CN113584446A - Metal hafnium film prepared on silicon substrate by utilizing magnetron sputtering, method and application - Google Patents

Metal hafnium film prepared on silicon substrate by utilizing magnetron sputtering, method and application Download PDF

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CN113584446A
CN113584446A CN202110841158.1A CN202110841158A CN113584446A CN 113584446 A CN113584446 A CN 113584446A CN 202110841158 A CN202110841158 A CN 202110841158A CN 113584446 A CN113584446 A CN 113584446A
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hafnium
silicon substrate
magnetron sputtering
sputtering
metal
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魏鸿源
杨少延
魏洁
陈怀浩
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NANJING YOUTIAN METAL TECHNOLOGY CO LTD
Institute of Semiconductors of CAS
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NANJING YOUTIAN METAL TECHNOLOGY CO LTD
Institute of Semiconductors of CAS
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Abstract

A hafnium metal film prepared on a silicon substrate by utilizing magnetron sputtering, a method and application thereof. The method for preparing the hafnium metal film on the silicon substrate by utilizing magnetron sputtering comprises the following steps: loading the silicon substrate and the metal hafnium target material into a growth chamber of magnetron sputtering equipment, and carrying out ultrahigh vacuum high-temperature baking treatment on the silicon substrate; carrying out surface sputtering treatment on the silicon substrate by utilizing a magnetron sputtering reverse sputtering dry cleaning process; preparing a hafnium nitride barrier layer on a silicon substrate by utilizing a magnetron sputtering deposition process; preparing a hafnium metal film on the hafnium nitride barrier layer by utilizing a magnetron sputtering deposition process; and carrying out in-situ vacuum high-temperature annealing treatment on the metal hafnium film, and cooling to room temperature to complete the preparation of the metal hafnium film. The invention realizes the single preferred orientation high crystallization quality preparation of the metal hafnium film on the silicon substrate by utilizing the magnetron sputtering process. The prepared hafnium metal film can be applied to a conductive buffer layer material in the preparation of an ohmic contact metal electrode material or a silicon substrate gallium nitride material heteroepitaxy.

Description

Metal hafnium film prepared on silicon substrate by utilizing magnetron sputtering, method and application
Technical Field
The invention relates to the technical field of semiconductor and thin film material preparation, in particular to a metal hafnium thin film prepared on a silicon substrate by utilizing magnetron sputtering, a method and application.
Background
The transition refractory metals (including titanium (alpha-Ti), zirconium (alpha-Zr) and hafnium (alpha-Hf)) generally have a hexagonal crystal structure, and not only have good thermal and chemical stability, but also have good conductivity and irradiation resistance. In the technical field of semiconductors, particularly silicon-based device processes, transition group refractory metal thin film materials have extremely important application values. Such as: the preparation process of the alpha-Ti film by magnetron sputtering and electron beam evaporation is mature, and is an ohmic contact metal electrode material commonly used in the silicon-based microelectronic device process and the power electronic device process; the alpha-Zr and alpha-Hf thin films have lower resistance, have smaller lattice mismatch and thermal expansion coefficient difference with Si and GaN materials, and are more ideal n-type ohmic contact metal electrode materials in the processes of Si devices and GaN devices. In comparison, the abundance of metallic zirconium on earth is more abundant than that of metallic copper and titanium, and metallic hafnium is symbiotic with metallic zirconium, but the abundance is only 1% -2% of that of metallic zirconium. Although the price of the raw material of the metal hafnium with the same purity is not much different from that of the metal titanium, and the metal hafnium has smaller lattice mismatch and thermal expansion coefficient difference compared with the metal titanium or the metal zirconium and the silicon nitride, the preparation technology of the metal hafnium thin film material is not as mature as the metal titanium and the metal zirconium, and the metal titanium and the metal zirconium can not be replaced and widely applied in the technical field of semiconductors, particularly in the processes of silicon devices and gallium nitride devices.
