CN111962153A - Single crystal TiN electrode film and preparation method thereof - Google Patents

Single crystal TiN electrode film and preparation method thereof Download PDF

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CN111962153A
CN111962153A CN202010631630.4A CN202010631630A CN111962153A CN 111962153 A CN111962153 A CN 111962153A CN 202010631630 A CN202010631630 A CN 202010631630A CN 111962153 A CN111962153 A CN 111962153A
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electrode film
single crystal
sapphire substrate
tin electrode
tin
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陆旭兵
成佳运
樊贞
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South China Normal University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/38—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C30B23/08—Epitaxial-layer growth by condensing ionised vapours
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • C30B33/02—Heat treatment

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Abstract

The invention relates to a single crystal TiN electrode film and a preparation method thereof, wherein the preparation method of the single crystal TiN electrode film comprises the following steps: s1: heating the sapphire substrate and heating the sapphire substrate at a temperature of 0.6 to 1.0J/cm in a vacuum environment2The laser energy density of (2) is that a TiN target material is sputtered on the sapphire substrate by adopting pulse laser; s2: and after the TiN film is deposited on the sapphire substrate, in-situ annealing is carried out, and then the temperature is cooled to room temperature, so that the monocrystal TiN electrode film is obtained. According to the invention, the TiN target material is etched by adopting the high-energy laser beam, so that the surface atomic mobility of the single crystal TiN electrode film can be improved, the growth quality of the single crystal TiN electrode film is favorably improved, and the single crystal TiN electrode film with single orientation and high conductivity is formed. The invention adopts the pulse laser deposition technology to prepare the monocrystal TiN electrode film, has no pollution and simple process, and canPrecise control of the film stoichiometry, and the like.

Description

Single crystal TiN electrode film and preparation method thereof
Technical Field
The invention relates to the technical field of electrode film preparation, in particular to a single crystal TiN electrode film and a preparation method thereof.
Background
With the increasing integration of microelectronic devices, the traditional microelectronic materials and micro-nano processing methods face a serious challenge, wherein the diffusion problem of the traditional metal electrode materials is one of the basic problems faced in the current large-scale integrated circuit production process.
Titanium nitride (TiN) is a wide bandgap semiconductor material consisting of metallic, ionic and covalent bonds. The TiN structure is stable, the change of the nitrogen content of the TiN in a certain range can not cause the change of the TiN lattice structure, and meanwhile, the TiN also has the excellent characteristics of good chemical stability, good thermal stability, good electrical conductivity, high mechanical strength and the like. In addition, TiN has optical properties similar to metals and a larger work function (about 4.7eV), can be compatible with semiconductor processes such as photoetching, stripping, etching and the like, and is an electrode material commonly used in the current microelectronic high-K metal gate technology and a metal material commonly used in a CMOS (complementary metal oxide semiconductor) process.
The conventional TiN film preparation method mainly adopts a Metal Organic Chemical Vapor Deposition (MOCVD) method, a vacuum evaporation coating method, a magnetron sputtering method and the like. In the preparation methods, the TiN film prepared by MOCVD has more carbon and hydrogen impurities which are difficult to eliminate, which affects the quality of the TiN film; and the process of preparing the film by the CVD technology is complex and is not beneficial to large-scale industrial production. The vacuum evaporation coating is difficult to obtain a film with a crystal structure, the adhesion of the film on a substrate is insufficient, and the use requirement of TiN as an electrode film is difficult to meet. The common magnetron sputtering method is difficult to prepare the single crystal TiN electrode film with high preferred orientation, the stoichiometric ratio of the single crystal TiN electrode film to the stoichiometric ratio of the single crystal.
Disclosure of Invention
Based on the above, in order to overcome the defects and shortcomings of the prior art, the invention provides a preparation method capable of preparing a single crystal TiN electrode film with a stoichiometric ratio close to 1:1 and high conductivity.
The invention provides a preparation method of a single crystal TiN electrode film, which comprises the following steps:
s1: heating the sapphire substrate and heating the sapphire substrate at a temperature of 0.6 to 1.0J/cm in a vacuum environment2The laser energy density of (2) is that a TiN target material is sputtered on the sapphire substrate by adopting pulse laser;
s2: and after the TiN film is deposited on the sapphire substrate, in-situ annealing is carried out, and then the temperature is cooled to room temperature, so that the monocrystal TiN electrode film is obtained.
