CN115747758A - Preparation method of patterned h-BN film and MIS semiconductor device - Google Patents
Preparation method of patterned h-BN film and MIS semiconductor device Download PDFInfo
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Abstract
The invention provides a preparation method of a graphical h-BN film and an MIS semiconductor device. The preparation method of the h-BN film comprises the following steps: preparing graphical GaN on a substrate; preparing Cu on the patterned GaN to form patterned Cu; growing a boron nitride precursor on the patterned Cu to obtain an h-BN film, and thus obtaining the patterned h-BN film; according to the preparation method of the h-BN film, the h-BN grows on the Cu substrate but cannot grow on the GaN by utilizing the difference of the catalytic characteristics of the Cu substrate and the GaN substrate, so that the aim of growing the micropatterned h-BN in situ is fulfilled, and the problems of carrier recombination, electric leakage and the like caused by edge defects brought by the traditional two-dimensional material pattern etching process are avoided; the h-BN film prepared by the method is used as a dielectric layer to prepare the MIS semiconductor device, so that the performance and the working stability of the semiconductor device can be improved.
Description
Technical Field
The invention relates to the technical field of two-dimensional material growth and semiconductor devices, in particular to a graphical h-BN film and a preparation method of an MIS semiconductor device.
Background
The h-BN (hexagonal boron nitride) film has very high transparency, thermal conductivity and mechanical strength, high oxidation resistance and good stability at high temperature. In addition, the h-BN film has the properties of super smooth planes, no dangling bonds and charge traps, molecular structure similarity with graphene and the like. The h-BN films can be used in a variety of applications such as dielectric layers, transparent and flexible electronic devices, deep ultraviolet emitters, capacitive energy storage devices, protective layers, and multifunctional nanopores. For these applications, the h-BN film used needs to have the characteristics of large size, uniform thickness, no defects and the like. However, even if a high-quality, large-area and good-uniformity monocrystalline h-BN film is grown, the monocrystalline h-BN film still faces to an etching process, the grown high-quality, large-area and good-uniformity monocrystalline h-BN film is etched into a required shape and size, the processes can damage the structure of the h-BN film, particularly the edge of the h-BN film, inevitable grain boundaries, defects and pollutants can be introduced, the problems of carrier recombination, electric leakage and the like are caused, the application of the h-BN film is restricted, and the usability of the h-BN film is reduced.
There are many methods for preparing h-BN films, including mechanical peeling, liquid phase peeling, unfolding of BN nanotubes, substitution reactions, radio frequency magnetron sputtering, electron beam irradiation, and Chemical Vapor Deposition (CVD). Among them, the CVD method has been identified as a common approach to synthesize large-sized nanosheets. Recently, atmospheric pressure CVD and low pressure CVD systems have been developed for growing large area h-BN films.
In addition, the h-BN film has the properties of super smooth plane, no dangling bond and charge trap, band gap width of 6eV and the like, so that the h-BN film has great advantages as an insulating layer in a semiconductor device and can be applied to a high-performance MIS type electronic device. In CVD systems, cu foil is often used as a catalytic metal substrate for growing h-BN films. Based on the characteristic that the Cu catalytic metal substrate is easy to etch, the micro-patterned Cu substrate is convenient to manufacture, and the growth of the micro-patterned h-BN film can be realized on the micro-patterned Cu substrate. Meanwhile, because the h-BN film grown on the Cu substrate has the transfer requirement, in the transfer process, a plurality of steps exist, including the processes of removing photoresist on four sides of the substrate, preparing solution (fast corrosion), slowly corroding, cleaning, transferring, removing photoresist, cleaning and the like, wherein the h-BN film is difficult to avoid being damaged.
Based on the defects of the existing h-BN film preparation method, the improvement on the method is needed.
Disclosure of Invention
In view of the above, the present invention provides a method for manufacturing a patterned h-BN thin film and a MIS semiconductor device, so as to solve or at least partially solve the problems in the prior art.