At present, the chemical vapor deposition processes capable of realizing the preparation of the transition group refractory metal hafnium thin film material mainly include Atomic Layer Deposition (ALD) and Metal Organic Chemical Vapor Deposition (MOCVD), and the physical vapor deposition processes mainly include Ion Beam Epitaxy (IBE) and Magnetron sputtering (Magnetron Sputter). The ALD material has a slow growth speed, and can only grow amorphous or polycrystalline materials with poor crystallization quality due to low growth temperature although a high-purity metal zirconium film with a nanoscale thickness can be prepared. The MOCVD process for preparing and growing the alpha-Hf thin film is still in research and development, and no research result report exists for realizing the single preferred orientation high-crystalline quality growth of the alpha-Hf on the Si substrate. Ion Beam Epitaxy (IBE) process has been used by the semiconductor research institute of Chinese academy of sciences to realize highly single preferred orientation growth of d-Hf thin film, but the ion beam epitaxy process is not suitable for manufacturing devices by using the existing semiconductor device process because of its small film-forming area (2cm × 2 cm). The alpha-Hf thin film prepared by the related magnetron sputtering method cannot realize single preferred orientation and high crystal quality growth of the alpha-Hf thin film on the Si substrate.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a hafnium metal film prepared on a silicon substrate by magnetron sputtering, a method and applications thereof, which aim to at least partially solve at least one of the above mentioned technical problems.
In order to achieve the above object, as a first aspect of the present invention, there is provided a method for preparing a hafnium metal thin film on a silicon substrate by magnetron sputtering, comprising: loading a silicon substrate and a metal hafnium target material into a growth chamber of magnetron sputtering equipment, and carrying out ultrahigh vacuum high-temperature baking treatment on the silicon substrate to remove gas adsorbed on the surface of the silicon substrate, residual impurities and an oxide layer; sputtering the surface of the silicon substrate by using a magnetron sputtering reverse sputtering dry cleaning process to remove impurities and an oxidation layer remained on the surface of the silicon substrate; preparing a hafnium nitride barrier layer on the silicon substrate by utilizing a magnetron sputtering process so as to prevent the surface of the silicon substrate from interfacial intermixing with a subsequently prepared hafnium metal film and realize the preparation and growth of the hafnium metal film; preparing a hafnium metal film on the hafnium nitride barrier layer by utilizing a magnetron sputtering deposition process; carrying out in-situ vacuum high-temperature annealing treatment on the hafnium metal film so as to further improve the crystallization quality of the hafnium metal film and reduce the stress of the hafnium metal film; and reducing the temperature of the metal hafnium film to room temperature to finish the preparation of the metal hafnium film sample.
As a second aspect of the present invention, there is provided a hafnium metal thin film prepared by the above method.
As a third aspect of the invention, the invention also provides an application of the hafnium metal film in preparing a grown conductive buffer layer material in an ohmic contact electrode material or in a silicon substrate gallium nitride material heteroepitaxy.
According to the technical scheme, the metal hafnium film prepared on the silicon substrate by utilizing magnetron sputtering, the method and the application have one or part of the following beneficial effects:
(1) according to the method for preparing the metal hafnium film on the silicon substrate by utilizing magnetron sputtering, ultrahigh vacuum high-temperature baking and magnetron sputtering reverse sputtering dry cleaning are sequentially carried out on the silicon substrate in a growth chamber of magnetron sputtering equipment, so that residual impurities and an oxidation layer on the silicon substrate can be completely removed, and high-density nucleation and high-crystallization-quality film forming growth of the metal hafnium film are facilitated.
(2) According to the method for preparing the metal hafnium film on the silicon substrate by utilizing magnetron sputtering, a hafnium nitride barrier layer is formed on the silicon substrate. The hafnium nitride barrier layer with a certain thickness and good crystallization quality not only provides a good nucleating layer and a template layer for the high crystallization quality growth of the hafnium metal film, but also can avoid the phenomenon that the interface of the silicon substrate surface and the hafnium metal film is mixed to form a hafnium silicon alloy layer which is not beneficial to the high crystallization quality growth of the hafnium metal film due to the direct deposition of the hafnium metal film on the silicon substrate.
