CN116815162A - Method for growing CaO film by utilizing ALD technology - Google Patents
Method for growing CaO film by utilizing ALD technology Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 77
- 239000011575 calcium Substances 0.000 claims abstract description 69
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 66
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 230000012010 growth Effects 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 24
- 238000010926 purge Methods 0.000 claims abstract description 22
- 239000011261 inert gas Substances 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- -1 amidino calcium Chemical compound 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052710 silicon Inorganic materials 0.000 claims description 33
- 239000010703 silicon Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000010409 thin film Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical class [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 229910002601 GaN Inorganic materials 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 abstract description 5
- 239000003446 ligand Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
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- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000001409 amidines Chemical class 0.000 abstract 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- WDYUROGBUSFJNT-UHFFFAOYSA-N 2,2,3,3-tetramethylheptanedioic acid Chemical compound OC(=O)C(C)(C)C(C)(C)CCCC(O)=O WDYUROGBUSFJNT-UHFFFAOYSA-N 0.000 description 1
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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Abstract
The invention relates to a method for growing a CaO film by utilizing an ALD (atomic layer deposition) technology, belonging to the technical field of nano materials. The preparation method of the invention comprises the following steps: s1, placing a substrate subjected to wet chemical treatment in a reaction cavity of atomic layer deposition equipment, and introducing an amidine calcium precursor to perform chemical adsorption on the surface of the substrate; s2, after chemical adsorption in the S1 is saturated, introducing inert gas into the reaction cavity for purging, and then introducing oxygen precursor for reaction; s3, after the reaction of the S2 is finished, introducing inert gas into the reaction cavity for purging, and completing a single growth cycle; s4, repeating the growth cycle, and growing a CaO film on the surface of the substrate. Wherein the amidino ligand and the metal atom exhibit an unstable four-membered ring structure, so that the amidino calcium precursor has higher reactivity. The catalyst can react with other coreactants at a lower temperature, and can consume all hydroxyl groups in the film, so that the film can be crystallized smoothly in a low-temperature environment.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a method for growing a CaO film by using an ALD technology.
Background
CaO films have a wide band gap and a high dielectric constant. It can be used as a composite material or a component of a doped materialOr as a gate oxide compound suitable for GaN substrate matching, has great potential in power device applications. At present, the growing preparation of ALD-CaO film mainly uses Ca # i Pr 3 Cp) 2 Or Ca (thd) 2 As a source of calcium precursor. However, these calcium precursor sources have high source temperature, and the prepared thin film has relatively poor crystallinity, and can be obtained by relatively high growth temperature and even annealing.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for growing a CaO film by utilizing an ALD technology.
It is a first object of the present invention to provide a method for growing CaO thin films using ALD technique, comprising the steps of,
s1, placing a substrate subjected to wet chemical treatment in a reaction cavity of atomic layer deposition equipment, and introducing a calcium precursor to perform chemical adsorption on the surface of the substrate; the calcium precursor is an amidino calcium precursor;
s2, after chemical adsorption in the S1 is saturated, introducing inert gas into the reaction cavity for purging, and then introducing oxygen precursor for reaction;
s3, after the reaction of the S2 is finished, introducing inert gas into the reaction cavity for purging, and completing a single growth cycle;
and S4, repeating the growth cycle, and growing the CaO film on the surface of the substrate.
In one embodiment of the present invention, in S1, the wet chemical treatment is specifically: and cleaning the substrate by adopting one or more solvents of hydrofluoric acid, ammonia water, methanol, acetone, isopropanol and water.
In one embodiment of the invention, in S1, the substrate is selected from silicon, silicon dioxide, silicon nitride, silicon carbide, glass, sapphire, gallium nitride, or stainless steel having a planar or non-planar surface.
In one embodiment of the invention, in S1, the amidinate calcium precursor is selected from the group consisting of bis (N, N-di-isopropylacetamido) calcium (II) dimer or bis (N, N-di-isopropylformamidino) calcium (II) dimer.
In one embodiment of the present invention, in S1, the reaction chamber and the calcium precursor are heat-treated before growing the CaO film.
In one embodiment of the invention, the heating temperature of the reaction chamber is 100-400 ℃; the heating temperature of the calcium precursor is 50-200 ℃.
