CN111640861B - Single-layer zinc-tin-antimony film with multistage phase change effect and preparation method and application thereof - Google Patents
Single-layer zinc-tin-antimony film with multistage phase change effect and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a single-layer zinc-tin-antimony film with a multilevel phase change effect, a preparation method and application thereof 4 Two targets of SiO 2 the/Si (100) is taken as a substrate and is prepared by co-sputtering in an argon environment by controlling Zn and SnSb 4 The sputtering time of the target is used for regulating and controlling the content of doped Zn in the Zn-Sn-Sn film, the content of Zn is set to be between 40 and 50 percent, and the total thickness of the film is controlled to be between 40 and 60nm. Compared with the existing phase change storage material, the single-layer zinc-tin-antimony novel phase change storage material PCRAM device can realize two crystallization (SET) processes in operation, and the storage density of a unit area of the film is improved.
Description
Technical Field
The invention relates to the technical field of microelectronic materials and preparation thereof, in particular to a high-storage-density single-layer Zn-Sn-Sb nano thin film material with a multilevel phase change effect, and a preparation method and application thereof.
Background
In recent years, with the annual increase of the import of integrated circuits, the integrated circuits have become the first major imported goods in China, and memories play more and more important roles as core components of the integrated circuits. Among them, the phase change memory is considered as one of the most promising three resistance transition materials because of its advantages of fast read speed, long cycle life, large storage density, low power consumption, and strong embeddable function (g.i. meijer: science,2008, p.1625).
Wherein, ge 2 Sb 2 Te 5 (GST) shows good comprehensive performance and is widely applied to the field of phase change storage. However, its disadvantages of low thermal stability, slow phase transition speed and low storage density limit its further development. Therefore, researchers have made great efforts to improve the performance of phase change memory materials and have made great breakthroughs in improving stability and phase transition speed, such as the W-GeTe system developed by c.peng et al, phase change temperature (T) c ) Increased to over 300 ℃ and corresponding ten-year data retention (T) ten ) 225 ℃ (C.Peng, F.Rao, et al.acta Materialia,2014, p 49); ti-Sb developed by M.Zhu et al (M.Zhu, M.Xia, et al. Nature Communications,2014, p 4086.) 2 Te 3 The system and Sc-Sb prepared by F.Rao et al (F.Rao, K.Ding, et.al.science,2014, p 204303) 2 Te 3 The phase transition speed of the system can reach picosecond magnitude; but is slow in increasing storage density.
At present, researchers mainly realize the multilevel phase change effect by preparing the nano composite multilayer film, and improve the storage density of the film per unit area, such as the nano composite multilayer film (Z.F.He, W.H.Wu, et al.materials Letters,2016, p 399) prepared by GST and ZnSb, and Ga 30 Sb 70 With SnSe 2 Nanocomposite multilayer films (X.Y.Feng, Y.F.Hu, et al. Journal of Applied Physics,2014, p 49) and the like. However, the operability of the multilayer thin film device is severely restricted by the defects of lattice mismatch property, large stress and the like existing among the nano composite multilayer thin film films. Based on the method, the single-layer film can realize the multi-stage phase change effect by adopting an atom doping mode, and the storage density of the unit area of the film is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-storage-density single-layer Zn-Sn-Sb nano film material with a multilevel phase change effect, and a preparation method and application thereof. The preparation method of the material is simple and easy to operate, the resistance of the film is obviously changed twice along with the precipitation of the crystallization phase of the prepared material, the multilevel phase change effect is realized, and the Zn-Sn-Sb film with high storage density is obtained.
The method mainly comprises the steps that the film can realize the first obvious difference (the first phase change is 140-160 ℃) in resistance due to the formation of the SnSb phase by controlling the doping content of Zn, then the resistance realizes the second obvious change (the second phase change is 220-230 ℃) due to the formation of the ZnSb phase along with the further rise of the annealing temperature, and finally the Zn-Sn-Sb film can realize the multi-stage phase change effect, so that the storage density of the film in unit area can be fully improved by the material prepared by the method.
The purpose of the invention can be realized by the following technical scheme:
a process for preparing single-layer Zn-Sn-Sb film with multi-stage phase-change effect from Zn and SnSb 4 Performing magnetron sputtering on a substrate in an argon environment to prepare the single-layer Zn-Sn-Sb film for sputtering a target material.