(3) The in-situ vacuum high-temperature annealing treatment of the prepared hafnium metal film is beneficial to relieving the crystal lattice damage and the introduced additional compressive stress which often occur in the film prepared by the magnetron sputtering process, further improves the crystallization quality of the hafnium metal film, reduces the film stress and is beneficial to the improvement of the film density and the surface flatness; the method relieves the large thermal mismatch stress accumulated on the film layer in the cooling process by controlling the proper cooling rate, and is more favorable for preparing the hafnium metal film with low stress and high crystallization quality.
Drawings
FIG. 1 is a process flow of preparing a hafnium metal film on a silicon substrate by magnetron sputtering in an embodiment of the present invention;
FIG. 2 is a result of X-ray diffraction (XRD) testing of a sample of hafnium metal film prepared on a silicon substrate by magnetron sputtering in an embodiment of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) cross-sectional morphology test result of a hafnium metal film sample prepared on a silicon substrate by magnetron sputtering in an embodiment of the present invention;
FIG. 4 shows a Scanning Electron Microscope (SEM) surface morphology test result of a sample of a hafnium metal film prepared on a silicon substrate by magnetron sputtering in an embodiment of the present invention.
Detailed Description
In the process of implementing the invention, it is found that magnetron sputtering is still the main process for preparing the growing metal hafnium (alpha-Hf) film, but most of the existing research results either do not favor alpha-Hf nucleation high crystal quality growth because the residual oxide layer on the surface of the Si substrate is not completely removed, or mostly do not realize alpha-Hf film single preferred orientation high crystal quality growth on the Si substrate because the substrate heating temperature is relatively low or the sputtering power is relatively high, for example, the higher growth temperature or the higher sputtering power can also cause the interface intermixing of the surface of the silicon substrate and the metal hafnium film, and a silicon hafnium alloy layer (for example, Hf) which does not favor alpha-Hf high crystal quality growth is formed at the interfacexSiy) Most studies only obtained α -Hf polycrystalline thin films with disordered orientation and large surface undulations (AFM surface Roughness (RMS) higher than 3 nm).
In order to fully utilize the functional characteristics of large film forming area, high growth rate and reverse sputtering dry cleaning of the substrate surface of the silicon substrate of magnetron sputtering, the invention provides a metal hafnium film prepared on the silicon substrate by magnetron sputtering, a method and application thereof. After the growth of the metal hafnium film is finished, in-situ high-temperature annealing treatment is adopted to further improve the crystallization quality of the metal hafnium film and reduce the stress of the film layer.
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
According to an embodiment of the present invention, there is provided a method for preparing a hafnium metal thin film on a silicon substrate by magnetron sputtering, including: loading a silicon substrate and a metal hafnium target material into a growth chamber of magnetron sputtering equipment, and carrying out ultrahigh vacuum high-temperature baking treatment on the silicon substrate to remove residual impurities and an oxidation layer on the silicon substrate; carrying out surface sputtering treatment on the silicon substrate by utilizing a magnetron sputtering reverse sputtering dry cleaning process to remove impurities and an oxidation layer remained on the surface of the silicon substrate; preparing a hafnium nitride barrier layer on a silicon substrate by utilizing a magnetron sputtering process so as to prevent the surface of the silicon substrate from interfacial intermixing with a subsequently prepared hafnium metal film and realize the preparation and growth of the hafnium metal film; preparing a hafnium metal film on the hafnium nitride barrier layer by utilizing a magnetron sputtering deposition process; carrying out in-situ vacuum high-temperature annealing treatment on the hafnium metal film, further improving the crystallization quality of the hafnium metal film and reducing the stress; and reducing the temperature of the hafnium metal film to room temperature to finish the preparation of the hafnium metal film sample.
According to the method for preparing the metal hafnium film on the silicon substrate by utilizing magnetron sputtering, the silicon substrate is sequentially subjected to ultrahigh vacuum high-temperature baking and magnetron sputtering reverse sputtering dry cleaning in a growth chamber of magnetron sputtering equipment, so that impurities and an oxide layer on the silicon substrate are completely removed, and high-density nucleation and high-crystallization-quality film forming growth of the metal hafnium film are facilitated.