Further, the heating temperature of the reaction cavity is 200-300 ℃; the heating temperature of the calcium precursor is 100-160 ℃.
In one embodiment of the present invention, in S2, the oxygen precursor is selected from one or more of oxygen, ozone, hydrogen peroxide, oxygen plasma.
In one embodiment of the invention, in S2 and S3, the inert gas is independently selected from argon, nitrogen or helium; the purity of the inert gas is not lower than 99.999%.
In one embodiment of the invention, the calcium precursor and the oxygen precursor are pulsed into the reaction chamber in the presence of a carrier gas, which is nitrogen gas having a purity of not less than 99.999%.
A second object of the present invention is to provide a CaO film prepared by the method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The calcium source adopted in the method for growing the CaO film by utilizing the ALD technology is an amidino-based calcium precursor, wherein the amidino ligand and the metal atom show an unstable four-membered ring structure, so that the amidino-based calcium precursor has higher reactivity. The catalyst can react with other coreactants at a lower temperature, and can consume all hydroxyl groups in the film, so that the film can be crystallized smoothly in a low-temperature environment.
(2) The method for growing the CaO film by utilizing the ALD technology does not relate to dangerous sources such as inflammable and explosive sources, and the used calcium precursor source is convenient for safe transportation, storage and use and can effectively avoid dangerous chemical accidents. The film plating process is simple to operate, the atomic layer monolayer deposition and the cyclic growth can be realized, and the film grown at a relatively low temperature shows better crystallinity.
(3) The method for growing the CaO film by utilizing the ALD technology comprises the following steps: and sequentially introducing a calcium precursor source, closing a valve for waiting, purging high-purity gas, introducing an oxygen source, closing the valve for waiting, purging high-purity gas and the like into the reaction cavity. The adopted calcium precursor is an amidino calcium precursor. Compared with the common calcium sources of tetramethyl-heptanedioic acid ligand and cyclopentadienyl ligand, the calcium source of the amidino-based calcium precursor has higher thermal stability and reactivity, can generate better adsorption reaction with the oxygen precursor source, and realizes atomic layer deposition and cyclic growth of a film layer.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a structural formula of calcium acetamido in an embodiment of the present invention;
FIG. 2 is the growth data of CaO film at different source heating temperatures in example 1 of the present invention;
FIG. 3 is the growth data of CaO film at different deposition temperatures in example 2 of the present invention;
FIG. 4 is the growth data of CaO film at different cycle times in example 3 of the present invention;
FIG. 5 is an XRD pattern of CaO film in test example 1 according to the invention.
Detailed Description
In order to solve the technical problems, the invention provides a method for growing a CaO film by utilizing an ALD technology.
It is a first object of the present invention to provide a method for growing CaO thin films using ALD technique, comprising the steps of,
s1, placing a substrate subjected to wet chemical treatment in a reaction cavity of atomic layer deposition equipment, and introducing a calcium precursor to perform chemical adsorption on the surface of the substrate; the calcium precursor is an amidino calcium precursor;
s2, after chemical adsorption in the S1 is saturated, introducing inert gas into the reaction cavity for purging, and then introducing oxygen precursor for reaction;
s3, after the reaction of the S2 is finished, introducing inert gas into the reaction cavity for purging, and completing a single growth cycle;
and S4, repeating the growth cycle, and growing the CaO film on the surface of the substrate.
In one embodiment of the present invention, in S1, the wet chemical treatment is specifically: and cleaning the substrate by adopting one or more solvents of hydrofluoric acid, ammonia water, methanol, acetone, isopropanol and water.
Further, in S1, the wet chemical treatment specifically includes: the surface of the substrate is cleaned by adopting methanol, acetone, isopropanol and pure water in turn, and then is soaked in hydrofluoric acid solution, pure water and ammonia water solution.
Preferably, in S1, the wet chemical treatment is specifically: sequentially cleaning the surface of the silicon wafer for 5-10 min by adopting methanol, acetone, isopropanol and pure water to remove surface organic matters; then placing the treated silicon wafer into hydrofluoric acid solution to soak for 5s-30s, and etching the natural oxide layer on the surface of the silicon wafer; and (3) treating the etched silicon wafer in pure water for 10-12 s, and then soaking the silicon wafer in an ammonia water solution for 5-30 min.