In a first aspect, the invention provides a preparation method of a graphical h-BN film, which comprises the following steps:
providing a substrate;
preparing patterned GaN on the substrate;
preparing Cu on the patterned GaN to form patterned Cu;
and growing the boron nitride precursor on the patterned Cu to obtain the h-BN film, thus obtaining the patterned h-BN film.
Preferably, the method for preparing the patterned h-BN film on the substrate specifically comprises the following steps:
growing a GaN film on the substrate;
growing SiO on the GaN film 2 A film;
in the SiO 2 Coating a first photoresist on the film, exposing to obtain a pattern matched with the patterned GaN, developing, and etching SiO 2 Removing the first photoresist to form a patterned SiO film 2 ；
Etching the GaN film, and etching off the patterned SiO 2 And obtaining the patterned GaN.
Preferably, the method for preparing the patterned h-BN thin film, wherein the step of preparing Cu on the patterned GaN to form the patterned Cu specifically comprises the following steps:
and coating a second photoresist on the patterned GaN, exposing a pattern matched with the patterned Cu, growing a Cu film on the second photoresist, and removing the second photoresist and the Cu film on the second photoresist to obtain the patterned Cu.
Preferably, the method for preparing the patterned h-BN film by growing the boron nitride precursor on the patterned Cu to obtain the h-BN film specifically comprises the following steps:
placing the substrate with patterned Cu on H 2 Flowing down, annealing at 950-1070 deg.C for 0.5-3 h;
and placing the annealed substrate in chemical vapor deposition equipment, heating a growth chamber to 1030-1070 ℃, introducing a boron nitride precursor, setting the temperature of a precursor heating zone to 70-90 ℃, and growing a decomposition product of the boron nitride precursor on the patterned Cu to obtain the h-BN film.
Preferably, the preparation method of the patterned h-BN film comprises the step of preparing a boron nitride precursor BH 3 NH 3 、(HBNH) 3 、BF 3 NH 3 、BCl 3 NH 3 At least one of (1).
Preferably, the method for preparing the patterned h-BN film on the substrate specifically comprises the following steps:
by NH 3 And TMGa is respectively used as an N source and a Ga source for GaN growth, and GaN is grown on the substrate.
Preferably, the substrate comprises one of a sapphire substrate, a silicon carbide substrate, a gallium nitride substrate, a silicon substrate, a sapphire/gallium nitride substrate and a silicon carbide/gallium nitride substrate;
in the step of preparing Cu on the patterned GaN, the thickness of Cu is 40-60 nm.
In a second aspect, the present invention further provides a method for manufacturing an MIS semiconductor device, comprising the steps of:
preparing a graphical h-BN film by adopting the method;
corroding copper below the h-BN film by using Cu metal corrosive liquid to enable the h-BN film to be deposited on the patterned GaN;
and coating a third photoresist on the h-BN film, exposing a pattern matched with the patterned h-BN film, growing a metal film on the third photoresist, and removing the third photoresist and the metal film on the third photoresist to obtain the patterned MIS semiconductor device.
Preferably, in the method for manufacturing the MIS-type semiconductor device, the Cu metal etching solution includes water, HCl and H 2 O 2 Wherein the water, HCl and H 2 O 2 The volume ratio of (3) to (160) to (20) to (30) to (20 to 30).
Preferably, in the method for manufacturing the MIS-type semiconductor device, the metal thin film includes one of a Ni thin film, a Ti thin film, an Al thin film, a V thin film, an Au thin film, and a Cu thin film.