According to the method for preparing the metal hafnium film on the silicon substrate by utilizing magnetron sputtering, a hafnium nitride barrier layer is formed on the silicon substrate firstly. The hafnium nitride barrier layer with certain thickness and good crystallization quality not only provides a good nucleating layer and a template layer for the high crystallization quality growth of the metal hafnium film, but also can avoid the phenomenon that the interface between the surface of the silicon substrate and the metal hafnium film is mixed to form a silicon hafnium alloy layer which is not beneficial to the high crystallization quality growth of the metal hafnium film due to the direct deposition of the metal hafnium film on the silicon substrate.
The prepared hafnium metal film is subjected to in-situ vacuum high-temperature annealing treatment, so that the common crystal lattice damage and introduced additional compressive stress of the film prepared by the magnetron sputtering process are relieved, the crystallization quality of the hafnium metal film is further improved, the film stress is reduced, and the film density and the surface flatness are improved; the method relieves the large thermal mismatch stress accumulated on the film layer in the cooling process by controlling the proper cooling rate, and is more favorable for preparing the hafnium metal film with low stress and high crystallization quality.
According to the embodiment of the invention, the step of preparing the hafnium nitride barrier layer on the silicon substrate by utilizing the magnetron sputtering process comprises the following steps: forming a thin metal hafnium layer on the silicon substrate by utilizing a magnetron sputtering deposition process; nitriding the thin metal hafnium layer by utilizing a magnetron sputtering reverse sputtering deposition process to form a thin hafnium nitride nucleating layer; and forming a hafnium nitride layer on the thin hafnium nitride nucleating layer by utilizing a magnetron sputtering reactive sputtering process to finish the preparation of the hafnium nitride barrier layer.
When the hafnium nitride barrier layer is prepared, a thin metal hafnium pre-deposition layer is formed on the silicon substrate, so that the problem that the surface of the silicon substrate is nitrided to form an amorphous silicon nitride layer which is not beneficial to high-density nucleation and continuous film formation of the hafnium nitride barrier layer is avoided.
According to the embodiment of the invention, when the hafnium nitride barrier layer is prepared, the distance between the metal hafnium target and the silicon substrate is 5-8cm, the rotation speed of the silicon substrate is 5-100 revolutions per minute, the temperature of the silicon substrate is 250-750 ℃, the sputtering gas is argon, the reaction gas is nitrogen, and the working pressure in the growth chamber of the magnetron sputtering equipment is 0.1-5 Pa.
According to the embodiment of the invention, the magnetron sputtering deposition process for preparing the thin metal hafnium layer is direct current magnetron sputtering or radio frequency magnetron sputtering, the sputtering power is 20-100W, and the sputtering time is 1-5 minutes.
According to the embodiment of the invention, the magnetron sputtering reverse sputtering power for forming the thin hafnium nitride nucleating layer is 20-100W, the reverse sputtering time is 1-5 minutes, and the reaction gas for nitriding the thin metal hafnium layer is nitrogen.
According to the embodiment of the invention, the magnetron sputtering reactive sputtering process for forming the hafnium nitride layer is direct current magnetron sputtering, the sputtering power is 20-200w, the sputtering time is 2-30 minutes, and the reaction gas is nitrogen.
According to the embodiment of the invention, when the silicon substrate is subjected to the ultrahigh vacuum high-temperature baking treatment, the vacuum degree of the ultrahigh vacuum of the high-temperature baking of the silicon substrate is not higher than 5 x 10 < -5 > Pa. The temperature for heating the silicon substrate by ultrahigh vacuum high temperature baking is 700-850 ℃, and the time for baking the silicon substrate at high temperature is 5-30 minutes.
According to the embodiment of the invention, when the surface sputtering treatment is carried out on the silicon substrate, the distance between the metal hafnium target and the silicon substrate is 5-Scm, the rotation speed of the silicon substrate is 5-100 revolutions per minute, the temperature of the silicon substrate is 250-750 ℃, the introduced sputtering gas is argon, the working pressure in a growth chamber of a magnetron sputtering device is 0.1-5Pa, the magnetron sputtering reverse power is 50-300W, and the reverse sputtering time is 5-30 minutes.
The invention combines the ultrahigh vacuum high temperature baking and the reverse sputtering dry cleaning process, can effectively remove gas and impurities adsorbed on the surface of the silicon substrate and residual oxide layers, and is more beneficial to high-density nucleation and high-crystallization-quality film-forming growth of the hafnium metal film.