Furthermore, the content of Zn element in the film is between 40 and 50 percent.
Further, the gas flow of argon during magnetron sputtering is 25-35SCCM; optimally 30SCCM; the sputtering pressure is 0.15-0.25Pa; most preferably 0.2Pa.
Further, zn and SnSb 4 The direct current power supply is adopted when the target material is sputtered, and the sputtering power is 15-25W, and the optimal sputtering power is 20W.
Furthermore, the thickness of the film is 40-60nm.
Further, zn and SnSb 4 The purity of the target material is more than 99.999 percent.
Furthermore, the vacuum degree is higher than 2 multiplied by 10 during magnetron sputtering -4 Pa and the purity of argon is more than 99.999 percent.
Further, the substrate material comprises: siO 2 2 /Si(100)。
The film thickness of the invention is SnSb 4 Controlling the sputtering time of the target material; the doping content of Zn element is controlled by the sputtering time of Zn target.
Further, snSb 4 The sputtering time of the target is 20-145 s; most preferably 29s; the sputtering time of the Zn target is not more than 65s; optimally 56s;
the invention also provides a single-layer zinc-tin-antimony film with the multilevel phase change effect prepared by the method and application of the Zn-Sn-Sb film in a phase change memory.
The zinc-tin-antimony (Zn-Sn-Sb) film finally prepared by the invention is Zn 4 SnSb 4 . The film can generate obvious two-time phase change process in the operation process of the PCRAM device.
Compared with the Zn-Sn-Sb film which is not doped with Zn, the Zn-Sn-Sb film of the invention 4 The thin film has higher storage density; compared with the multilayer nano composite film with the multilevel phase change effect, the multilayer nano composite film has more stable device characteristics.
The preparation method of the Zn-Sn-Sb film disclosed by the invention particularly preferably comprises the following steps of:
1. mixing SiO 2 Cutting a Si (100) substrate into proper sizes, and carrying out ultrasonic cleaning in absolute alcohol to remove dust, organic and inorganic impurities;
2. installing target material and substrate to be sputtered in the cavity of sputtering instrument, closing the cavity, and pumping the pressure in the cavity to 2 × 10 -4 Setting parameters such as power, gas flow, sputtering pressure and the like below Pa;
3. obtaining Zn-Sn-Sb film by means of co-sputtering, sputtering for a certain time according to the set thickness and the doping proportion, and closing SnSb after the sputtering is finished 4 And a DC power supply for the Zn target.
Compared with the traditional phase change material, the Zn-Sn-Sb film prepared by the invention has the advantages that the operation of the PCRAM device generates obvious two-time phase change processes, and the storage density in an effective unit of the film is increased. In addition, lower device crystallization (SET, 0.5V/0.7V) and amorphization (RESET, 1.5V) operating voltages also indicate lower PCRAM operating power consumption of the film.
Drawings
FIG. 1 shows SnSb 4 The resistance (R) changes with the temperature (T) after the film is doped with Zn atoms with different contents (R-T): (a) Undoped SnSb 4 Film, (b) a small amount of Zn-doped ZnSnSb 4 Film, (c) Zn doped with proper amount of Zn 4 SnSb 4 Film, (d) excess Zn-doped Zn 6 SnSb 4 A film.
FIG. 2 shows Zn 4 SnSb 4 XRD curves of the films after different annealing temperatures (150 ℃ and 300 ℃).
FIG. 3 is Zn 4 SnSb 4 Thin film and comparative multilayer thin film [ Sb ] 50 Se 50 (5nm)/Ga 30 Sb 70 (10nm)] 3 And [ Ga ] 30 Sb 70 (25nm)/SnSe 2 (25nm)] 1 Current-resistance (I-V), resistance-voltage (R-V) characteristics of the PCRAM device cellThe curve: (a) Zn 4 SnSb 4 I-V and R-V curves of the film, (b) [ Sb ] 50 Se 50 (5nm)/Ga 30 Sb 70 (10nm)] 3 I-V and R-V curves of the film, (c) [ Ga ] 30 Sb 70 (25nm)/SnSe 2 (25nm)] 1 I-V and R-V curves of the film.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The embodiments of the present invention are specifically described below by specific examples, and other advantages and characteristics of the phase change material of the present invention can be easily understood by those skilled in the art from the description of the present invention. The invention may be embodied or carried out in various other ways, and its several details may be modified and varied in many ways without departing from the spirit and scope of the invention.