Compared with the prior art, the invention has mature production technology, better device quality, high mechanical strength, easy processing and cleaning and good stability, and can be applied to the sapphire substrate grown at high temperature; then, the density of the mixture is 0.6 to 1.0J/cm2Carrying out pulse laser sputtering on the TiN target material with high laser energy flux density and high substrate temperature; the formed monocrystal TiN electrode film is an epitaxial film which grows in a preferred orientation with the stoichiometric ratio close to 1:1 and the (111) crystal face height, has a compact and flat surface, and has good ductility, crystallinity, thermal stability, chemical stability and electrical conductivity. Therefore, the high-energy laser beam is adopted to etch the TiN target material, high-temperature and high-pressure plasma is further generated, the plasma directionally expands locally and is deposited on the sapphire substrate to form the single crystal TiN electrode film, the surface atomic mobility of the single crystal TiN electrode film can be improved, the growth quality of the single crystal TiN electrode film is improved, and the single crystal TiN electrode film which is single in orientation and has the stoichiometric ratio close to 1:1 is formed. The invention adopts the pulse laser deposition technology to prepare the monocrystal TiN electrode film, and has the advantages of no pollution, simple process, accurate control of film stoichiometry, preparation of multilayer films, epitaxial growth of monocrystal films with abrupt heterojunction interfaces and the like.
Further, before step S1, cleaning the sapphire substrate; the specific steps of cleaning the sapphire substrate are as follows: ultrasonically cleaning the sapphire substrate by using an organic solvent for 13-17 min, and then washing by using deionized water; then putting the sapphire substrate into concentrated H2SO4With concentrated H3PO4Boiling the mixed solution in a volume ratio of 3:1 for 8-12 min, and then washing with deionized water; and finally, blowing the mixture by using nitrogen for standby.
Because the flatness of the surface of the sapphire substrate has great influence on the flatness of the growth of the monocrystal TiN electrode film, three liquids are selected to clean and process the surface of the sapphire substrate. Firstly, the sapphire substrate is put into acetone, isopropyl alcohol or alcohol and the likeUltrasonic cleaning in an organic solvent, and then washing the substrate with deionized water; impurities on the surface of the sapphire substrate can be removed, so that internal stress generated by dislocation and defects in the film growth process is reduced, and the electrode film and a semiconductor layer of a device have good adhesiveness and are not easy to peel off due to the small internal stress. Then placing the sapphire substrate into H2SO4And H3PO4Boiling in the mixed acid solution, washing the substrate with deionized water, and finally drying with nitrogen; the charged particles such as metal ions and the like on the surface of the substrate can be effectively removed, so that the phenomena of breakdown, voltage reduction, electric leakage and the like during the operation of the device are avoided.
Further, in step S1, the TiN target is a TiN ceramic target having a purity of 99.99%. The invention selects TiN ceramic target material with the purity of 99.99 percent as the precursor. The purity of the TiN sputtering target has a large influence on the performance of the single crystal TiN electrode film, and if the purity of the TiN target is not enough, impurity particles in the target can be attached to the surface of the substrate under the action of laser sputtering, so that the film layer of the single crystal TiN electrode film at partial positions is not firm, and the phenomenon of film stripping occurs. Therefore, the higher the purity of the TiN target material is, the better the performance of the prepared monocrystal TiN electrode film is.
Further, in step S1, the energy density is 0.8J/cm2. At an optimum energy density of 0.8J/cm2The surface of the prepared monocrystal TiN electrode film is compact and uniform; because after the sputtered ions reach the substrate, a relatively flat, smooth film is produced. Then, if the kinetic energy of the incident ions is increased, the migration speed of atoms on the surface of the substrate is increased, the combination of ions is accelerated, large particles with lower free energy are more easily formed, and the roughness of the surface of the film is increased.
Further, in step S1, the vacuum degree of the vacuum environment is 10-4Pa. Vacuumizing the cavity of the pulse laser deposition system to 10 DEG-4Pa, growing TiN into a film under high vacuum. Impurities can be introduced into the high vacuum environment as little as possible, and plasma generated by laser bombardment of the TiN target material directionally expands to the sapphire substrate to prepare the monocrystal TiN electrode film with the stoichiometric ratio close to 1:1The closer the stoichiometric ratio of the single crystal TiN electrode film is to 1:1, the more favorable the excellent conductivity is obtained.