According to the embodiment of the invention, when the metal hafnium film is prepared on the hafnium nitride barrier layer, the magnetron sputtering deposition process is radio frequency magnetron sputtering or direct current magnetron sputtering, the sputtering gas is argon, the working pressure in a magnetron sputtering growth chamber is 0.1-5Pa, the sputtering power is 20-150W, the distance between the metal hafnium target and the silicon substrate is 5-8cm, the rotation speed of the silicon substrate is 5-100 revolutions per minute, and the temperature of the silicon substrate is 250-750 ℃.
According to the embodiment of the invention, the temperature for carrying out in-situ vacuum high-temperature annealing treatment on the hafnium metal film is 700-850 ℃, and the cooling speed for cooling to room temperature is 3-30 ℃ per minute.
According to an embodiment of the present invention, the silicon substrate is a silicon single crystal substrate and the crystal orientation is (111), (100), or (113); the silicon substrate has a diameter of at least 1 inch.
According to the embodiment of the invention, the hafnium metal film prepared by the method for preparing the hafnium metal film on the silicon substrate by utilizing magnetron sputtering is also provided.
According to the embodiment of the invention, the application of the hafnium metal film in the preparation of a conductive buffer layer material grown by the heteroepitaxy of an ohmic contact metal electrode material or a silicon substrate gallium nitride material is also provided.
The technical solution of the present invention will be described in detail below with reference to specific examples. It should be noted that the following specific examples are only for illustration and are not intended to limit the invention.
Example 1
Fig. 1 is a process flow of preparing a hafnium metal film on a silicon substrate by magnetron sputtering in an embodiment of the present invention. As shown in fig. 1, the invention discloses a method for preparing a hafnium metal film on a silicon substrate by magnetron sputtering, comprising the following steps:
step 1: and (3) loading the silicon substrate and the metal hafnium target material into a growth chamber of a magnetron sputtering device, and carrying out ultrahigh vacuum high-temperature baking treatment on the silicon substrate to remove adsorbed gas, residual impurities and an oxide layer on the surface of the silicon substrate. The specific process flow is as follows: putting a cleaned 2-inch Si (111) substrate and a hafnium metal target with the diameter of 83mm and the purity of 99.99 percent into a growth chamber of magnetron sputtering equipment, and adjusting the distance between the silicon substrate and the hafnium metal target to be 7 cm; vacuumizing a growth chamber of magnetron sputtering equipment to 5.0 multiplied by 10 < -5 > Pa ultrahigh vacuum; and starting a substrate heating power supply, raising the substrate heating temperature to 800 ℃, and carrying out ultrahigh vacuum high temperature baking treatment on the silicon substrate for 30 minutes.
Step 2: and carrying out surface sputtering treatment on the silicon substrate by utilizing a magnetron sputtering reverse sputtering dry cleaning process to remove impurities and an oxidation layer remained on the surface of the silicon substrate. The specific process flow is as follows: reducing the heating temperature of the silicon substrate to 600 ℃ of the substrate heating temperature for the subsequent growth of the hafnium nitride barrier layer and the hafnium metal film; opening the substrate shutter; starting the substrate to rotate for 7 revolutions per minute; introducing argon gas with the purity of 99.99 percent into a growth chamber of magnetron sputtering equipment; and when the vacuum degree in the growth chamber is reduced to 0.5Pa vacuum degree capable of realizing the glow discharge of the sputtering gas argon, starting the reverse sputtering function of the magnetron sputtering equipment, wherein the reverse sputtering power is 50W, performing reverse sputtering dry cleaning on the surface of the silicon substrate for 10 minutes by using low-energy argon ions generated by the glow discharge of the sputtering gas argon, and then stopping the magnetron sputtering reverse sputtering.