Further, the wet chemical treatment can effectively reduce the roughness of the surface of the substrate, remove pollutants on the surface, reduce impurities and defects, and improve the nucleation condition so as to enhance the combination of the deposited film and obtain a smooth and flat film.
In one embodiment of the invention, in S1, the substrate is selected from silicon, silicon dioxide, silicon nitride, silicon carbide, glass, sapphire, gallium nitride, or stainless steel having a planar or non-planar surface.
In one embodiment of the invention, in S1, the amidinate calcium precursor is selected from the group consisting of bis (N, N-di-isopropylacetamido) calcium (II) dimer or bis (N, N-di-isopropylformamidino) calcium (II) dimer.
Further, in S1, the calcium amidinate precursor is selected from calcium acetamidinate.
Further, the amidinate calcium precursor is taken as a first reaction precursor source to carry out chemical adsorption on the surface of the substrate, and calcium atoms in the amidinate calcium precursor are adsorbed on the surface of the substrate.
In one embodiment of the present invention, in S1, the reaction chamber and the calcium precursor are heat-treated before growing the CaO film.
In one embodiment of the invention, the heating temperature of the reaction chamber is 100-400 ℃; the heating temperature of the calcium precursor is 50-200 ℃.
Further, the heating temperature of the reaction cavity is 200-300 ℃; by heating the reaction cavity, the substrate obtains high enough heat, promotes the chemical adsorption of the calcium precursor and the reaction of the calcium precursor and the oxygen precursor, and improves the film deposition rate.
Further, the heating temperature of the calcium precursor is 100-160 ℃. By heating the calcium precursor, the saturated vapor pressure of the precursor source in the calcium precursor source bottle is improved, the amount of the carrier gas carrying the calcium precursor is increased, and the deposition rate is improved.
Further, the heating temperature of the calcium precursor is 140-160 ℃.
In one embodiment of the present invention, in S2, the oxygen precursor is selected from one or more of oxygen, ozone, hydrogen peroxide, oxygen plasma.
Further, in S2, the oxygen precursor is selected from ozone.
In one embodiment of the invention, in S2 and S3, the inert gas is independently selected from argon, nitrogen or helium; the purity of the inert gas is not lower than 99.999%.
In one embodiment of the invention, the purge time is independently 10S-50S in S2 and S3.
Further, in S2 and S3, the purge times are independently 10S, 11S, 12S, 13S, 14S, 15S, 16S, 17S, 18S, 19S, 20S, 21S, 22S, 23S, 24S, 25S, 26S, 27S, 28S, 29S, 30S, 31S, 32S, 33S, 34S, 35S, 36S, 37S, 38S, 39S, 40S, 41S, 42S, 43S, 44S, 45S, 46S, 47S, 48S, 49S, 50S; or any time value between any two values.
Further, inert gas is introduced into the reaction chamber for purging, so that the reaction chamber and the redundant precursor source on the substrate are removed.
In one embodiment of the invention, the calcium precursor and the oxygen precursor are pulsed into the reaction chamber in the presence of a carrier gas, which is nitrogen gas having a purity of not less than 99.999%.
Further, the pulse conditions are: the pulse time is 1s-3s and the waiting time is 3s-10s.
In one embodiment of the invention, the carrier gas flow is 10sccm to 50sccm.
Further, the flow rate of the carrier gas is 10sccm, 11sccm, 12sccm, 13sccm, 14sccm, 15sccm, 16sccm, 17sccm, 18sccm, 19sccm, 20sccm, 21sccm, 22sccm, 23sccm, 24sccm, 25sccm, 26sccm, 27sccm, 28sccm, 29sccm, 30sccm, 31sccm, 32sccm, 33sccm, 34sccm, 35sccm, 36sccm, 37sccm, 38sccm, 39sccm, 40sccm, 41sccm, 42sccm, 43sccm, 44sccm, 45sccm, 46sccm, 47sccm, 48sccm, 49sccm, 50sccm; or any flow value between any two values.
In one embodiment of the present invention, in S4, the number of repetitions is 50-500.