Compared with the prior art, the preparation method of the graphical h-BN film and the MIS semiconductor device has the following technical effects:
according to the preparation method of the patterned h-BN film, the Cu film is deposited in the pattern on the patterned GaN substrate, and the h-BN grows on the Cu substrate but cannot grow on the GaN by utilizing the difference of catalytic characteristics of the Cu substrate and the GaN substrate, so that the aim of growing the micro-patterned h-BN in situ is fulfilled, and the problems of carrier recombination, electric leakage and the like caused by edge defects caused by the traditional two-dimensional material pattern etching process are solved; the h-BN film prepared by the method is used as a dielectric layer to prepare the MIS semiconductor device, so that the performance and the working stability of the semiconductor device can be improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing a patterned h-BN film according to the invention;
FIG. 2 is a schematic diagram of the present invention for producing patterned GaN on a substrate;
FIG. 3 is a schematic diagram of the present invention for preparing Cu on patterned GaN to form patterned Cu;
fig. 4 to 5 are schematic views of the fabrication method of the MIS semiconductor device of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present invention, it should be understood that the relation indicating the orientation or position such as "up" is based on the orientation or position relation shown in the drawings, or the orientation or position relation which the product of the present invention is used to usually put, or the orientation or position relation which is usually understood by those skilled in the art, and is only for the convenience of describing the present invention and simplifying the description, but does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a preparation method of a graphical h-BN film, as shown in figure 1, comprising the following steps:
s1, providing a substrate;
s2, preparing graphical GaN on the substrate;
s3, preparing Cu on the patterned GaN to form patterned Cu;
and S4, growing the boron nitride precursor on the patterned Cu to obtain the h-BN film, and thus obtaining the patterned h-BN film.
According to the preparation method of the patterned h-BN film, the Cu film is deposited in the pattern on the patterned GaN substrate, and the h-BN grows on the Cu substrate but cannot grow on the GaN by utilizing the difference of the catalytic characteristics of the two substrates, so that the aim of growing the micro-patterned h-BN in situ is fulfilled, the problems of carrier recombination, electric leakage and the like caused by edge defects caused by the traditional two-dimensional material pattern etching process are avoided, and the performance and the working stability of a micro-size semiconductor device are improved.
In some embodiments, referring to fig. 2, the step S2 of preparing patterned GaN on the substrate specifically includes:
growing a GaN thin film 11 on a substrate 10 as shown by S20 in fig. 2;
growing SiO on GaN film 11 2 A film 12, as shown at S21 in fig. 2;
in SiO 2 The film 12 is coated with a first photoresist 13, as shown by S22 in FIG. 2, and then exposed to a pattern matching the patterned GaN, developed, and etched to form SiO 2 The thin film 12, as shown by S23-S24 in FIG. 2, is removed from the first photoresist 13 to form a patterned SiO 2 As indicated by S25 in fig. 2;
after etching the GaN film 11, the patterned SiO is etched away 2 As shown in S26 to S27 in FIG. 2, patterned GaN was obtained.
Specifically, in the above embodiment, MOCVD is adopted to grow a GaN thin film with a certain thickness (for example, the thickness is 350 to 450 nm) on a substrate; then, a certain thickness (for example, 150-250 nm) of SiO is grown on the substrate/GaN by PECVD method 2 A film; then on the substrate/GaN/SiO 2 Coating a first photoresist, exposing to obtain a pattern suitable for patterned GaN by using a mask, developing, and performing RIE (reactive ion etching) with Ar and fluorocarbon (CHF) 3 Or CF 4 ) Etching away SiO 2 A film; removing the first photoresist by using acetone and ethanol to form a patterned substrate/GaN/SiO 2 A template; etching with ICP and Cl 2 /BCl 3 Mixed gas, etching GaN with a certain thickness; finally, ar and fluorocarbon (CHF) are utilized in the same RIE process as described above 3 Or CF 4 ) Removing the patterned SiO 2 And finally obtaining the patterned GaN from the rest part of the film.
In some embodiments, referring to fig. 3, the step S3 of preparing Cu on the patterned GaN to form patterned Cu specifically includes:
and coating a second photoresist 14 on the patterned GaN, exposing a pattern matched with the patterned Cu as shown in S30 in FIG. 3, growing a Cu thin film 15 on the second photoresist 14 as shown in S31 in FIG. 3, and removing the second photoresist 14 and the Cu thin film 15 on the second photoresist as shown in S32 in FIG. 3 to obtain the patterned Cu.