And step 3: and preparing a hafnium nitride barrier layer on the silicon substrate by utilizing a magnetron sputtering deposition process so as to prevent the surface of the silicon substrate from interfacial intermixing with a subsequently prepared hafnium metal film and realize the preparation and growth of the hafnium metal film with high crystallization quality. The specific process flow is as follows: firstly, closing a substrate baffle; opening a baffle of the magnetron sputtering target; starting a direct-current sputtering deposition function of magnetron sputtering equipment, wherein the direct-current sputtering power is 150W, and performing radio-frequency sputtering pretreatment on the surface of the hafnium metal target for 20 minutes by using low-energy argon ions generated by argon glow discharge of sputtering gas to completely remove impurities and an oxidation layer remained on the surface of the hafnium metal target; opening the substrate baffle again, reducing the magnetron sputtering direct-current sputtering power to direct current of 100W, sputtering the surface of the metal hafnium target material by using low-energy argon ions generated by argon glow discharge of sputtering gas to generate neutral hafnium atoms, and pre-depositing the sputtered metal hafnium atoms for 2 minutes when reaching the surface of the silicon substrate to obtain a thin metal hafnium layer so as to prevent the surface of the silicon substrate from being nitrided first in the subsequent direct-current magnetron reactive sputtering process to form a thin silicon nitride layer which is not beneficial to the high-quality crystal growth of the hafnium nitride barrier layer; stopping magnetron sputtering direct-current sputtering deposition, properly reducing the flow of introduced sputtering gas argon, introducing certain flow of reaction gas nitrogen with the purity of 99.99% into a growth chamber of a magnetron sputtering device to enable the pressure ratio of the argon to the nitrogen to be 10, reducing the vacuum degree in the growth chamber to 0.5Pa vacuum degree of gas glow discharge again by using mixed gas formed by the introduced argon and the nitrogen, starting the reverse sputtering function of the magnetron sputtering device again, enabling the reverse sputtering power to be 50W, and enabling the time to be 2 minutes, wherein low-energy argon ions and nitrogen ions generated by glow discharge of the sputtering gas argon and the reaction gas nitrogen and a thin metal hafnium layer pre-deposited on the surface of a silicon substrate are subjected to nitridation reaction to form a thin hafnium nitride nucleation layer; stopping the magnetron sputtering reverse sputtering function, recovering the vacuum degree in the growth chamber to the vacuum degree of 0.5Pa of gas glow starting discharge again by the mixed gas formed by the sputtering gas argon and the reaction gas nitrogen, starting the magnetron sputtering direct current reactive sputtering deposition function, wherein the direct current reactive sputtering power is 100W, and the direct current reactive sputtering time is 15 minutes. Sputtering argon gas and low-energy argon ions and nitrogen ions generated by nitrogen glow discharge of reaction gas sputter the surface of the metal hafnium target material, sputtering and combining reaction are carried out to generate neutral hafnium nitride molecules, and the neutral hafnium nitride molecules are deposited on the thin hafnium nitride nucleating layer to form a thicker hafnium nitride barrier layer.
And 4, step 4: and preparing the hafnium metal film on the hafnium nitride barrier layer by utilizing a magnetron sputtering deposition process. The specific process flow is as follows: stopping magnetron sputtering direct-current reactive sputtering, and closing reactive gas nitrogen; and reducing the vacuum degree in the growth chamber to 0.5Pa vacuum degree capable of realizing glow starting discharge of the sputtering gas argon again by the aid of the sputtering gas argon to be introduced, starting a radio-frequency sputtering deposition function of the magnetron sputtering equipment, wherein the radio-frequency sputtering power is 120W, and the direct-current sputtering time is 20 minutes. Neutral metal hafnium atoms are sputtered on the surface of the low-energy argon ion sputtering metal hafnium target material generated by argon glow discharge of sputtering gas, and the neutral metal hafnium atoms are deposited on the hafnium nitride barrier layer to form a metal hafnium film.
And 5: and carrying out in-situ vacuum high-temperature annealing treatment on the hafnium metal film so as to further improve the crystallization quality of the hafnium metal film and reduce the stress. The specific process flow is as follows: stopping the radio frequency magnetron sputtering; the sputtering gas argon is closed; stopping the rotation of the substrate; closing the magnetron sputtering target baffle; and raising the heating temperature of the substrate to 800 ℃ again, and carrying out in-situ vacuum high-temperature annealing on the hafnium metal film for 30 minutes.