Further, in S4, the number of repetitions is 50, 100, 150, 200, 250, 300, 350, 400, 450, 500; or any number of repetitions between any two values.
In one embodiment of the invention, the ALD technique is an atomic layer deposition technique selected from a thermal deposition process or a plasma deposition process.
A second object of the present invention is to provide a CaO film prepared by the method.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In the present invention, the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items, unless otherwise indicated.
In the present invention, unless otherwise indicated, all the experimental methods used in the examples of the present invention are conventional methods, and materials, reagents and the like used, unless otherwise indicated, are commercially available.
In the present invention, the purity of the high purity nitrogen gas used in the examples is not lower than 99.999% unless otherwise specified.
In the present invention, the carrier gas used in the examples was nitrogen having a purity of not less than 99.999% unless otherwise specified.
Example 1
The invention relates to a method for growing a CaO film by utilizing an ALD technology, which selects a silicon wafer as a substrate, calcium acetamido as a calcium precursor source and ozone as an oxygen precursor source, and specifically comprises the following steps:
s1, preprocessing a substrate: sequentially cleaning the surface of the silicon wafer for 5min by using acetone, methanol, isopropanol and pure water to remove surface organic matters; then placing the treated silicon wafer into hydrofluoric acid solution to soak for 25 seconds, etching to remove a natural oxide layer on the surface of the silicon wafer, treating the etched silicon wafer in pure water for 10 seconds, then placing the silicon wafer into ammonia water solution to soak for 25 minutes, drying the silicon wafer, placing the silicon wafer into a reaction cavity of ALD equipment within 1 minute, and vacuumizing to be lower than 1 Torr.
S2, inputting deposition working parameters: the heating temperature of the acetamido calcium (CAS number: 1959584-79-2, structure as shown in figure 1) is set to 80-160 ℃; the heating temperature of the reaction chamber was set at 250℃and the flow was set at 20sccm with the aid of a carrier gas in the pipeline. Before coating, the reaction cavity and the source bottle are stably heated for about 1h, and high-purity nitrogen is introduced into the reaction cavity of the ALD equipment for purging.
S3, introducing a calcium precursor source: and (3) opening a pneumatic valve, introducing high-purity nitrogen into the reaction cavity in a pulse mode, introducing calcium acetamidinate into the reaction cavity, wherein the pulse time is 3s, the waiting time is 5s, and introducing 20sccm of high-purity nitrogen to purge 25s after chemical adsorption saturation of the calcium acetamidinate on the surface of the substrate.
S4, introducing an oxygen precursor source: ozone is prepared through an ozone generator, ozone is introduced into a reaction cavity, and is adsorbed with calcification adsorbed on a silicon wafer to generate a single-layer CaO film, and then high-purity nitrogen with the concentration of 20sccm is introduced for 20s to purge, so that a single growth cycle is completed.
S5, repeating the growth cycle 300 times to obtain the CaO film.
In this example, the heating temperature of calcium acetamido was set to 80℃at 100℃at 120℃at 140℃at 160℃respectively, and the effect of CaO on CaO film growth at different heating temperatures was examined, and the number of repetition growth cycles was controlled to be the same, and the results are shown in FIG. 2. As can be seen from fig. 2, when the heating temperature of calcium acetamido is lower than 100 ℃, the thickness of the thin film is very small, and effective growth of the thin film cannot be achieved, when the heating temperature is higher than 100 ℃, growth of the thin film can be achieved, and the thickness of the thin film increases with the increase of the heating temperature, and when the heating temperature is 140-160 ℃, the thickness difference of the thin film is not large, which means that saturated adsorption of the precursor can be achieved in the temperature range.
Example 2
The invention relates to a method for growing a CaO film by utilizing an ALD technology, which selects a silicon wafer as a substrate, calcium acetamido as a calcium precursor source and ozone as an oxygen precursor source, and specifically comprises the following steps:
s1, preprocessing a substrate: sequentially cleaning the surface of the silicon wafer for 5min by using acetone, methanol, isopropanol and pure water to remove surface organic matters; then placing the treated silicon wafer into hydrofluoric acid solution to soak for 30s, etching to remove a natural oxide layer on the surface of the silicon wafer, treating the etched silicon wafer in pure water for 10s, then placing the silicon wafer into ammonia water solution to soak for 25min, placing the silicon wafer into a reaction cavity of ALD equipment within 1min after blow-drying, and vacuumizing to be lower than 1 Torr.
