CN112831768A - Preparation method and application of hafnium nitride film with high crystallization quality - Google Patents
Preparation method and application of hafnium nitride film with high crystallization quality Download PDFInfo
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Abstract
The invention discloses a preparation method of a hafnium nitride film with high crystallization quality, which comprises the following steps: 1. baking the silicon substrate at high temperature; 2. reducing the temperature of the silicon substrate, introducing sputtering gas argon, and carrying out reverse sputtering dry cleaning on the silicon substrate under a first reverse sputtering power; 3. performing radio frequency magnetron sputtering pretreatment on the metal hafnium target under a second sputtering power; 4. pre-depositing a thin metal hafnium layer on the surface of the silicon substrate by adopting radio frequency magnetron sputtering under a third sputtering power; 5. introducing reaction gas nitrogen and sputtering gas argon to form mixed gas, and forming a thin hafnium nitride nucleating layer by adopting reverse sputtering under fourth reverse sputtering power; 6. performing deposition growth of the hafnium nitride film by adopting direct-current magnetron sputtering under a fifth sputtering power; 7. stopping introducing the sputtering gas argon, and annealing the hafnium nitride film at high temperature in the nitrogen atmosphere; 8. and reducing the temperature of the silicon substrate to room temperature. The method can realize the preparation of the hafnium nitride film with high crystallization quality on the silicon substrate.
Description
Technical Field
The invention belongs to the technical field of semiconductor and thin film material preparation, and particularly relates to a method for preparing a hafnium nitride thin film on a silicon substrate by utilizing magnetron sputtering.
Background
Transition refractory metal nitrides (including titanium nitride (TiN), zirconium nitride (ZrN), and hafnium nitride (HfN)) generally have a cubic rock salt structure, and not only have good thermal and chemical stability, but also have good electrical conductivity, and the resistivity is comparable to that of some metal materials with good electrical conductivity. In the technical field of semiconductors, particularly silicon-based device processes, transition group refractory metal nitride thin film materials have extremely important application values. Such as: the magnetron sputtering and atomic layer deposition preparation process of the TiN film is mature, and is the most common interdiffusion barrier layer material (low-K material) in the manufacture of ohmic contact metal electrode structures in the silicon-based microelectronic device process and the power electronic device process; ZrN has high reflectivity to visible light, and can play a better role in conductive and reflective stress covariation in the aspect of improving the performance of a GaN-LED device with a vertical structure Si substrate; the HfN, the Si and the GaN materials have smaller lattice mismatch and thermal expansion coefficient difference, and the material is a good conductive buffer layer material for preparing the GaN material on the Si substrate, or a more ideal component interdiffusion and interface chemical reaction low-K barrier layer material for manufacturing an n-type ohmic contact metal electrode structure in the processes of a Si device and the GaN device. In comparison, the abundance of metal zirconium on earth is more abundant than that of metal copper and titanium, and metal hafnium and metal zirconium are symbiotic, but the abundance is only 1% -2% of that of metal zirconium. Although the price of the raw material of metal hafnium with the same purity is almost the same as that of metal titanium, and compared with hafnium nitride, titanium nitride and zirconium nitride have smaller lattice mismatch and thermal expansion coefficient difference with silicon and gallium nitride, the preparation technology of the existing hafnium nitride film material is not as mature as that of titanium nitride and zirconium nitride, and the technology of substituting titanium nitride or zirconium nitride and applying the technology in a large range in the technical field of semiconductors, especially in the processes of silicon devices and gallium nitride devices has not been realized.
