sputtered, the substrate sputtered with the Si film layer is rotated to Ge2Sb2Te5Target position, obtaining Ge after sputtering2Sb2Te5A thin film layer; repeating the sputtering of the Si layer and Ge2Sb2Te5Layer manipulation n-1 times, followed by a layer of Ge on the outermost surface2Sb2Te5Sputtering a layer of Si film on the film to obtain [ Si (x)/Ge ]2Sb2Te5（x）/Si（x）] nAnd compounding the phase change film material.
In the third step, the sputtering rate of the Si layer is 0.46nm/s, the sputtering time is 11s, and Ge is2Sb2Te5The layer sputtering rate was 0.4nm/s and the sputtering time was 13 s.
The invention has the positive effects that: the composite phase change thin film material (Si/Ge) of the invention2Sb2Te5/Si）nFrom n groups of Si/Ge2Sb2Te5Each group of composite film units comprises two layers of Si nano films and one layer of Ge2Sb2Te5Nano thin film of Ge2Sb2Te5The surfaces of the two sides of the film are completely coated by the Si film; two adjacent groups of Si/Ge2Sb2Te5the/Si composite film unit shares a layer of Si film; or the composite phase-change film material contains n layers of Ge2Sb2Te5Thin film, each layer of Ge2Sb2Te5Of filmsBoth sides are completely covered by a layer of Si film.
Conventional Ge2Sb2Te5The phase-change material has the characteristics of low thermal expansion coefficient and easy deformation, and undergoes slow thermal expansion after temperature rise, and then severe structural phase change occurs near a phase-change temperature (about 160 ℃) and is accompanied by a sharp volume shrinkage effect.
The composite phase change thin film material (Si/Ge) of the invention2Sb2Te5/Si）nHas amorphous and polycrystalline structure, and has independent Si phase and Ge2Sb2Te5Phase (1); the composite phase-change film material can realize reversible amorphous and polycrystalline structure phase change under the condition of providing energy (or heating) externally, and can generate reversible high-resistance and low-resistance state change.
The composite phase change thin film material (Si/Ge) of the invention2Sb2Te5/Si）nUsing Si-Ge2Sb2Te5The interface effect and the stress regulate and control the phase change characteristic, the used Si nano film has relatively high thermal expansion coefficient, and the Si nano film can be used for regulating Ge in the temperature rise process2Sb2Te5Providing a tensile stress in Ge2Sb2Te5The contraction of the structure is hindered during phase change, so that the Ge can be obviously regulated2Sb2Te5The phase change temperature and the phase change rate of the composite phase change film material are improved, so that the composite phase change film material is prepared from Si/Ge2Sb2Te5The existence of interface effect, and Si and Ge in the process of temperature rise and phase change2Sb2Te5The mismatch of the coefficients of thermal expansion leads to stress effects at the interface that appear different from Ge2Sb2Te5The phase transition temperature and the phase transition rate have excellent, reliable and controllable phase transition performance, can realize the regulation and control of crystallization temperature, crystallization rate, thermal stability and data retention, and can regulate and control crystalline resistance.
Drawings
FIG. 1 shows a composite phase change thin film material (Si/Ge) according to the present invention2Sb2Te5/Si）nStructural example ofAn intent;
FIG. 2 is a graph of resistance versus temperature for the composite phase change film material of example 1 at different temperature rise rates;
FIG. 3 is a graph of resistance versus temperature for composite phase change film materials of the present invention at different thicknesses;
FIG. 4 shows the activation energy of the composite phase change film material of the present invention at different thicknesses;
FIG. 5 is a graph of data retention for composite phase change film materials of the present invention at different thicknesses;
FIG. 6 shows Raman characteristics of the composite phase-change thin film material of the present invention at different thicknesses;
the reference numbers in the above figures are as follows: substrate 1, Si Nanoflim 2, Ge2Sb2Te5A nano-film 3.