Example 1
Zn prepared in this example 4 SnSb 4 The Zn content of the film is about 45 percent, and the total thickness is about 50nm.
1. Cleaning SiO 2 Si (100) substrate:
(a) Putting the substrate into deionized water, and ultrasonically cleaning for 20 minutes to remove dust particles on the surface of the substrate;
(b) Placing the substrate in absolute ethyl alcohol, and ultrasonically cleaning for 20 minutes to remove dust particles and inorganic impurities on the surface of the substrate;
(c) Repeating step (b) three more times;
(d) Taking out the substrate, and drying the substrate by pure Ar gas for later use.
2. Sputtering of Zn 4 SnSb 4 Preparing a film at the early stage:
(a) SnSb 4 And Zn sputtering target material are respectively placed on the target position No. 1,2, the processed substrate is fixed on a sample table, and a sealed vacuum chamber is closed;
(b) Starting the mechanical pump, preheating the molecular pump for 5min, starting the molecular pump when the vacuum reaches 5Pa or below, and vacuumizing to 2 × 10 -4 Pa or less.
(c) Setting SnSb 4 The sputtering power of the Zn target and the sputtering power of the Zn target are both 20W.
(d) Argon gas (sputtering gas) was introduced, the flow rate was set at 30SCCM, and the sputtering pressure was 0.2Pa.
3. Coating with a coating monitoring program, wherein the required sputtering thickness is 50nm, and the required sputtering thickness can be SnSb 4 The sputtering time of the target material is changed, wherein SnSb 4 The sputtering rate of the target was 20s/7nm, the sputtering time was 29s, the sputtering rate of the Zn target was 7s/5nm, and the sputtering time was 56s.
Comparative example 1
Single layer non-Zn doped SnSb prepared in this comparative example 4 And the total thickness of the phase change film is 50nm.
1. Cleaning SiO 2 Si (100) substrate:
(a) Putting the substrate into deionized water, and ultrasonically cleaning for 20 minutes to remove dust particles on the surface of the substrate;
(b) Placing the substrate in absolute ethyl alcohol, and ultrasonically cleaning for 20 minutes to remove dust particles and inorganic impurities on the surface of the substrate;
(c) Repeating step (b) three more times;
(d) Taking out the substrate, and drying the substrate by pure Ar gas for later use.
2. Sputtered Snb 4 Preparing a film at an earlier stage:
(a) Will Snb 4 Placing the target material on the No. 1 target position, fixing the processed substrate on a sample table, and closing the sealed vacuum chamber;
(b) Starting the mechanical pump, preheating the molecular pump for 5min, starting the molecular pump when the vacuum reaches 5Pa or below, and vacuumizing to 2 × 10 -4 Pa or less.
(c) The DC power was set to 20W.
(d) Argon gas (sputtering gas) was introduced at a flow rate of 30SCCM and a sputtering gas pressure of 0.2Pa.
3. Coating with a coating monitoring program, wherein the required sputtering thickness is 50nm and can be changed by sputtering time, and SnSb 4 Sputtering the target material by using a direct current power supply, wherein the sputtering speed is 7nm/20s, the sputtering time is set to 143s according to the set thickness, and after the sputtering is finished, closing SnSb 4 A direct current power supply.
Comparative example 2
Zn lightly doped ZnSnSb prepared in this comparative example 4 The phase change film has Zn content of about 18% and total thickness of 50nm.
1. Cleaning SiO 2 Si (100) substrate:
(a) Placing the substrate in deionized water, and ultrasonically cleaning for 20 minutes to remove dust particles on the surface of the substrate;
(b) Placing the substrate in absolute ethyl alcohol, and ultrasonically cleaning for 20 minutes to remove dust particles and inorganic impurities on the surface of the substrate;
(c) Repeating step (b) three more times;
(d) Taking out the substrate, and drying the substrate by pure Ar gas for later use.
2. Sputtering ZnSnSb 4 Early preparation of the phase change film:
(a) SnSb 4 And Zn target materials are respectively placed on the No. 1 target position and the No. 2 target position, the processed substrate is fixed on a sample table, and a sealed vacuum chamber is closed;
(b) Starting the mechanical pump, preheating the molecular pump for 5min, starting the molecular pump when the vacuum reaches 5Pa or below, and vacuumizing to 2 × 10 -4 Pa or less.