At present, the chemical vapor deposition process capable of realizing the preparation of the transition group refractory metal nitride hafnium nitride thin film material mainly includes Atomic Layer Deposition (ALD) and Metal Organic Chemical Vapor Deposition (MOCVD), and the physical vapor deposition process mainly includes Ion Beam Epitaxy (IBE) and Magnetron sputtering (Magnetron Sputter). The ALD material has a slow growth rate, and although a high-purity HfN film with a nanoscale thickness can be prepared, only amorphous or polycrystalline materials with poor crystallization quality can be grown due to low growth temperature. The MOCVD process for preparing and growing the HfN film is still in research and development, and no high-quality single crystal film growth result that the half-height-width-half-maximum (FWHM) of an HfN (111) diffraction peak is reduced to below 1 DEG on a Si substrate is reported. Ion Beam Epitaxy (IBE) process has been used by the semiconductor institute of chinese academy of sciences to achieve highly single preferred orientation growth of HfN thin films, but the ion beam epitaxy process is not suitable for fabricating devices using the existing semiconductor device process because of its small film formation area (2cm × 2 cm). At present, magnetron sputtering is still the main process for preparing and growing HfN film, but most of the existing research results show that amorphous Si which is not beneficial to HfN nucleation and growth is generated either because the residual oxide layer on the surface of the Si substrate is not completely removed or the surface of the Si substrate is prevented from being nitrided firstlyxNyMost of the research results show that the HfN polycrystalline thin film with disordered orientation is obtained, and the surface fluctuation is large (AFM surface Roughness (RMS) is higher than 3 nm). Even with the result that a single preferred orientation growth is achieved, no indication that the thin film material has a single crystal quality is seenThe X-ray rocking curve (XRC) full width at half maximum (FWHM) test results of (a).
In summary, the present invention provides a method for preparing a hafnium nitride film on a silicon substrate by magnetron sputtering, so as to fully utilize the functional characteristics of magnetron sputtering, such as large film-forming area, high growth rate, and capability of dry cleaning the surface of the substrate with a back-sputtering function.
Disclosure of Invention
The purpose of the invention is as follows: the present invention is directed to a method for preparing a hafnium nitride film, which enables the preparation of a hafnium nitride film of high crystal quality on a silicon substrate.
The technical scheme is as follows: the invention discloses a preparation method of a hafnium nitride film with high crystallization quality, which comprises the following steps:
s1, placing the cleaned silicon substrate and the metal hafnium target material into a growth chamber of a magnetron sputtering device, vacuumizing to ultrahigh vacuum, heating the silicon substrate to a first baking temperature, and baking the silicon substrate at high temperature under the ultrahigh vacuum condition;
s2, reducing the temperature of the silicon substrate to a second growth temperature, introducing argon as sputtering gas into the growth chamber, and carrying out reverse sputtering dry cleaning on the silicon substrate under a first reverse sputtering power; the second growth temperature is less than the first baking temperature;
s3, stopping the reverse sputtering, continuously introducing argon as sputtering gas into the growth chamber, and performing radio frequency magnetron sputtering pretreatment on the metal hafnium target under a second sputtering power;
s4, continuously introducing argon as sputtering gas into the growth chamber, sputtering the surface of the metal hafnium target by adopting radio frequency magnetron sputtering under a third sputtering power, and pre-depositing a thin metal hafnium layer on the surface of the silicon substrate;
s5, stopping the radio frequency magnetron sputtering, introducing a reaction gas nitrogen and a sputtering gas argon into the growth chamber to form a mixed gas, and nitriding the thin metal hafnium nitride layer by adopting reverse sputtering under fourth reverse sputtering power to form a thin hafnium nitride nucleating layer;
s6, stopping reverse sputtering, continuously introducing mixed gas consisting of reaction gas nitrogen and sputtering gas argon into the growth chamber, adopting direct current magnetron sputtering the surface of the metal hafnium target material under fifth sputtering power, and performing hafnium nitride film deposition growth on the surface of the thin hafnium nitride nucleation layer;
s7, stopping the direct current magnetron sputtering, stopping introducing sputtering gas argon into the growth chamber, heating the silicon substrate to a third annealing temperature, and performing high-temperature annealing on the hafnium nitride film under the protection of a nitrogen atmosphere; the third annealing temperature is greater than the second growth temperature;
s8, regulating and controlling the nitrogen pressure of the growth chamber to regulate and control the cooling rate, and cooling the temperature of the silicon substrate to room temperature;
and the third sputtering power, the fourth reverse sputtering power and the fifth sputtering power are all smaller than the second sputtering power and are all smaller than 200W.
Preferably, the first baking temperature is 700-850 ℃; the second growth temperature is 350-650 ℃.
Preferably, the third annealing temperature is 650-850 ℃.
Preferably, the values of the first reverse sputtering power and the second sputtering power are both 100-300W.
Further, the value of the third sputtering power is 25-150W.
Preferably, the value of the fourth reverse sputtering power is 25-150W.
Preferably, the values of the fifth sputtering power are all 25-150W.
Preferably, in the step S9, the silicon substrate cooling rate is 2 to 20 ℃ per minute.