Detailed Description
(example 1)
Referring to FIG. 1, the composite phase change thin film material (Si/Ge) of the present embodiment2Sb2Te5/Si）nFor multilayer film structures, from n groups of Si/Ge2Sb2Te5Each group of composite film units comprises two layers of Si nano films 2 (Si films for short) and one layer of Ge2Sb2Te5Nano-film 3 (hereinafter referred to as Ge)2Sb2Te5Thin film), Ge2Sb2Te5The two side surfaces of the film 3 are completely coated by the Si film 2; two adjacent groups of Si/Ge2Sb2Te5the/Si composite film unit shares a layer of Si film 2; or the composite phase-change film material contains n layers of Ge2Sb2Te5Film 3, each layer of Ge2Sb2Te5Both sides of the film 3 are completely covered by a layer of Si film 2.
Composite phase-change film material (Si/Ge)2Sb2Te5/Si）nAll Si nano-film 2 thickness and all Ge2Sb2Te5The thickness of the nano-film 3 is the same, the thickness of the Si nano-film 2 is 2 nm-10 nm, Ge2Sb2Te5The thickness of the nano film 3 is 2 nm-10 nm. Si content in Si nano film 2 is more than 99.999 percent, Ge2Sb2Te5Ge in nano-film 32Sb2Te5The content is more than 99.999 percent.
The composite phase-change film material (Si/Ge)2Sb2Te5/Si）nThe film structure of (a) is represented by the general formula [ Si (x)/Ge2Sb2Te5（x）/Si（x）] nWherein x is a single layer of Si thin film and Ge2Sb2Te5The thickness of the film is 2 nm-10 nm, x is more than or equal to 2nm, and n is Si/Ge2Sb2Te5The number of groups of the/Si composite thin film units, and n is a positive integer.
Composite phase change thin film material (Si/Ge) of the present example2Sb2Te5/Si）nIs [ Si (10 nm)/Ge ]2Sb2Te5（10nm）/Si（10nm）]10Using Si and Ge2Sb2Te5As a target material, the material is prepared by alternate sputtering.
The preparation method comprises the following steps:
preparation of a substrate. Selecting SiO with the size of 5mm multiplied by 5mm2Firstly, ultrasonically cleaning a substrate 1 in acetone (with the purity of more than 99%) for 3-5 minutes in an ultrasonic cleaning machine, and taking out the substrate and washing the substrate with deionized water after the cleaning is finished; then, ultrasonically cleaning the substrate in ethanol (the purity is more than 99%) for 3-5 minutes in an ultrasonic cleaning machine, taking out the substrate after cleaning, washing the substrate with deionized water, and then washing the substrate with high-purity N2Drying the surface and the back; and (3) conveying the dried substrate into an oven to dry water vapor, wherein the temperature of the oven is set to be 120 ℃, and the drying time is 20 minutes.
Preparing magnetron sputtering.
In a magnetron sputtering coating system (JGP-450 type), SiO to be sputtered prepared in the step (r)2the/Si (100) substrate is placed on a base, and Si (99.999 atomic%) and Ge are added2Sb2Te5The alloy (purity 99.999%) is respectively arranged on the magnetic control as the sputtering target materialIn a Radio Frequency (RF) sputtering target, a sputtering chamber of a magnetron sputtering coating system is vacuumized until the vacuum degree in the chamber reaches 1 multiplied by 10-4 Pa。
High-purity argon gas (up to 99.999% by volume) is used as a sputtering gas, the flow rate of the Ar gas is set to 25 to 35SCCM (30 SCCM in the present embodiment), and the sputtering gas pressure is adjusted to 0.15 to 0.4Pa (0.4 Pa in the present embodiment).
The sputtering power of the RF power source is set to 25W to 35W (30W in this embodiment).
③ preparing composite phase-change film material [ Si (x)/Ge ] by magnetron sputtering2Sb2Te5（x）/Si（x）] n。
Firstly, cleaning the surfaces of the Si target and the Sb target. Rotating the hollow base support to a Si target position, turning on a direct current power supply on the Si target position, setting sputtering time to be 100s, starting sputtering the surface of the Si target material, and cleaning the surface of the Si target material; after the surface of the Si target material is cleaned, the hollow base support is directly rotated to Ge without turning off a direct current power supply on the Si target material2Sb2Te5Target site, turn on Ge2Sb2Te5Setting the sputtering time for 100s by the radio frequency power supply on the target position, and starting to process Ge2Sb2Te5Sputtering the surface of the target material to clean Ge2Sb2Te5Surface of target material, Ge2Sb2Te5After the surface of the target material is cleaned, SiO to be sputtered2the/Si (100) substrate is rotated to the Si target.