Further, in step S1, the sapphire substrate is heated by gradually raising the temperature at a rate of 8-12 ℃/min. The gradual temperature rise is beneficial to protecting the sapphire substrate, and the phenomenon that the sapphire substrate is cracked due to the sudden temperature rise is prevented, so that the performance and the quality of the finally obtained single crystal TiN electrode film are influenced.
Further, in step S2, after the in-situ annealing is performed for 30min, the temperature is gradually decreased to room temperature at a rate of 4-6 ℃/min. The in-situ annealing for 30min is beneficial to the recovery of the crystal structure of the single crystal TiN electrode film and the elimination of the internal defects of the single crystal TiN electrode film; the gradual temperature reduction is helpful for stabilizing the quality of the monocrystal TiN electrode film.
Further, in step S1, the target distance is adjusted to 5.5cm, the laser fluence frequency is 5Hz, and the heating temperature of the sapphire substrate is 600-700 ℃. The adoption of higher sapphire substrate temperature is beneficial to improving the surface atomic mobility in the deposition process, the three-dimensional island growth of the single crystal TiN electrode film can be effectively inhibited, and the quality of the single crystal TiN electrode film is improved. Meanwhile, proper sapphire village bottom temperature, inter-target distance, laser energy and frequency are set, so that the deposition of a compact and flat single crystal TiN electrode film is facilitated.
The invention also provides a single crystal TiN electrode film, which is obtained by the preparation method of the single crystal TiN electrode film.
Compared with the prior art, the method adopts the high-energy laser beam to etch the TiN target material, can improve the surface atomic mobility of the single crystal TiN electrode film, is beneficial to improving the growth quality of the single crystal TiN electrode film, and the formed single crystal TiN electrode film is an epitaxial film which has the stoichiometric ratio close to 1:1 and the (111) crystal face height preferred orientation growth, has compact and flat surface, good ductility and crystallinity, and excellent thermal stability, chemical stability and electrical conductivity. The single crystal TiN electrode is metallically conductive, has small square resistance of only about 20 omega at the daily working temperature (100-350 ℃) of a related electrode device, and is suitable for being used as an electrode film; the method has great application value in thin film resistors, diffusion barrier layers in large-scale integrated circuit processes and field effect transistor gate electrodes.
Drawings
FIG. 1 is an X-ray diffraction pattern of a single-crystal TiN electrode film of the present invention.
FIG. 2 shows a single crystal TiN electrode film of the present invention
Figure BDA0002569084980000031
And scanning the graph.
FIG. 3 is a diagram of reciprocal space RSM of the single crystal TiN electrode film of the present invention.
FIG. 4 is an atomic force microscope topography of the single crystal TiN electrode film of the invention.
FIG. 5 is a graph showing the conductivity test of the single crystal TiN electrode film of the present invention.
Detailed Description
The present inventors have concentrated their efforts on the electrode thin film for many years, and in particular, they have made efforts to develop a high-quality single crystal electrode thin film with excellent conductivity, so as to improve the high conductivity of the single crystal TiN electrode thin film of the prior art.
The method comprises the steps of firstly preparing the single crystal TiN electrode film, and then detecting the shape, the roughness, the thickness, the crystallization category, the crystallinity, the interface ductility, the conductivity and the like of the single crystal TiN electrode film.
The preparation method of the single crystal TiN electrode film comprises the following preparation steps:
(1) and cleaning the sapphire substrate.
Preferably, the specific steps of cleaning the sapphire substrate are as follows: ultrasonically cleaning the sapphire substrate by using an organic solvent for 13-17 min, and then washing by using deionized water; then putting the sapphire substrate into concentrated H2SO4With concentrated H3PO4Boiling the mixed solution in a volume ratio of 3:1 for 8-12 min, and then washing with deionized water; and finally, blowing the mixture by using nitrogen for standby.
(2) Heating the sapphire substrate and heating the sapphire substrate at a temperature of 0.6 to 1.0J/cm in a vacuum environment2Laser energy density of, in the sapphire substrateAnd a TiN target material is sputtered by adopting pulse laser on the bottom.