Specifically, in the above embodiment, a second photoresist is coated on the patterned substrate/GaN, and the corresponding pattern is exposed; then, selecting a Cu metal evaporation source by adopting electron beam evaporation equipment, and growing a Cu thin film with the thickness of 40-60 nm based on monitoring of a film thickness instrument; then, the photoresist and the Cu film on the photoresist are removed by acetone, and the patterned substrate/GaN/Cu is formed.
In some embodiments, referring to fig. 4, the growing the h-BN film on the patterned Cu using the boron nitride precursor specifically includes:
placing the substrate with patterned Cu on H 2 Flowing down, annealing at 900-1200 deg.c for 0.5-2 hr;
and (3) placing the annealed substrate in chemical vapor deposition equipment, introducing a boron nitride precursor, setting the temperature of a heating zone of the precursor to be 70-90 ℃, and growing a decomposition product of the boron nitride precursor on the patterned Cu to obtain the h-BN film 16.
Specifically, in the above embodiment, the patterned substrate/GaN/Cu is grown at 250-350 standard cubic centimeters per minute (sccm) of H prior to growth 2 Flowing down, annealing at 950-1070 deg.C for 0.5-3 h; placing the annealed substrate/GaN/Cu in chemical vapor deposition equipment, heating a growth chamber to 1030-1070 ℃ (preferably, heating the growth chamber to 1050 ℃), introducing a boron nitride precursor, setting the temperature of a precursor heating zone to 70-90 ℃, introducing a decomposition product of the boron nitride precursor into an h-BN growth zone, and growing for 25-35 min so as to grow h-BN on the patterned substrate/GaN/Cu but not grow an h-BN film on the GaN; after the H-BN thin film grows, the heating program of the precursor and the growth area is closed, and the growth area of the H-BN thin film is H of 25-35 sccm 2 Flowing down and naturally cooling to room temperature.
In some embodiments, the boron nitride precursor comprises BH 3 NH 3 、(HBNH) 3 、BF 3 NH 3 、BCl 3 NH 3 At least one of (1).
In some embodiments, fabricating patterned GaN on a substrate specifically includes:
by NH 3 And TMGa are grown as GaN, respectivelyAnd an N source and a Ga source are grown on the substrate to obtain the GaN.
Specifically, a GaN film, NH, is grown on a substrate by MOCVD 3 And TMGa (trimethylgallium) as an N source and a Ga source for GaN growth, respectively; h 2 As a carrier gas; the temperature of the reaction chamber substrate tray is fixed at 1000-1100 ℃, and the reaction chamber substrate tray rotates at the speed of 5-15 r/min; the temperature of the top wall of the reaction chamber is fixed at 300-400 ℃, and the flow rate of TMGa is fixed at 100-200 mu mol/min; and growing the GaN film with the thickness of 350-450 nm by using the conditions.
In some embodiments, the substrate comprises one of a sapphire substrate, a silicon carbide substrate, a gallium nitride substrate, a silicon substrate, a sapphire/gallium nitride substrate, a silicon carbide/gallium nitride substrate; if the substrate is made of materials such as Sapphire (Sapphire), silicon carbide (SiC), silicon Si and the like, a Sapphire/GaN template substrate material and a SiC/GaN template substrate material are grown by using a Metal Organic Chemical Vapor Deposition (MOCVD) method, wherein the properties of a GaN wide bandgap semiconductor are mainly used; preferably, a Cu film of a deposited catalytic metal is adopted on the surface of the Sapphire/GaN template by utilizing Sapphire/GaN template substrate materials for selectively catalytically growing h-BN micro-pattern arrays.