Preferably, in the step S4, the deposition time of the thin metal hafnium layer is 1-15 minutes; preferably, in the step S5, the nitriding time of the thin metal hafnium layer is 1 to 15 minutes.
Preferably, in step S7, the hafnium nitride film is annealed at a high temperature, and the pressure in the growth chamber filled with a nitrogen atmosphere is 0.001 to 1000 Pa.
The degree of vacuum of the gas glow discharge is 0.2 to 6 Pa.
On the other hand, the invention discloses the application of the hafnium nitride film prepared by the method, and the hafnium nitride film is used as a low-K interdiffusion blocking layer of an ohm contact metal electrode manufacturing process in a silicon device process, a silicon substrate gallium nitride material heteroepitaxial growth conductive buffer layer and a silicon device anti-electromagnetic radiation protective layer.
Has the advantages that: the preparation method of the hafnium nitride film disclosed by the invention comprises the steps of firstly baking a substrate at a high temperature, then reducing the heating temperature of the substrate, carrying out reverse sputtering dry cleaning on the substrate, carrying out pretreatment on a metal hafnium target material, then carrying out deposition of the hafnium nitride film (see steps S4-S6), and finally carrying out annealing and cooling to room temperature. The deposition process of the hafnium nitride film (steps S4-S6) is performed under the conditions of low heating temperature (second growth temperature) and low sputtering power, and has the following advantages compared with the prior art:
1. the method comprises the steps of firstly pre-depositing a thin metal hafnium layer on the surface of a silicon substrate, and then nitriding the thin metal hafnium layer to form a thin hafnium nitride nucleating layer, so that the phenomenon that the surface of the silicon substrate is firstly nitrided to form an amorphous silicon nitride layer which is not beneficial to high-density nucleation and continuous film formation of hafnium nitride can be avoided and prevented; the method can also avoid and prevent the intermixing of metal hafnium atoms and the surface interface of the silicon substrate caused by high sputtering power and growth temperature, and generate a thin silicon hafnium alloy layer which is not beneficial to realizing the growth of the hafnium nitride film with single preferred orientation and high crystal quality;
2. under the condition that the substrate heating temperature is the second growth temperature, proper low sputtering power and low heating temperature are adopted, so that the crystallization quality of the hafnium nitride film is improved, and the deposition growth rate of the film is higher;
3. after the deposition growth is finished, the heating temperature of the substrate is properly raised to carry out in-situ annealing on the prepared hafnium nitride film under nitrogen atmosphere, so that the common crystal lattice damage and introduced additional compressive stress of the film prepared by the magnetron sputtering process can be relieved, the crystallization quality of the hafnium nitride film is further improved, the stress of the film layer is reduced, and the improvement of the density and the surface flatness of the film layer is further facilitated; in addition, the large thermal mismatch stress accumulated on the film layer in the cooling process is relieved by controlling the proper cooling rate, and the preparation of the hafnium nitride film with low stress and high crystallization quality is facilitated.
Drawings
FIG. 1 is a flow chart of a process for preparing a hafnium nitride film according to the present invention;
FIG. 2 is a graph showing the results of X-ray diffraction (XRD) measurements on samples of the hafnium nitride thin film of example 1;
FIG. 3 is a graph of the X-ray rocking curve (XRC) test results for the HfN (111) diffraction peak of the hafnium nitride thin film sample of example 1;
FIG. 4 is a Scanning Electron Microscope (SEM) surface and cross-sectional profile test results of the sample of the hafnium nitride film of example 1.
Detailed Description
The invention is further elucidated with reference to the drawings and the detailed description.
Example 1
The invention discloses a preparation method of a hafnium nitride film with high crystallization quality, which comprises the following steps of:
s1, placing the cleaned silicon substrate and the metal hafnium target material into a growth chamber of a magnetron sputtering device, vacuumizing to ultrahigh vacuum, heating the silicon substrate to a first baking temperature, and baking the silicon substrate at high temperature under the ultrahigh vacuum condition;
the silicon substrate is a silicon single crystal substrate whose crystal orientation is not limited to (111), (100), (110) and (113), and has a size of not less than 1 inch in diameter and a purity of the hafnium metal target material of not less than 99.99%. In this example, a 2-inch Si (111) substrate and a hafnium metal target having a diameter of 83mm and a purity of 99.99% were used. The distance between the silicon substrate and the metal hafnium target is 5 to 15cm, in this embodiment, the distance between the silicon substrate and the metal hafnium target is 8cm, and the growth chamber is evacuated to an ultra-high vacuum of 4X 10-5 Pa. And starting a substrate heating power supply, heating the substrate to 800 ℃, and carrying out ultrahigh vacuum high temperature baking surface treatment on the silicon substrate for 30 minutes to remove gas adsorbed on the surface of the silicon substrate, residual impurities and an oxidation layer.