Preferably, the TiN target material is a TiN ceramic target material with the purity of 99.99 percent; heating the sapphire substrate by gradually increasing the temperature, wherein the heating rate is 8-12 ℃/min; the vacuum degree of the vacuum environment is 10-4Pa; the energy density is 0.8J/cm2. Further, the target distance is adjusted to 5.5cm, the laser energy flow frequency is 5Hz, and the heating temperature of the sapphire substrate is 600-700 ℃.
(3) And after the TiN film is deposited on the sapphire substrate, in-situ annealing is carried out, and then the temperature is cooled to room temperature, so that the monocrystal TiN electrode film is obtained.
Preferably, after the in-situ annealing is carried out for 30min, the temperature is gradually reduced to room temperature, and the temperature reduction rate is 4-6 ℃/min.
The invention also provides a single crystal TiN electrode film, which is obtained by the preparation method of the single crystal TiN electrode film.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The preparation method of the single crystal TiN electrode film comprises the following steps: and depositing and growing a single crystal TiN electrode film on the surface of the clean sapphire substrate by controlling the temperature of the sapphire substrate, the laser energy density, the vacuum degree of a growing environment and the working procedures of cooling and annealing. The method specifically comprises the following steps:
(1) and cleaning the sapphire substrate.
Ultrasonically cleaning the sapphire substrate for 13min by using an organic solvent, and then washing by using deionized water; the sapphire substrate was then placed in 75 wt% H2SO4And 85 wt% of H3PO4Boiling for 8min in a mixed solution with a volume ratio of 3:1, and then washing with deionized water; and finally, blowing the mixture by using nitrogen for standby.
(2) And depositing a TiN film on the surface of the sapphire substrate.
Heating the sapphire substrate to 600 ℃ at a temperature rise rate of 8 ℃/min and keeping the vacuum degree at 10-4Pa vacuum environment at 0.6J/cm2The laser light energy density of (a) is,and (3) sputtering a TiN ceramic target material with the purity of 99.99% on the surface of the sapphire substrate by adopting pulse laser. Further, the target spacing was adjusted to 5.5cm, and the laser fluence frequency was 5 Hz.
(3) Annealing and cooling to obtain the monocrystal TiN electrode film.
After the TiN film is deposited on the sapphire substrate, annealing in situ for 30min, and then cooling to room temperature at the cooling rate of 4 ℃/min to obtain the monocrystal TiN electrode film.
Example 2
This example 2 is the same as example 1 in the preparation of a single-crystal TiN electrode film, except for the difference in the condition parameters during the preparation.
(1) And cleaning the sapphire substrate.
Ultrasonically cleaning the sapphire substrate by using an organic solvent for 15min, and then washing by using deionized water; the sapphire substrate was then placed in 75 wt% H2SO4And 85 wt% of H3PO4Boiling for 10min in a mixed solution with a volume ratio of 3:1, and then washing with deionized water; and finally, blowing the mixture by using nitrogen for standby.
(2) And depositing a TiN film on the surface of the sapphire substrate.
Heating the sapphire substrate to 650 ℃ at a heating rate of 10 ℃/min and under a vacuum degree of 10 DEG C-4Vacuum environment of Pa, at 0.8J/cm2The laser energy density of (1) is that a TiN ceramic target material with the purity of 99.99 percent is sputtered on the surface of the sapphire substrate by adopting pulse laser. Further, the target spacing was adjusted to 5.5cm, and the laser fluence frequency was 5 Hz.
(3) Annealing and cooling to obtain the monocrystal TiN electrode film.
After the TiN film is deposited on the sapphire substrate, annealing in situ for 30min, and then cooling to room temperature at the cooling rate of 5 ℃/min to obtain the monocrystal TiN electrode film.
Example 3
This example 3 is the same as example 1 and example 2 in the preparation of single crystal TiN electrode thin films, except for the difference in the condition parameters during the preparation.
(1) And cleaning the sapphire substrate.
Ultrasonically cleaning the sapphire substrate for 17min by using an organic solvent, and then washing by using deionized water; the sapphire substrate was then placed in 75 wt% H2SO4And 85 wt% of H3PO4Boiling for 12min in a mixed solution with a volume ratio of 3:1, and then washing with deionized water; and finally, blowing the mixture by using nitrogen for standby.