S2, inputting deposition working parameters: the heating temperature of the calcium acetamido is set to 140 ℃; the heating temperature of the reaction cavity is set to be 100-350 ℃, the auxiliary of the carrier gas in the pipeline is set, and the flow is 20sccm. Before coating, the reaction cavity and the source bottle are stably heated for about 1h, and high-purity nitrogen is introduced into the reaction cavity of the ALD equipment for purging.
S3, introducing a calcium precursor source: and (3) opening a pneumatic valve, introducing high-purity nitrogen into the reaction cavity in a pulse mode, introducing calcium acetamidinate into the reaction cavity, wherein the pulse time is 3s, the waiting time is 5s, and introducing 20sccm of high-purity nitrogen to purge 20s after chemical adsorption saturation of the calcium acetamidinate on the surface of the substrate.
S4, introducing an oxygen precursor source: ozone is prepared through an ozone generator, ozone is introduced into a reaction cavity, and is adsorbed with calcification adsorbed on a silicon wafer to generate a single-layer CaO film, and then high-purity nitrogen with the concentration of 20sccm is introduced for 20s to purge, so that a single growth cycle is completed.
S5, repeating the growth cycle 300 times to obtain the CaO film.
In this example, the heating temperature of the reaction chamber was set to 100℃at 150℃at 200℃at 250℃at 300℃at 350℃respectively, and the effect of the temperature of the reaction chamber on CaO film growth was examined, and the number of repetition growth cycles was controlled to be the same, and the results are shown in FIG. 3. As can be seen from fig. 3, when the temperature of the reaction chamber is 100-200 ℃, the thickness of the deposited film increases with the increase of the temperature, but the non-uniformity of the film prepared at this temperature range is > 5%; when the temperature of the reaction cavity is 200-300 ℃, the thickness of the deposited film is basically constant, and the non-uniformity of the film is less than 4 percent; when the temperature of the reaction chamber is greater than 300 c, the thickness of the deposited film starts to decrease with an increase in temperature. From this, it was found that the heating temperature of the reaction chamber was suitably set to a range of 200℃to 300℃in order to obtain a CaO thin film having a suitable film thickness and uniformity.
Example 3
The invention relates to a method for growing a CaO film by utilizing an ALD technology, which selects a silicon wafer as a substrate, calcium acetamido as a calcium precursor source and ozone as an oxygen precursor source, and specifically comprises the following steps:
s1, preprocessing a substrate: sequentially cleaning the surface of the silicon wafer for 5min by using acetone, methanol, isopropanol and pure water to remove surface organic matters; then placing the treated silicon wafer into hydrofluoric acid solution to soak for 30s, etching to remove a natural oxide layer on the surface of the silicon wafer, treating the etched silicon wafer in pure water for 10s, then placing the silicon wafer into ammonia water solution to soak for 25min, placing the silicon wafer into a reaction cavity of ALD equipment within 1min after blow-drying, and vacuumizing to be lower than 1 Torr.
S2, inputting deposition working parameters: the heating temperature of the calcium acetamido is set to 140 ℃; the heating temperature of the reaction chamber was set at 250℃and the flow was set at 20sccm with the aid of a carrier gas in the pipeline. Before coating, the reaction cavity and the source bottle are stably heated for about 1h, and high-purity nitrogen is introduced into the reaction cavity of the ALD equipment for purging.
S3, introducing a calcium precursor source: and (3) opening a pneumatic valve, introducing high-purity nitrogen into the reaction cavity in a pulse mode, introducing calcium acetamidinate into the reaction cavity, wherein the pulse time is 3s, the waiting time is 5s, and introducing 20sccm of high-purity nitrogen to purge 20s after chemical adsorption saturation of the calcium acetamidinate on the surface of the substrate.
S4, introducing an oxygen precursor source: ozone is prepared through an ozone generator, ozone is introduced into a reaction cavity, and is adsorbed with calcification adsorbed on a silicon wafer to generate a single-layer CaO film, and then high-purity nitrogen with the concentration of 20sccm is introduced for 20s to purge, so that a single growth cycle is completed.