In some embodiments, in the step of preparing Cu on patterned GaN, the thickness of Cu is 40 to 60nm; although the Cu film evaporated by the electron beam is deposited on the patterned GaN substrate, the excessive h-BN film is generated because the Cu film exceeds the edge of the upper part of the patterned GaN, so that when the patterned h-BN film after the patterned Cu substrate is corroded falls on the GaN, the h-BN edge generates a grain boundary, thereby affecting the quality of a semiconductor device; the thickness of the patterned Cu substrate needs to be controlled so that it does not generate excessive h-BN film. The method improves the possibility of growing the graphical h-BN film by utilizing different growth mechanisms between h-BN films grown on the GaN substrate and the Cu substrate; meanwhile, due to the difference of growth mechanisms and the control of the thickness of the Cu substrate, the method plays a crucial role in controlling the size and the shape of the h-BN film, so that the patterned h-BN film semiconductor device is realized, and the performance and the stability of the device can be greatly improved. The method mainly solves the problem that certain possible defects are inevitably introduced when the h-BN film is used in the preparation of the semiconductor device and the special size and shape are required. The invention has the advantages of simple process, obvious effect, wide application prospect and the like.
Based on the same inventive concept, the embodiment of the application also provides a preparation method of the MIS semiconductor device, which comprises the following steps:
preparing a graphical h-BN film by adopting the method;
corroding copper below the h-BN film by using Cu metal corrosive liquid to enable the h-BN film to be deposited on the patterned GaN;
and coating a third photoresist on the h-BN film, exposing a pattern matched with the patterned h-BN film, growing a metal film on the third photoresist, and removing the third photoresist and the metal film on the third photoresist to obtain the patterned MIS semiconductor device.
The MIS semiconductor device is a semiconductor-insulation-Metal (MIS) type semiconductor device, an h-BN film is used as a dielectric layer, and the micro-patterned h-BN is used as the dielectric layer to prepare a high-performance MIS type semiconductor device array. Specifically, referring to fig. 4 to 5, the Cu metal etchant is used to etch the Cu film 15 under the h-BN film 16, as shown in S41 in fig. 4, the etched h-BN film 16 is dropped on the patterned GaN, and the interaction between the h-BN film and the patterned GaN surface is used to ensure that the h-BN film can remain on the top of the patterned GaN after the Cu is etched, as shown in S42 in fig. 4; and coating a third photoresist 17 on the h-BN film 16, exposing a pattern which is matched with the patterned h-BN film as shown by S50 in figure 5, growing a metal film 18 on the third photoresist 17, removing the third photoresist 17 and the metal film 18 on the third photoresist as shown by S51 in figure 5, and obtaining the patterned MIS semiconductor device as shown by S52 in figure 5.
In some embodiments, the Cu metal etchant solution includes water, HCl, and H 2 O 2 Wherein water, HCl and H 2 O 2 The volume ratio of (3) to (160) to (20) to (30) to (20 to 30).
In particular, etching of Cu substrate in h-BN filmEtching: comprises rapid corrosion and slow corrosion; preparing a rapid corrosion solution: 150ml of deionized water +25ml of HCl +25ml of H 2 O 2 (ii) a (HCl and H may be added as appropriate) 2 O 2 Ensuring the volume ratio of 1; the preparation method of the slow corrosion solution comprises the following steps: in 1000ml of deionized water, enough Na was added 2 (SO 4 ) 2 Powder, preparing to obtain saturated Na 2 (SO 4 ) 2 The solution is the slow corrosion solution.
Rapidly corroding to a degree similar to the thickness of paper; when the corrosion is slow, a fan of the fume hood needs to be closed, and when Cu is corroded, the remained material is very thin and is easy to damage due to vibration; the height of the rapid corrosion solution is approximately parallel to that of the substrate/GaN/Cu/h-BN, and the corroded h-BN film floats above the patterned GaN, so that the subsequent fishing operation is facilitated; the height of the slow corrosive liquid is required to be approximately parallel to that of the substrate/GaN/Cu/h-BN; slowly transferring the substrate/GaN and h-BN film subjected to Cu corrosion into deionized water, and cleaning; the cleaned material film is slowly wrapped by the substrate/GaN in deionized water, and naturally dried after being placed (the h-BN film cannot be dried by heating and evaporation, otherwise special wrinkles can be generated), so that the h-BN film can be deposited on the patterned substrate/GaN.
Specifically, when the Cu substrate in the patterned h-BN film is corroded, the fast corrosion time is 30s, and the slow corrosion time is 5min.