S2, reducing the temperature of the silicon substrate to 500 ℃ of a second growth temperature, opening a substrate baffle, starting the substrate to rotate for 7 revolutions per minute, introducing argon gas of sputtering gas with the purity of 99.99% into a growth chamber of the magnetron sputtering equipment, starting the reverse sputtering function of the magnetron sputtering equipment when the vacuum degree in the growth chamber is reduced to the vacuum degree of argon glow discharge of the sputtering gas, and performing reverse sputtering dry cleaning on the surface of the silicon substrate for 10 minutes by using low-energy argon ions generated by argon glow discharge of the sputtering gas under the condition that the first reverse sputtering power is 120W so as to completely remove impurities and oxidation layers remained on the surface of the silicon substrate;
the gas glow starting discharge effect is better in the range of the vacuum degree of 0.2 to 6Pa, and in the embodiment, the reverse sputtering function or the sputtering function of the magnetron sputtering equipment is started when the vacuum degree of the growth chamber is 0.5 Pa.
The steps S1 and S2 combine the ultrahigh vacuum high temperature baking and the reverse sputtering dry cleaning, so that the gas and the impurities adsorbed on the surface of the silicon substrate and the residual oxide layer can be more effectively removed, and the high-density nucleation and the high-crystallization-quality film forming growth of the hafnium nitride film are more facilitated.
S3, stopping reverse sputtering, closing the substrate baffle, opening the baffle of the magnetron sputtering metal hafnium target, continuously introducing sputtering gas argon into the growth chamber, starting the radio frequency magnetron sputtering function of the magnetron sputtering equipment, and performing radio frequency magnetron sputtering pretreatment on the surface of the metal hafnium target for 20 minutes by using low-energy argon ions generated by glow discharge of the sputtering gas argon under the condition that the second sputtering power is 150W so as to completely remove residual impurities and an oxidation layer on the surface of the metal hafnium target;
s4, opening a substrate baffle, continuously introducing sputtering gas argon into the growth chamber, under the condition that the third sputtering power is 120W, sputtering gas argon is subjected to glow starting discharge to generate low-energy argon ions to sputter the surface of the metal hafnium target material to generate neutral hafnium atoms, pre-depositing for 10 minutes on 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 to form a thin silicon nitride layer which is not beneficial to high-quality crystal growth of hafnium nitride in the subsequent direct-current magnetron reactive sputtering process;
s5, stopping radio frequency magnetron sputtering, firstly reducing the flow of sputtering gas argon introduced into the growth chamber, then introducing reaction gas nitrogen with the purity of 99.99% into the growth chamber of the magnetron sputtering equipment, wherein the pressure ratio of the argon to the nitrogen is 10, reducing the vacuum degree in the growth chamber to the vacuum degree of 0.5Pa of gas glow discharge by using mixed gas formed by the introduced argon and the nitrogen, starting the reverse sputtering function of the magnetron sputtering equipment again, and nitriding the thin metal hafnium nitride layer pre-deposited on the surface of the silicon substrate for 10 minutes by using low-energy argon ions and nitrogen ions generated by the glow discharge of the sputtering gas argon and the reaction gas nitrogen under the condition that the fourth reverse sputtering power is 60W to form the thin hafnium nitride nucleation layer;
s6, stopping reverse sputtering, recovering the vacuum degree in the growth chamber to the vacuum degree of 0.5Pa of gas glow starting discharge again by mixed gas formed by introduced sputtering gas argon and reaction gas nitrogen, starting the direct-current magnetron sputtering function of the magnetron sputtering equipment, sputtering the surface of the metal hafnium target by using low-energy argon ions and nitrogen ions generated by the glow starting discharge of the sputtering gas argon and the reaction gas nitrogen under the condition that the fifth sputtering power is 120W, and simultaneously carrying out sputtering and chemical combination reaction to generate neutral hafnium nitride molecules, wherein the neutral hafnium nitride molecules are transported to the surface of the silicon substrate covered with the thin hafnium nitride nucleating layer to carry out hafnium nitride film deposition growth for 90 minutes;
s7, stopping direct current magnetron reactive sputtering, closing argon sputtering gas, stopping substrate rotation, closing a magnetron sputtering metal hafnium target baffle, raising the substrate heating temperature to a third annealing temperature again, and performing high-temperature annealing on the hafnium nitride film for 30 minutes under the protection of 0.5Pa nitrogen atmosphere to recover lattice damage, reduce defects, avoid high-temperature decomposition of the film surface, and promote merging and growth of crystal grains of the hafnium nitride film and improve the crystallization quality; the third annealing temperature in this example was 750 ℃.