(2) And depositing a TiN film on the surface of the sapphire substrate.
Heating the sapphire substrate to 700 deg.C at a temperature rise rate of 12 deg.C/min, and maintaining the vacuum degree at 10-4Pa vacuum environment at 1.0J/cm2The laser energy density of (1) is that a TiN ceramic target material with the purity of 99.99 percent is sputtered on the surface of the sapphire substrate by adopting pulse laser. Further, the target spacing was adjusted to 5.5cm, and the laser fluence frequency was 5 Hz.
(3) Annealing and cooling to obtain the monocrystal TiN electrode film.
After the TiN film is deposited on the sapphire substrate, annealing in situ for 30min, and then cooling to room temperature at the cooling rate of 6 ℃/min to obtain the monocrystal TiN electrode film.
Further, the single crystal TiN electrode films prepared in examples 1 to 3 were tested for morphology, roughness, thickness, type of crystallization, crystallinity, interfacial ductility, and conductivity.
Referring to fig. 1-3, fig. 1 is an X-ray diffraction diagram of the single crystal TiN electrode film of the present invention. As can be seen from FIG. 1, the TiN peak is sharp and has satellite peaks, which proves good crystal quality and smooth interface and surface. From FIG. 2 of the single crystal TiN electrode film of the present invention
Figure BDA0002569084980000061
Scanning view shows that TiN (311)cThe peak shows six-fold symmetry and is located at Al2O3(1 1 1 9)hThe superposition of peaks shows that the single crystal TiN electrode film is single crystal epitaxy, and the epitaxial relationship is TiN (111)c[2-1-1]c//Al2O3(0 0 6)h[1 1 0]h. Further, from FIG. 3, the reciprocity space RSM diagram of the single crystal TiN electrode film of the present invention, it was confirmed that the single crystal TiN electrode film is a single crystal epitaxial film.
Referring to fig. 4, fig. 4 is an atomic force microscopy topographic map of the single crystal TiN electrode thin film of the present invention, wherein a) is a 10 × 10 μm micro-domain atomic force microscopy map, and b) is a 3 × 3 μm micro-domain atomic force microscopy map in fig. 4. Further, as can be seen from the analysis of fig. 4, the single crystal TiN electrode film has good crystallinity and good surface flatness, and the roughness of the single crystal TiN electrode film is only 0.1nm, so that the single crystal TiN electrode film is smooth and flat, and is beneficial to the subsequent fine processing such as photoetching, etching and the like.
Referring to fig. 5, fig. 5 is a graph showing the conductivity of the single crystal TiN electrode film according to the present invention, wherein the conductivity graph shows that the single crystal TiN electrode film exhibits metallic conductivity, and the sheet resistance of the single crystal TiN electrode film is relatively low, only about 20 Ω at the daily operating temperature (100-350 ℃) of the related electrode device, and the single crystal TiN electrode film is suitable for being used as an electrode film.
In summary, the single crystal TiN electrode film and the preparation method thereof of the present invention have the following characteristics:
(1) the invention selects three liquids to clean and process the surface of the sapphire substrate, so that the surface of the sapphire substrate keeps higher flatness, and the invention is beneficial to the flat and preferred epitaxial growth of the single crystal TiN electrode film.
(2) The invention adopts higher laser energy flux density and high substrate temperature to carry out pulse laser sputtering on the TiN target material; the method is favorable for the stoichiometric ratio of the monocrystal TiN electrode film to be close to 1:1 and the (111) crystal face height preferred orientation growth, and has compact and flat surface, good ductility and crystallinity.
(3) The single crystal TiN electrode film prepared by the invention is metallically conductive, has small square resistance of only about 20 omega at the daily working temperature (100-350 ℃) of related electrode devices, and is suitable for being used as an electrode film; and has excellent thermal stability, chemical stability and electrical conductivity.
(4) The single crystal TiN electrode film prepared by the invention has great application value in a film resistor, a diffusion barrier layer in a large-scale integrated circuit process and a field effect tube gate electrode.
(5) The invention adopts the pulse laser deposition technology to prepare the monocrystal TiN electrode film, and has the advantages of no pollution, simple process, accurate control of film stoichiometry, preparation of multilayer films, epitaxial growth of monocrystal films with abrupt heterojunction interfaces and the like.