S5, repeating the growth cycle for 50-500 times to obtain the CaO film.
This example investigated the effect of different deposition cycles on film growth. The number of cycles was controlled to 50, 100, 300, 500, and the results are shown in fig. 4. As can be seen from fig. 4, the film thickness increases linearly with increasing deposition cycle number, and no significant film nucleation delay was found at low cycle numbers.
Comparative example 1
Basically, the heating temperature of calcium acetamido was set to 140 ℃ as in example 1, except that the oxygen precursor source was ethanol, and experiments found that CaO thin film could not be grown smoothly.
Comparative example 2
Substantially the same as in example 1, the heating temperature of calcium acetamido was set to 140℃except that the oxygen precursor source was H 2 O, preparing a CaO film.
Comparative example 3
Substantially the same as in example 1, the heating temperature of calcium acetamido was set to 140℃except that the source of calcium precursor was Ca (thd) 2 The oxygen precursor source is H 2 O, preparing a CaO film.
Test example 1
The results of performing X-ray diffraction (XRD) on the CaO thin film prepared by setting the heating temperature of the reaction chamber to 250 c based on example 2 and the CaO thin films prepared in comparative examples 2 to 3 are shown in fig. 5. From fig. 5, diffraction peaks ascribed to the (111) crystal plane of the CaO thin film of example 2 can be observed, further illustrating that the CaO thin film was successfully produced by the above-described precursor source in combination with the ALD technique, and crystallization of the thin film occurred at a relatively low temperature. Whereas the CaO films of comparative examples 2-3 exhibited amorphous states.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A method for growing CaO film by ALD technology is characterized by comprising the following steps,
s1, placing a substrate subjected to wet chemical treatment in a reaction cavity of atomic layer deposition equipment, and introducing a calcium precursor to perform chemical adsorption on the surface of the substrate; the calcium precursor is an amidino calcium precursor;
s2, after chemical adsorption in the S1 is saturated, introducing inert gas into the reaction cavity for purging, and then introducing oxygen precursor for reaction;
s3, after the reaction of the S2 is finished, introducing inert gas into the reaction cavity for purging, and completing a single growth cycle;
and S4, repeating the growth cycle, and growing the CaO film on the surface of the substrate.
2. The method for growing CaO thin films using ALD techniques according to claim 1, characterized in that in S1 the wet chemical treatment is specifically: and cleaning the substrate by adopting one or more solvents of hydrofluoric acid, ammonia water, methanol, acetone, isopropanol and water.
3. The method of growing CaO thin film according to claim 1, characterized in that in S1 the substrate is selected from silicon, silicon dioxide, silicon nitride, silicon carbide, glass, sapphire, gallium nitride or stainless steel with planar or non-planar surfaces.
4. The method for growing CaO thin films using ALD according to claim 1, characterized in that in S1 the amidinate calcium precursor is selected from the group consisting of bis (N, N-di-isopropylacetamido) calcium (II) dimer or bis (N, N-di-isopropylformamidino) calcium (II) dimer.
5. The method for growing a CaO thin film according to claim 1, characterized in that the reaction chamber and the calcium precursor are heat-treated before the CaO thin film is grown in S1.
6. The method for growing CaO thin film according to claim 5, characterized in that the heating temperature of the reaction chamber is 100-400 ℃; the heating temperature of the calcium precursor is 50-200 ℃.
7. The method of growing CaO thin films using ALD techniques according to claim 1, characterized in that in S2 the oxygen precursor is selected from one or more of oxygen, ozone, hydrogen peroxide, oxygen plasma.
8. The method for growing CaO thin film according to claim 1, characterized in that in S2 and S3, the inert gas is independently selected from argon, nitrogen or helium; the purity of the inert gas is not lower than 99.999%.
9. The method for growing CaO thin film according to claim 1, characterized in that the calcium precursor and the oxygen precursor are pulsed into the reaction chamber in the presence of a carrier gas, which is nitrogen gas having a purity of not less than 99.999%.
10. A CaO film prepared by the method of any one of claims 1-9.
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