And S8, regulating and controlling the cooling rate by regulating and controlling the nitrogen pressure of the growth chamber, and cooling the substrate to room temperature. In this embodiment, the pressure of nitrogen in the growth chamber is adjusted to 5Pa, the substrate temperature is reduced to room temperature at a cooling rate of 5 ℃ per minute, and the nitrogen is turned off, thereby completing the preparation of the hafnium nitride film on the silicon substrate.
The film layer accumulates larger thermal mismatch stress in the cooling process is relieved by controlling a proper cooling rate, and the preparation of the hafnium nitride film with low stress and high crystallization quality is facilitated.
In order to obtain single preferred orientation high crystal quality growth, the step S4 adopts radio frequency magnetron sputtering to deposit a hafnium metal film, and the step S6 adopts direct current magnetron sputtering to deposit a hafnium nitride film.
The prepared sample was subjected to an X-ray diffraction (XRD) test, and referring to fig. 2, the HfN thin film prepared on the Si (111) substrate using magnetron sputtering had a high degree of HfN (111) single preferred orientation, and the 2 θ angle was 34.7492 ° close to the 2 θ angle 34.367 ° of the unstressed HfN. X-ray rocking curve (XRC) testing of the HfN (111) diffraction peak, see fig. 3, resulted in an XRC full width at half maximum (FWHM) of only 2.69 °, indicating that the sample not only had very high crystalline quality but also had lower stress.
The prepared sample is subjected to surface and cross-sectional morphology testing by a Scanning Electron Microscope (SEM), referring to FIG. 4, the HfN film layer is dense, the film thickness is 330nm, the deposition growth of the hafnium nitride film in the embodiment is 90 minutes, and the sample has a higher deposition rate of 220nm per hour.
Example 2
Example 2 the same procedure as in example 1 was used to prepare a hafnium nitride film, except that:
the distance between the silicon substrate and the metal hafnium target in step S1 is 5 cm; performing ultrahigh vacuum high temperature baking surface treatment on the silicon substrate at a first baking temperature of 700 ℃ for 40 minutes to remove gas adsorbed on the surface of the silicon substrate and residual impurities and an oxide layer;
in step S2, the second growth temperature is 350 ℃, and the substrate tray rotation speed at which the substrate rotates is 120 revolutions per minute; carrying out reverse sputtering dry cleaning on the surface of the silicon substrate for 3 minutes by using low-energy argon ions generated by argon glow discharge of sputtering gas under the condition that the first reverse sputtering power is 200W so as to completely remove impurities and an oxidation layer remained on the surface of the silicon substrate;
in step S3, performing rf magnetron sputtering pretreatment on the surface of the hafnium metal target for 5 minutes by using low-energy argon ions generated by argon glow discharge of sputtering gas at a second sputtering power of 300W to completely remove the impurities and the oxide layer remaining on the surface of the hafnium metal target;
in step S4, under the condition that the third sputtering power is 150W, neutral hafnium atoms are generated on the surface of the low-energy argon ion sputtering metal hafnium target material generated by argon glow discharge of sputtering gas, and a thin metal hafnium layer is obtained by pre-depositing on the surface of the silicon substrate for 1 minute;
in the step S5, the pressure ratio of argon to nitrogen is 2, the mixed gas formed by the argon and the nitrogen to be introduced reduces the vacuum degree in the growth chamber to 0.5Pa vacuum degree of gas glow discharge again, the reverse sputtering function of the magnetron sputtering equipment is started again, and the low-energy argon ions and nitrogen ions generated by the glow discharge of the argon and the nitrogen serving as sputtering gases are utilized to nitride the thin metal hafnium nitride layer pre-deposited on the surface of the silicon substrate for 1 minute under the condition that the fourth reverse sputtering power is 150W to form a thin hafnium nitride nucleation layer;
in the step S6, the fifth sputtering power is 150W;
in the step S7, the third annealing temperature is 850 ℃, and the annealing is carried out for 60 minutes;
in step S8, the substrate temperature is lowered to room temperature at a temperature lowering rate of 2 ℃ per minute.