(c) The sputtering power was set to 20W.
(d) Argon gas (sputtering gas) was introduced, the flow rate was set at 30SCCM, and the sputtering pressure was 0.2Pa.
3. The required sputtering thickness of 50nm can be changed by sputtering time by using a coating monitoring program to coat, wherein SnSb 4 The direct current sputtering speed of the target material is 7nm/20s, the required sputtering time is 72s, the direct current sputtering speed of the Zn target material is 5nm/7s, the required sputtering time is 35s, and after the direct current sputtering speed is finished, the SnSb is closed 4 And a Zn target DC power supply.
Comparative example 3
Zn over-doped Zn prepared in this comparative example 6 SnSb 4 The phase change film has Zn content of about 55% and total thickness of 50nm.
1. Cleaning SiO 2 a/Si (100) substrate:
(a) Putting the substrate into deionized water, and ultrasonically cleaning for 20 minutes to remove dust particles on the surface of the substrate;
(b) Placing the substrate in absolute ethyl alcohol, and ultrasonically cleaning for 20 minutes to remove dust particles and inorganic impurities on the surface of the substrate;
(c) Repeating step (b) three more times;
(d) Taking out the substrate, and drying the substrate by pure Ar gas for later use.
2. Sputtering of Zn 6 SnSb 4 Early preparation of the phase change film:
(a) SnSb 4 And Zn target materials are respectively placed on the No. 1 target position and the No. 2 target position, the processed substrate is fixed on a sample table, and a sealed vacuum chamber is closed;
(b) Starting the mechanical pump, preheating the molecular pump for 5min, starting the molecular pump when the vacuum reaches 5Pa or below, and vacuumizing to 2 × 10 -4 Pa or less.
(c) The sputtering power was set to 20W.
(d) Argon gas (sputtering gas) was introduced, the flow rate was set at 30SCCM, and the sputtering pressure was 0.2Pa.
3. The required sputtering thickness of 50nm can be changed by sputtering time by using a coating monitoring program to coat, wherein SnSb 4 The direct current sputtering speed of the target material is 7nm/20s, the required sputtering time is 21s, the direct current sputtering speed of the Zn target material is 5nm/7s, the required sputtering time is 60s, and after the completion, the SnSb is closed 4 And a Zn target DC power supply.
Zn described in example 1 and comparative example 1, comparative example 2 and comparative example 3 4 SnSb 4 、SnSb 4 、ZnSnSb 4 And Zn 6 SnSb 4 Testing the phase change film to obtain a resistance variation relation curve along with temperature, as shown in figure 1; for Zn with multi-stage phase change effect 4 SnSb 4 XRD (X-ray diffraction) tests of the phase-change film at different annealing temperatures are carried out to obtain the crystal phase composition of the film in different states, as shown in figure 2; to the above Zn 4 SnSb 4 Phase change thin film and comparative example multilayer thin film [ Sb ] 50 Se 50 (5nm)/Ga 30 Sb 70 (10nm)] 3 And [ Ga 30 Sb 70 (25nm)/SnSe 2 (25nm)] 1 Performing deviceThe test results show that I-V and R-V characteristic curves are obtained, as shown in FIG. 3.
The results of the above-described assays of FIGS. 1-3 are as follows:
FIG. 1 is a comparative film SnSb 4 、ZnSnSb 4 、Zn 6 SnSb 4 And Zn in the invention 4 SnSb 4 The resistance of the phase-change film changes with the temperature at a heating rate of 10 ℃/min (R-T curve). As can be seen from the figure, snSb not doped with Zn atoms 4 Film and ZnSnSb doped with small amount of Zn atoms 4 The R-T curves of the films all show a single phase change process; and Zn doped with an appropriate amount of Zn atoms 4 SnSb 4 The phase-change film has two obvious phase-change processes, the best performance is achieved on the improvement of storage density, and Zn is doped with Zn atoms 6 SnSb 4 The phase change film has no obvious phase change process.