Compared with the prior art, the invention has mature production technology, better device quality, high mechanical strength, easy processing and cleaning and good stability, and can be applied to the sapphire substrate grown at high temperature; then, the density of the mixture is 0.6 to 1.0J/cm2Carrying out pulse laser sputtering on the TiN target material with high laser energy flux density and high substrate temperature; the formed monocrystal TiN electrode film is an epitaxial film which grows in a preferred orientation mode with the stoichiometric ratio close to 1:1 and (111) crystal face height, the surface is compact and flat, and the monocrystal TiN electrode film has good ductility and crystallinity and presents metallic conduction; and the square resistance is small and is only about 20 omega at the daily working temperature (100-350 ℃) of the related electrode device; and excellent thermal stability, chemical stability and electrical conductivity. Therefore, the high-energy laser beam is adopted to etch the TiN target material, high-temperature and high-pressure plasma is further generated, the plasma directionally expands locally and is deposited on the sapphire substrate to form the single crystal TiN electrode film, the surface atomic mobility of the single crystal TiN electrode film can be improved, the growth quality of the single crystal TiN electrode film is improved, and the single crystal TiN electrode film which is single in orientation and has the stoichiometric ratio close to 1:1 is formed. The single crystal TiN electrode has great application value in a thin film resistor, a diffusion barrier layer in a large-scale integrated circuit process and a field effect tube gate electrode. Meanwhile, the invention adopts the pulse laser deposition technology to prepare the monocrystal TiN electrode film, and has the advantages of no pollution, simple process, capability of accurately controlling the film stoichiometry, capability of preparing multilayer films, capability of epitaxially growing monocrystal films with abrupt heterojunction interfaces and the like.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (9)

1. A preparation method of a monocrystal TiN electrode film is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
s1: heating the sapphire substrate and heating the sapphire substrate at a temperature of 0.6 to 1.0J/cm in a vacuum environment2The laser energy density of (2) is that a TiN target material is sputtered on the sapphire substrate by adopting pulse laser;
s2: and after the TiN film is deposited on the sapphire substrate, in-situ annealing is carried out, and then the temperature is cooled to room temperature, so that the monocrystal TiN electrode film is obtained.
2. The method for preparing a single-crystal TiN electrode film according to claim 1, wherein: before step S1, cleaning the sapphire substrate; the specific steps of cleaning the sapphire substrate are as follows: ultrasonically cleaning the sapphire substrate by using an organic solvent for 13-17 min, and then washing by using deionized water; then putting the sapphire substrate into concentrated H2SO4With concentrated H3PO4Boiling the mixed solution in a volume ratio of 3:1 for 8-12 min, and then washing with deionized water; and finally, blowing the mixture by using nitrogen for standby.
3. The method for preparing a single crystal TiN electrode film according to claim 2, wherein: in step S1, the TiN target is a TiN ceramic target having a purity of 99.99%.
4. A method for preparing a single crystal TiN electrode film according to claim 3, wherein: in step S1, the energy density is 0.8J/cm2。
5. The method for preparing a single crystal TiN electrode film according to claim 4, wherein: in step S1, the vacuum degree of the vacuum environment is 10-4Pa。
6. A method for preparing a single crystal TiN electrode film according to claim 5, wherein: in step S1, the sapphire substrate is heated by gradually raising the temperature at a rate of 8-12 ℃/min.
7. The method for preparing a single crystal TiN electrode film according to claim 6, wherein: in step S2, after the in-situ annealing is carried out for 30min, the temperature is gradually reduced to room temperature at a rate of 4-6 ℃/min.
8. A method for preparing a single crystal TiN electrode film according to claim 7, wherein: in step S1, the target distance is adjusted to 5.5cm, the laser energy flux frequency is 5Hz, and the heating temperature of the sapphire substrate is 600-700 ℃.
9. A single crystal TiN electrode film is characterized in that: the single crystal TiN electrode film of any one of claims 1 to 8.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000228A (en) * 2022-05-13 2022-09-02 厦门大学 High-performance Ga 2 O 3 Thin film active solar blind ultraviolet detector and preparation method thereof

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CN110444618A (en) * 2019-08-09 2019-11-12 南京大学 Solar blind ultraviolet detector and preparation method thereof based on amorphous oxide gallium film
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