Example 3
Example 3 the same procedure as in example 1 was used to prepare a hafnium nitride film, except that:
the distance between the silicon substrate and the metal hafnium target in step S1 is 15 cm; performing ultrahigh vacuum high temperature baking surface treatment on the silicon substrate at a first baking temperature of 850 ℃ for 15 minutes to remove adsorbed gas on the surface of the silicon substrate and residual impurities and an oxide layer;
in step S2, the second growth temperature is 650 ℃, and the substrate tray rotation speed at which the substrate rotates is 5 revolutions per minute; carrying out reverse sputtering dry cleaning on the surface of the silicon substrate for 20 minutes by using low-energy argon ions generated by argon glow discharge of sputtering gas under the condition that the first reverse sputtering power is 100W so as to completely remove residual impurities and an oxidation layer on the surface of the silicon substrate;
in step S3, performing rf magnetron sputtering pretreatment on the surface of the hafnium metal target for 30 minutes by using low-energy argon ions generated by argon glow discharge of sputtering gas at a second sputtering power of 100W to completely remove the impurities and the oxide layer remaining on the surface of the hafnium metal target;
the third sputtering power in step S4 is 50W;
in the step S5, the pressure ratio of argon to nitrogen is 5, the mixed gas formed by the argon and the nitrogen to be introduced reduces the vacuum degree in the growth chamber to 0.5Pa vacuum degree of gas glow starting discharge again, the reverse sputtering function of the magnetron sputtering equipment is started again, and the thin metal hafnium nitride layer pre-deposited on the surface of the silicon substrate is nitrided for 15 minutes by using low-energy argon ions and nitrogen ions generated by the glow starting discharge of the argon and the nitrogen serving as the sputtering gas under the condition that the fourth reverse sputtering power is 75W to form a thin hafnium nitride nucleation layer;
in the step S6, the fifth sputtering power is 50W;
in the step S7, the third annealing temperature is 850 ℃, and the annealing is carried out for 20 minutes;
the substrate temperature was lowered to room temperature at a temperature lowering rate of 20 c per minute in step S8.
Example 4
Example 4 the same procedure as in example 1 was used to prepare a hafnium nitride film, except that:
in step S2, the first reverse sputtering power is 300W;
in step S3, performing rf magnetron sputtering pretreatment on the surface of the hafnium metal target for 30 minutes by using low-energy argon ions generated by argon glow discharge of sputtering gas at a second sputtering power of 100W to completely remove the impurities and the oxide layer remaining on the surface of the hafnium metal target;
in step S4, under the condition that the third sputtering power is 25W, neutral hafnium atoms are generated on the surface of the low-energy argon ion sputtering metal hafnium target material generated by argon glow discharge of sputtering gas, and a thin metal hafnium layer is obtained by pre-depositing on the surface of the silicon substrate for 15 minutes;
in the step S5, the pressure ratio of argon to nitrogen is 20, the mixed gas formed by the argon and the nitrogen to be introduced reduces the vacuum degree in the growth chamber to 0.5Pa vacuum degree of gas glow discharge again, the reverse sputtering function of the magnetron sputtering equipment is started again, and the low-energy argon ions and nitrogen ions generated by the glow discharge of the argon and the nitrogen serving as sputtering gases are utilized to nitride the thin metal hafnium nitride layer pre-deposited on the surface of the silicon substrate for 15 minutes under the condition that the fourth reverse sputtering power is 25W to form a thin hafnium nitride nucleation layer;
in the step S6, the fifth sputtering power is 25W;
the third annealing temperature in the step S7 is 650 ℃, and the annealing is carried out for 90 minutes;
the substrate temperature was lowered to room temperature at a temperature lowering rate of 10 c per minute in step S8.