Then sputtering of the first set of Si/Ge is started2Sb2Te5Si thin film of the/Si composite thin film unit: the sputtering rate of the Si layer is 0.46nm/s during sputtering, the sputtering time is 22s, and a Si thin film with the thickness of 10nm is obtained after the sputtering is finished.
After the Si film sputtering is finished, the substrate sputtered with the Si film is rotated to Ge2Sb2Te5Target site, set Ge2Sb2Te5The layer sputtering rate is 0.4nm/s, the sputtering time is 25s, and Ge with the thickness of 10nm is obtained after the sputtering is finished2Sb2Te5A film.
In alreadySputtering a Si film and a Ge film2Sb2Te5Repeating the sputtering of the Si layer and Ge layer on the substrate2Sb2Te5Layer operations 9 times, followed by a layer of Ge on the outermost surface2Sb2Te5Sputtering a layer of Si film on the film to obtain [ Si (10 nm)/Ge ]2Sb2Te5（10nm）/Si（10nm）]10And compounding the phase change film material.
By controlling Si and Ge for a certain number of cycles of the film with a fixed total thickness2Sb2Te5The sputtering time of the target material is used for adjusting Si and Ge in the film period2Sb2Te5The thickness of the single-layer film, thereby forming the phase-change film material with the required structure.
(example 2)
Composite phase change thin film material (Si/Ge) of the present example2Sb2Te5/Si）nIs [ Si (8 nm)/Ge ]2Sb2Te5（8nm）/Si（8nm）]10。
The preparation process is otherwise the same as in example 1, except that: step three, preparing [ Si (8 nm)/Ge ] by magnetron sputtering2Sb2Te5（8nm）/Si（8nm）]10In the case of a multilayer composite film, the sputtering time of each Si film layer was 17 seconds, and each Ge film layer was2Sb2Te5The sputtering time of the film was 20 seconds.
(example 3)
Composite phase change thin film material (Si/Ge) of the present example2Sb2Te5/Si）nIs [ Si (6 nm)/Ge ]2Sb2Te5（6nm）/Si（6nm）]10。
The preparation process is otherwise the same as in example 1, except that: step three, preparing [ Si (6 nm)/Ge ] by magnetron sputtering2Sb2Te5（6nm）/Si（6nm）]10In the case of a multilayer composite film, the sputtering time of each layer of Si film is 13s, and each layer of Ge film2Sb2Te5The sputtering time of the film was 15 s.
(example 4)
Composite phase change thin film material (Si/Ge) of the present example2Sb2Te5/Si）nIs [ Si (5 nm)/Ge ]2Sb2Te5（5nm）/Si（5nm）]10。
The preparation process is otherwise the same as in example 1, except that: step three, preparing [ Si (5 nm)/Ge ] by magnetron sputtering2Sb2Te5（5nm）/Si（5nm）]10In the case of a multilayer composite film, the sputtering time of each layer of Si film is 11s, and each layer of Ge2Sb2Te5The sputtering time of the film was 13 s.
(Experimental example)
In order to understand the composite phase change thin film material (Si/Ge) of the present invention2Sb2Te5/Si）nThe composite phase-change film materials prepared in the examples were tested.
(1) For the composite phase change thin film material [ Si (10 nm)/Ge ] prepared in example 12Sb2Te5（10nm）/Si（10nm）]10The temperature and resistance relationships at different heating rates of 10 ℃/min, 25 ℃/min, 30 ℃/min and 40 ℃/min were tested, see fig. 2, and the curve of the resistance-temperature relationship shows that the faster the heating rate, the higher the phase transition temperature of the composite phase change film material of example 1.
The same experiment was also performed on the composite phase change film materials of examples 2 to 4, and similarly, the faster the temperature increase rate, the higher the phase change temperature of the composite phase change film materials of each example.
(2) The temperature and resistance relationship of the composite phase-change thin film materials of examples 1 to 4 was tested at a temperature rise rate of 25 ℃/min, see fig. 3, along with the Si nano-film 2 and Ge in the composite phase-change thin film material2Sb2Te5The thickness of the film 3 is reduced, and the phase change temperature is gradually increased; the phase change temperature of the composite phase change film material can be gradually regulated and controlled to be increased, so that the thermal stability of the phase change material is improved. In addition, the resistance after crystallization also gradually occursAnd (4) changing.