And 6, reducing the temperature of the substrate to room temperature at a cooling rate of 5 ℃ per minute, and finishing the preparation of the metal hafnium film material on the silicon substrate.
Fig. 2 is a result of an X-ray diffraction (XRD) test of a sample of a hafnium metal film prepared on a silicon substrate by magnetron sputtering in an embodiment of the present invention. As shown in fig. 2, the hafnium metal (α -Hf) thin film prepared on the Si (111) substrate using magnetron sputtering has a high degree of α -Hf (002) single preferred orientation and a 2 θ angle size of 35.54 ° which is closer to the 2 θ angle size of 35.51 ° for stress-free α -Hf, indicating that the sample has not only very high crystalline quality but also very low tensile stress.
FIG. 3 is a Scanning Electron Microscope (SEM) cross-sectional morphology test result of a hafnium metal film sample prepared on a silicon substrate by magnetron sputtering in an embodiment of the present invention. As shown in FIG. 3, where the hafnium nitride (HfN) barrier layer and the hafnium metal (α -Hf) thin film had uniform film thickness and dense film, the HfN barrier layer had a film thickness of 187.3nm, and the α -Hf thin film had a film thickness of 302.4nm, it was demonstrated that the α -Hf thin film samples prepared had a relatively high deposition rate of about 900nm per hour.
FIG. 4 shows the surface morphology test result of a Scanning Electron Microscope (SEM) for preparing a sample of a hafnium metal (alpha-Hf) thin film on a silicon substrate by magnetron sputtering in an embodiment of the present invention. As shown in FIG. 4, the surface of the sample of the α -Hf thin film prepared on the silicon substrate in the present example was observed to have rounded grain undulations.
Compared with the existing ion beam epitaxy process for preparing the grown metal hafnium film, the magnetron sputtering preparation and growth process for the metal hafnium film on the silicon substrate has higher deposition growth rate and larger film forming area.
Compared with the existing electron beam evaporation process for preparing the grown metal hafnium film, the magnetron sputtering preparation and growth process of the metal hafnium film on the silicon substrate is more beneficial to realizing that the metal hafnium film has high single preferred orientation and high crystallization quality growth and is tightly combined with the surface of the silicon substrate, and the film layer is more compact and has smoother surface.
Compared with the existing atomic layer deposition process, the magnetron sputtering preparation growth process of the metal hafnium thin film material on the silicon substrate has higher deposition growth rate and higher crystallization quality.
Compared with the existing metal organic chemical vapor deposition process, the process for preparing and growing the metal hafnium film on the silicon substrate by magnetron sputtering has higher deposition growth rate, lower growth temperature and higher crystallization quality.
In summary, the method for preparing the hafnium metal film on the silicon substrate by magnetron sputtering provided by the invention is beneficial to obtaining the low-stress high-crystallization-quality hafnium metal film with single preferred orientation, is also beneficial to realizing the improvement of the growth rate and the film forming area of the hafnium metal film, and can be compatible with the existing silicon-based microelectronic and power electronic device process and the silicon substrate gallium nitride heteroepitaxial growth process. Therefore, the method has good application and popularization values.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for preparing a hafnium metal film on a silicon substrate by magnetron sputtering comprises the following steps:
loading a silicon substrate and a metal hafnium target material into a growth chamber of magnetron sputtering equipment, and carrying out ultrahigh vacuum high-temperature baking treatment on the silicon substrate to remove adsorbed gas on the surface of the silicon substrate, residual impurities and an oxide layer;
carrying out surface sputtering treatment on the silicon substrate by utilizing a magnetron sputtering reverse sputtering dry cleaning process to remove impurities and an oxidation layer remained on the surface of the silicon substrate;
preparing a hafnium nitride barrier layer on the silicon substrate by utilizing a magnetron sputtering process so as to prevent the surface of the silicon substrate from interfacial intermixing with a subsequently prepared hafnium metal film and realize the preparation and growth of the hafnium metal film;
preparing a hafnium metal film on the hafnium nitride barrier layer by utilizing a magnetron sputtering deposition process;
carrying out in-situ vacuum high-temperature annealing treatment on the hafnium metal film so as to further improve the crystallization quality of the hafnium metal film and reduce the stress of the hafnium metal film;
and reducing the temperature of the metal hafnium film to room temperature to finish the preparation of the metal hafnium film sample.