In some embodiments, a photolithography process is used to coat a third photoresist on the h-BN film, exposing the patterned sapphire substrate/GaN/h-BN and the substrate/third photoresist; and then, depositing a metal film (as a metal electrode) with the thickness of 90-110 nm on the patterned sapphire substrate/GaN/h-BN by adopting an electron beam evaporation process, wherein the evaporated metal can be as follows: metals such as Ni, ti, al, V, au, cu, etc.; and then, washing away the third photoresist and the metal film thereon by using acetone to form a patterned substrate/GaN/h-BN metal structure, thereby forming the MIS type semiconductor device array.
In some embodiments, the first photoresist, the second photoresist, and the third photoresist used in the present application may be conventional photoresists, such as AZ703 photoresist, SU-8 photoresist, and the like.
The following further describes a method for producing the patterned h-BN film and a method for producing an MIS semiconductor device according to the present invention with specific examples. This section further illustrates the present invention with reference to specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. Reagents, methods and apparatus employed in the present invention are conventional in the art unless otherwise indicated.
Example 1
The embodiment of the application provides a preparation method of a graphical h-BN film, which comprises the following steps:
s1, providing a sapphire substrate;
s2, growing a GaN film and NH on the sapphire substrate by MOCVD 3 And TMGa (trimethylgallium) as an N source and a Ga source for GaN growth, respectively; h 2 As a carrier gas; the temperature of the reaction chamber substrate tray was fixed at 1050 ℃ and rotated at a rate of 10 r/min; the temperature of the top wall of the reaction chamber is fixed at 350 ℃, and the flow rate of TMGa is fixed at 150 mu mol/min; growing a GaN film with the thickness of 400nm by using the conditions;
s3, growing SiO with the thickness of 200nm on the sapphire substrate/GaN by adopting a PECVD method 2 A film; then on the sapphire substrate/GaN/SiO 2 Coating a first photoresist, exposing to obtain a pattern suitable for patterned GaN by using a mask, developing, and performing RIE (reactive ion etching) with Ar and fluorocarbon (CHF) 3 Or CF 4 ) Etching away SiO 2 A film; removing the first photoresist by using acetone and ethanol to form a patterned substrate/GaN/SiO 2 A template; etching with ICP and Cl 2 /BCl 3 Mixed gas is used for etching GaN with the thickness of 400 nm; finally, ar and fluorocarbon (CHF) are utilized in the same RIE process as described above 3 Or CF 4 ) Removing the patterned SiO 2 Finally obtaining a patterned sapphire substrate/GaN from the rest part of the film;
s4, coating a second photoresist on the patterned sapphire substrate/GaN, and exposing corresponding patterns; then, selecting a Cu metal evaporation source by adopting electron beam evaporation equipment, and growing a Cu thin film with the thickness of 50nm based on the monitoring of a film thickness instrument; then, removing the photoresist and the Cu film on the photoresist by using acetone to form a patterned sapphire substrate/GaN/Cu;
s5, forming the patterned sapphire substrate/GaN/Cu at the H of 300 standard cubic centimeters per minute (sccm) 2 Flowing down, and annealing at 1050 ℃ for 1h; then placing the annealed substrate/GaN/Cu in chemical vapor deposition equipment, heating a growth chamber to 1050 ℃, and introducing ammonia borane (H) 3 N-BH 3 ) Setting the temperature of a precursor heating zone at 80 ℃, introducing a decomposition product of a boron nitride precursor into an h-BN growth zone, and growing for 30min so as to grow an h-BN film on the patterned sapphire substrate/GaN/Cu; after the H-BN thin film is grown, the heating program of the precursor and the growth region is closed, and the growth region of the H-BN thin film is at H of 30sccm 2 Flowing down and naturally cooling to room temperature.