(3) The composite phase change film materials of examples 1 to 4 were tested for activation energy, and as shown in fig. 4, the activation energy of the material of example 1 was 1.94eV, the activation energy of the material of example 2 was 2.06eV, the activation energy of the material of example 3 was 2.24eV, and the activation energy of the material of example 4 was 2.51eV, as measured by the Si nano-film 2 and Ge in the composite phase change film material2Sb2Te5The activation energy becomes larger as the thickness of the film 3 is reduced; the activation energy of the material can be regulated and controlled by changing the thickness of each layer in the material; and the material corresponding to the high phase transition temperature has high activation energy.
(4) The composite phase change film materials of examples 1 to 4 were tested for data retention and, referring to fig. 5, the material of example 1 retained data for 10 years at an ambient temperature of 56 c, the material of example 2 retained data for 10 years at an ambient temperature of 73.3 c, the material of example 3 retained data for 10 years at an ambient temperature of 87.5 c, and the material of example 4 retained data for 10 years at an ambient temperature of 106.8 c. It can be seen that materials with high activation energy simultaneously have high data retention.
(5) The composite phase change thin film materials of examples 1 to 4 were tested for Raman characteristics. It can be seen that with Si nano-film and Ge2Sb2Te5The change of the thickness of the nano film and the regular change of the Raman scattering peak show that the lattice vibration mode of the film is gradually modulated by the interface effect and the stress, thereby changing the Ge of the storage layer2Sb2Te5Electrical and thermal properties of the composition.
Claims (1)
1. Composite phase-change film material (Si/Ge)2Sb2Te5/Si）nCharacterized in that the composite phase change thin film material (Si/Ge)2Sb2Te5/Si）nFrom 10 groups of Si/Ge2Sb2Te5Each group of composite film units comprises two layers of Si nano films and one layer of Ge2Sb2Te5Nano thin film of Ge2Sb2Te5Of filmsThe surfaces of both sides are completely coated by a Si film; two adjacent groups of Si/Ge2Sb2Te5the/Si composite film unit shares a layer of Si film; composite phase-change film material (Si/Ge)2Sb2Te5/Si）nThe thickness of the Si nano-film is 5nm, Ge2Sb2Te5The thickness of the nano film is 5 nm; the preparation method comprises the following steps:
firstly, preparing a substrate, namely cleaning and drying the substrate for later use;
preparing magnetron sputtering, namely placing the substrate to be sputtered cleaned in the step I on a base support, and placing Si and Ge2Sb2Te5The sputtering target materials are respectively arranged in a magnetron radio frequency sputtering target, a sputtering chamber of a magnetron sputtering coating system is vacuumized, and high-purity argon is used as sputtering gas;
(iii) preparation of [ Si (x)/Ge by magnetron sputtering2Sb2Te5（x）/Si（x）] nCleaning the Si target and Ge in the multilayer composite film2Sb2Te5After the surface of the target material is cleaned, rotating the substrate to be sputtered to a Si target position, wherein the sputtering rate of the Si layer is 0.46nm/s, the sputtering time is 11s, and obtaining a Si thin film layer after the sputtering is finished; after the Si film layer is sputtered, the substrate sputtered with the Si film layer is rotated to Ge2Sb2Te5Target site, Ge2Sb2Te5The layer sputtering rate is 0.4nm/s, the sputtering time is 13s, and Ge is obtained after the sputtering is finished2Sb2Te5A thin film layer; repeating the sputtering of the Si layer and Ge2Sb2Te5Layer operations 9 times, followed by a layer of Ge on the outermost surface2Sb2Te5Sputtering a layer of Si film on the film to obtain [ Si (x)/Ge ]2Sb2Te5（x）/Si（x）] nAnd compounding the phase change film material.
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| Phase-change behavior in Si/Sb80Te20 nanocomposite multilayer films;Wang, Changzhou etal.;《APPLIED PHYSICS A - MATERIALS SCIENCE & PROCESSING》;20100814;第103卷(第1期);第193-198页 * |
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