The hafnium nitride film prepared by the method can be used as a low-K interdiffusion blocking layer of an ohm contact metal electrode manufacturing process in a silicon device process, a silicon substrate gallium nitride material heteroepitaxial growth conductive buffer layer, a silicon device anti-electromagnetic radiation protection layer and the like.
Claims (10)
1. A method for preparing a hafnium nitride film with high crystal quality is characterized by comprising the following steps:
s1, placing the cleaned silicon substrate and the metal hafnium target material into a growth chamber of a magnetron sputtering device, vacuumizing to ultrahigh vacuum, heating the silicon substrate to a first baking temperature, and baking the substrate at high temperature under the ultrahigh vacuum condition;
s2, reducing the temperature of the silicon substrate to a second growth temperature, introducing argon as sputtering gas into the growth chamber, and carrying out reverse sputtering dry cleaning on the silicon substrate under a first reverse sputtering power; the second growth temperature is less than the first baking temperature;
s3, stopping the reverse sputtering, continuously introducing argon as sputtering gas into the growth chamber, and performing radio frequency magnetron sputtering pretreatment on the metal hafnium target under a second sputtering power;
s4, continuously introducing argon as sputtering gas into the growth chamber, sputtering the surface of the metal hafnium target by adopting radio frequency magnetron sputtering under a third sputtering power, and pre-depositing a thin metal hafnium layer on the surface of the silicon substrate;
s5, stopping the radio frequency magnetron sputtering, introducing a mixed gas of a reaction gas nitrogen and a sputtering gas argon into the growth chamber, and nitriding the thin metal hafnium nitride layer by adopting reverse sputtering under fourth reverse sputtering power to form a thin hafnium nitride nucleating layer;
s6, stopping reverse sputtering, continuously introducing mixed gas consisting of reaction gas nitrogen and sputtering gas argon into the growth chamber, adopting direct current magnetron sputtering the surface of the metal hafnium target material under fifth sputtering power, and performing hafnium nitride film deposition growth on the surface of the thin hafnium nitride nucleation layer;
s7, stopping the direct current magnetron sputtering, stopping introducing sputtering gas argon into the growth chamber, heating the silicon substrate to a third annealing temperature, and performing high-temperature annealing on the hafnium nitride film under the protection of a nitrogen atmosphere; the third annealing temperature is greater than the second growth temperature;
s8, regulating and controlling the nitrogen pressure of the growth chamber to regulate and control the cooling rate, and cooling the temperature of the silicon substrate to room temperature;
and the third sputtering power, the fourth reverse sputtering power and the fifth sputtering power are all smaller than the second sputtering power and are all smaller than 200W.
2. The method for preparing the hafnium nitride film according to claim 1, wherein the first baking temperature is 700-850 ℃; the second growth temperature is 350-650 ℃.
3. The method of claim 1, wherein the third annealing temperature is 650-850 ℃.
4. The method for preparing the hafnium nitride film according to claim 1, wherein the first reverse sputtering power and the second sputtering power are both 100-300W.
5. The method for preparing the hafnium nitride film according to claim 1, wherein the third sputtering power is 25-150W.
6. The method for preparing the hafnium nitride film according to claim 1, wherein the fourth reverse sputtering power is 25-150W.
7. The method for preparing the hafnium nitride film according to claim 1, wherein the fifth sputtering power is 25-150W.
8. The method of claim 1, wherein in step S9, the silicon substrate is cooled at a rate of 2-20 ℃ per minute.
9. The method of claim 1, wherein in step S4, the deposition time of the thin metal hafnium layer is 1-15 minutes; preferably, in the step S5, the nitriding time of the thin metal hafnium layer is 1 to 15 minutes.