Example 2
The embodiment of the application provides a preparation method of an MIS semiconductor device, which comprises the following steps:
s1, obtaining a graphical h-BN film by adopting the method in the embodiment 1;
s2, corroding copper below the h-BN film by using a Cu metal corrosive liquid to enable the h-BN film to be deposited on the patterned GaN; the Cu metal corrosive liquid comprises 150mL of water, 25mL of HCl and 25mL of H 2 O 2 A mixture of (a);
s3, coating a third photoresist on the h-BN film, exposing a pattern matched with the patterned h-BN film, and depositing a metal film Ni with the thickness of 100nm on the patterned sapphire substrate/GaN/h-BN by adopting an electron beam evaporation process; and then, washing the photoresist and the metal film Ni on the photoresist by using acetone to form a patterned sapphire substrate/GaN/h-BN/metal structure, thus obtaining the MIS semiconductor device.
The present invention is not limited to the above-described preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a graphical h-BN film is characterized by comprising the following steps:
providing a substrate;
preparing graphical GaN on the substrate;
preparing Cu on the patterned GaN to form patterned Cu;
and growing the boron nitride precursor on the patterned Cu to obtain the h-BN film, thus obtaining the patterned h-BN film.
2. The method of claim 1, wherein the step of forming the patterned GaN film on the substrate comprises:
growing a GaN film on the substrate;
growing SiO on the GaN film 2 A film;
in the SiO 2 Coating a first photoresist on the film, exposing to obtain a pattern matched with the patterned GaN, developing, and etching SiO 2 Removing the first photoresist to form a patterned SiO 2 ；
Etching the GaN film, and etching off the patterned SiO 2 And obtaining the patterned GaN.
3. The method of preparing the patterned h-BN film of claim 1, wherein preparing Cu on the patterned GaN to form patterned Cu specifically comprises:
and coating a second photoresist on the patterned GaN, exposing a pattern matched with the patterned Cu, growing a Cu film on the second photoresist, and removing the second photoresist and the Cu film on the second photoresist to obtain the patterned Cu.
4. The method of claim 1, wherein growing the h-BN film on the patterned Cu using a boron nitride precursor specifically comprises:
placing the substrate with patterned Cu on H 2 Flowing down, annealing at 950-1070 deg.C for 0.5-3 h;
and placing the annealed substrate in chemical vapor deposition equipment, heating a growth chamber to 1030-1070 ℃, introducing a boron nitride precursor, setting the temperature of a precursor heating zone to 70-90 ℃, and growing the decomposition product of the boron nitride precursor on the patterned Cu to obtain the h-BN film.
5. The method of claim 1, wherein the boron nitride precursor comprises BH 3 NH 3 、(HBNH) 3 、BF 3 NH 3 、BCl 3 NH 3 At least one of (1).
6. The method of preparing a micropatterned h-BN film according to claim 1, wherein preparing patterned GaN on the substrate specifically comprises:
by NH 3 And TMGa is respectively used as an N source and a Ga source for GaN growth, and GaN is obtained by growing on the substrate.
7. The method of claim 1, wherein the substrate comprises one of a sapphire substrate, a silicon carbide substrate, a gallium nitride substrate, a silicon substrate, a sapphire/gallium nitride substrate, a silicon carbide/gallium nitride substrate;
in the step of preparing Cu on the patterned GaN, the thickness of Cu is 40-60 nm.
8. A preparation method of an MIS semiconductor device is characterized by comprising the following steps:
preparing a patterned h-BN film by adopting the method as claimed in any one of claims 1 to 7;
corroding copper below the h-BN film by using Cu metal corrosive liquid to enable the h-BN film to be deposited on the patterned GaN;
and coating a third photoresist on the h-BN film, exposing a pattern matched with the patterned h-BN film, growing a metal film on the third photoresist, and removing the third photoresist and the metal film on the third photoresist to obtain the patterned MIS semiconductor device.
9. The method of manufacturing a MIS type semiconductor device as claimed in claim 8, wherein said Cu metal etching liquid comprises water, HCl and H 2 O 2 Wherein the water, HCl and H 2 O 2 The volume ratio of (3) to (160) to (20) to (30) to (20 to 30).
10. The method of fabricating a MIS semiconductor device of claim 8, wherein the metal film comprises one of a Ni film, a Ti film, an Al film, a V film, an Au film, a Cu film.
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