FIG. 2 shows Zn of the present invention 4 SnSb 4 XRD curves of the phase-change film at different crystallization temperatures. As can be seen from the figure, zn 4 SnSb 4 Annealing the phase-change film at a lower temperature (150 ℃) to generate Sb and SnSb two phases, and forming Sb, snSb and ZnSb three phases after complete crystallization, which shows that Zn 4 SnSb 4 The first phase change process of the phase change film corresponds to the generation of an SnSb phase, and the second phase change process corresponds to the generation of a ZnSb phase.
FIG. 3 (a) is Zn 4 SnSb 4 I-V, R-V characteristic curve of PCRAM device cell of phase change thin film, and device operation characteristics (b) [ Sb ] of comparative multilayer thin film 50 Se 50 (5nm)/Ga 30 Sb 70 (10nm)] 3 (Y.F.Hu,X.Y.Feng,S.M.Li,et.al.Applied Physics Letters,2013,p 152107)、(c)[Ga 30 Sb 70 (25nm)/SnSe 2 (25nm)] 1 (X.Y.Feng, Y.F.Hu, J.W.ZHai, et.al.journal of Applied Physics,2014, p 204303). Zn can be seen by I-V and R-V curves 4 SnSb 4 The phase-change film can form complete SET and RESET operation processes under the action of 50ns pulse. And [ Sb ] having a multilayer thin-film structure 50 Se 50 (5nm)/Ga 30 Sb 70 (10nm)] 3 Thin film and [ Ga 30 Sb 70 (25nm)/SnSe 2 (25nm)] 1 The thin film can only complete part of the PCRAM device operation (RESET or SET). In addition, zn enhanced in the present invention 4 SnSb 4 SET voltage of the phase-change film is 0.8V and 1.4V, RESET voltage is 2.3V, and resistance after crystallization is 10 4 -10 5 Ω, according to the notations P = V 2 and/R, the material has very low phase change storage power consumption.
The combination of FIGS. 1-3 shows Zn 4 SnSb 4 The phase change film has the multi-stage phase change effect, the storage density of the film in unit area is increased, the film also has the characteristics of lower power consumption and the like, and the description shows that Zn 4 SnSb 4 The phase change film has better comprehensive characteristics.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes be accomplished by those skilled in the art without departing from the spirit and technical concepts disclosed in the present invention, and it is intended to cover the appended claims.
Claims (9)
1. The preparation method of the single-layer zinc-tin-antimony film with the multilevel phase change effect is characterized in that Zn and SnSb are used 4 The single-layer Zn-Sn-Sb film is prepared by carrying out magnetron sputtering on a substrate in an argon atmosphere for sputtering a target material, wherein the Zn element content in the film is between 40 and 50 percent.
2. The method according to claim 1, wherein a gas flow rate of argon gas in magnetron sputtering is 25 to 35SCCM; the sputtering pressure is 0.15-0.25Pa.
3. The method according to claim 1, wherein Zn and SnSb are present 4 The sputtering power of the target material is 15-25W by adopting a direct current power supply.
4. According to claim 1The preparation method is characterized in that SnSb 4 The sputtering time of the target is 20 s-145 s; the sputtering time of the Zn target is not more than 65 s.
5. The method according to claim 1, wherein the film has a thickness of 40 to 60nm.
6. The method according to claim 1, wherein Zn and SnSb are present 4 The purity of the target material is more than 99.999 percent; vacuum degree higher than 2 x 10 during magnetron sputtering -4 Pa and the purity of argon is more than 99.999 percent.
7. The method of claim 1, wherein the substrate material comprises: siO 2 2 /Si(100)。
8. A single-layer zinc-tin-antimony film with a multi-stage phase transition effect prepared by the method of any one of claims 1 to 7.
9. The use of a single layer zinc-tin-antimony film with a multilevel phase transition effect as claimed in claim 8, wherein the zinc-tin-antimony film is used in a phase change memory.
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CN104328326A (en) * | 2014-09-17 | 2015-02-04 | 宁波大学 | Zn-Sb-Se phase-change memory thin-film material for phase change memory |
CN109585649A (en) * | 2018-10-30 | 2019-04-05 | 同济大学 | Class superlattices germanium antimony/zinc antimony nano phase change film and its preparation and application |
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CN104328326A (en) * | 2014-09-17 | 2015-02-04 | 宁波大学 | Zn-Sb-Se phase-change memory thin-film material for phase change memory |
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