2. The method of claim 1, wherein the step of preparing a hafnium nitride barrier layer on the silicon substrate using a magnetron sputtering process comprises:
forming a thin metal hafnium layer on the silicon substrate by utilizing a magnetron sputtering deposition process;
nitriding the thin metal hafnium layer by utilizing a magnetron sputtering reverse sputtering deposition process to form a thin hafnium nitride nucleating layer;
and forming a hafnium nitride layer on the thin hafnium nitride nucleating layer by utilizing a magnetron sputtering reactive sputtering process to finish the preparation of the hafnium nitride barrier layer.
3. The method as claimed in claim 2, wherein, when the hafnium nitride barrier layer is prepared, the distance between the hafnium target material and the silicon substrate is 5-8cm, the rotation speed of the silicon substrate is 5-100 rpm, the temperature of the silicon substrate is 250-750 ℃, the sputtering gas is argon, the reaction gas is nitrogen, and the working pressure in the growth chamber of the magnetron sputtering device is 0.1-5 Pa;
preferably, the magnetron sputtering deposition process for preparing the thin metal hafnium layer is direct current magnetron sputtering or radio frequency magnetron sputtering, the sputtering power is 20-100W, and the sputtering time is 1-5 minutes;
preferably, the magnetron sputtering reverse sputtering power for forming the thin hafnium nitride nucleation layer is 20-100W, the reverse sputtering time is 1-5 minutes, and the reaction gas for nitriding the thin metal hafnium layer is nitrogen;
preferably, the magnetron sputtering reactive sputtering process for forming the hafnium nitride layer is direct current magnetron sputtering, the sputtering power is 20-200w, the sputtering time is 2-30 minutes, and the reaction gas is nitrogen.
4. The method of claim 1, wherein the silicon substrate is subjected to the ultra-high vacuum high temperature bake treatment in a degree of vacuum of not more than 5 x 10-5Pa；
Preferably, the baking time of the silicon substrate at the temperature of 700-850 ℃ is 5-30 minutes.
5. The method as claimed in claim 1, wherein the distance between the hafnium target material and the silicon substrate is 5-8cm when the silicon substrate is subjected to surface sputtering, the rotation speed of the silicon substrate is 5-100 rpm, the temperature of the silicon substrate is 250-750 ℃, the sputtering gas is argon, the working pressure in the growth chamber of the magnetron sputtering apparatus is 0.1-5Pa, the reverse sputtering power is 50-300W, and the reverse sputtering time is 5-30 minutes.
6. The method as claimed in claim 1, wherein, when the hafnium nitride barrier layer is formed on the hafnium nitride barrier layer, the magnetron sputtering deposition process is rf magnetron sputtering or dc magnetron sputtering, the sputtering gas is argon, the working pressure in the magnetron sputtering growth chamber is 0.1-5Pa, the sputtering power is 20-150W, the distance between the hafnium target and the silicon substrate is 5-8cm, the rotation speed of the silicon substrate is 5-100 rpm, and the temperature of the silicon substrate is 250-750 ℃.
7. The method as claimed in claim 1, wherein the temperature for performing the in-situ vacuum high temperature annealing treatment on the hafnium metal film is 700-850 ℃;
preferably, the cooling speed of the metal hafnium film to the room temperature is 3-30 ℃ per minute.
8. The method of claim 1, wherein the silicon substrate is a silicon single crystal substrate;
preferably, the crystal orientation of the silicon substrate is (111), (100) or (113);
preferably, the silicon substrate has a diameter of at least 1 inch.
9. A hafnium metal film prepared by the method of preparing a hafnium metal film on a silicon substrate using magnetron sputtering as claimed in any one of claims 1 to 8.
10. The use of the hafnium metal film according to claim 9 in the heteroepitaxial preparation of a grown conductive buffer layer material for an ohmic contact metal electrode material or a silicon substrate gallium nitride material.
CN202110841158.1A 2021-07-23 2021-07-23 Metal hafnium film prepared on silicon substrate by utilizing magnetron sputtering, method and application Pending CN113584446A (en)

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