10. The use of the hafnium nitride film prepared according to any of claims 1 to 9, wherein the hafnium nitride film is used as a low-K interdiffusion barrier layer in a ohm's contact metal electrode fabrication process in a silicon device process, a conductive buffer layer grown heteroepitaxially on a gallium nitride material on a silicon substrate, and a protective layer against electromagnetic radiation for a silicon device.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113584446A (en) * | 2021-07-23 | 2021-11-02 | 中国科学院半导体研究所 | Metal hafnium film prepared on silicon substrate by utilizing magnetron sputtering, method and application |
| CN113755804A (en) * | 2021-08-13 | 2021-12-07 | 中国电子科技集团公司第五十五研究所 | Preparation method of near-zero stress scandium-doped aluminum nitride film |
| CN114959616A (en) * | 2022-06-23 | 2022-08-30 | 贵州大学 | High-crystallinity single-phase high-entropy nitride coating and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796593A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院半导体研究所 | Method for preparing film material of metal hafnium |
| CN101211989A (en) * | 2006-12-28 | 2008-07-02 | 中国科学院半导体研究所 | Silicon based compliant substrate material possessing thin hafnium nitride compliant layer |
| CN103526171A (en) * | 2013-10-21 | 2014-01-22 | 上海理工大学 | Preparation method of aluminum-doped zinc oxide film with tunable preferred orientations |
| CN103572234A (en) * | 2013-10-22 | 2014-02-12 | 西南交通大学 | Preparation method of gamma-In2Se3 film with (006) preferred direction |
| CN105957924A (en) * | 2016-06-28 | 2016-09-21 | 常州工学院 | Method for preparing preferred orientation ITO photoelectric thin film by ZnO buffer layer |
| CN106835042A (en) * | 2017-01-16 | 2017-06-13 | 厦门大学 | A kind of preparation method of transition metal nitride ultracapacitor coating material |
| CN108342687A (en) * | 2018-01-30 | 2018-07-31 | 吉林大学 | A kind of Hf of the monatomic doping of noble metal3N4Film and preparation method thereof |
| CN108441830A (en) * | 2018-03-01 | 2018-08-24 | 大连理工大学 | A method of hafnium oxide based ferroelectric film is prepared using reaction magnetocontrol sputtering |
| CN109913826A (en) * | 2019-03-27 | 2019-06-21 | 吉林大学 | A kind of high hydrophobic long life material of novel silver introducing hafnium nitride film |
-
2021
- 2021-01-04 CN CN202110003038.4A patent/CN112831768B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796593A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院半导体研究所 | Method for preparing film material of metal hafnium |
| CN101211989A (en) * | 2006-12-28 | 2008-07-02 | 中国科学院半导体研究所 | Silicon based compliant substrate material possessing thin hafnium nitride compliant layer |
| CN103526171A (en) * | 2013-10-21 | 2014-01-22 | 上海理工大学 | Preparation method of aluminum-doped zinc oxide film with tunable preferred orientations |
| CN103572234A (en) * | 2013-10-22 | 2014-02-12 | 西南交通大学 | Preparation method of gamma-In2Se3 film with (006) preferred direction |
| CN105957924A (en) * | 2016-06-28 | 2016-09-21 | 常州工学院 | Method for preparing preferred orientation ITO photoelectric thin film by ZnO buffer layer |
| CN106835042A (en) * | 2017-01-16 | 2017-06-13 | 厦门大学 | A kind of preparation method of transition metal nitride ultracapacitor coating material |
| CN108342687A (en) * | 2018-01-30 | 2018-07-31 | 吉林大学 | A kind of Hf of the monatomic doping of noble metal3N4Film and preparation method thereof |
| CN108441830A (en) * | 2018-03-01 | 2018-08-24 | 大连理工大学 | A method of hafnium oxide based ferroelectric film is prepared using reaction magnetocontrol sputtering |
| CN109913826A (en) * | 2019-03-27 | 2019-06-21 | 吉林大学 | A kind of high hydrophobic long life material of novel silver introducing hafnium nitride film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113584446A (en) * | 2021-07-23 | 2021-11-02 | 中国科学院半导体研究所 | Metal hafnium film prepared on silicon substrate by utilizing magnetron sputtering, method and application |
| CN113755804A (en) * | 2021-08-13 | 2021-12-07 | 中国电子科技集团公司第五十五研究所 | Preparation method of near-zero stress scandium-doped aluminum nitride film |
| CN113755804B (en) * | 2021-08-13 | 2023-09-12 | 中国电子科技集团公司第五十五研究所 | Preparation method of near-zero stress scandium-doped aluminum nitride film |
| CN114959616A (en) * | 2022-06-23 | 2022-08-30 | 贵州大学 | High-crystallinity single-phase high-entropy nitride coating and preparation method thereof |
| CN114959616B (en) * | 2022-06-23 | 2023-07-21 | 贵州大学 | High-crystallinity single-phase high-entropy nitride coating and preparation method thereof |
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