CN115142033B - Non-stoichiometric alumina material and preparation method thereof - Google Patents
Non-stoichiometric alumina material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 109
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 238000000151 deposition Methods 0.000 claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000008021 deposition Effects 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 34
- 238000004544 sputter deposition Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000002834 transmittance Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010963 304 stainless steel Substances 0.000 claims description 5
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- 229910052760 oxygen Inorganic materials 0.000 abstract description 30
- 239000001301 oxygen Substances 0.000 abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 24
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- 150000002500 ions Chemical class 0.000 description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- -1 argon ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
- C01F7/422—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation by oxidation with a gaseous oxidator at a high temperature
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/548—Controlling the composition
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a non-stoichiometric alumina material and a preparation method thereof. The preparation method comprises the following steps: placing a substrate in a chamber, and vacuumizing the chamber; after the vacuumizing, carrying out surface treatment on the base material; and sputtering an aluminum target by adopting a continuous high-power magnetron sputtering technology, and simultaneously introducing an oxygen-containing reaction gas to deposit an alumina material with a non-stoichiometric ratio on the substrate. The invention adopts the continuous high-power magnetron sputtering technology, expands the chemically active window of oxygen-containing reaction gas flow in the Al-O reaction magnetron sputtering process by virtue of the high-efficiency sputtering yield characteristic, delays the poisoning phenomenon, and realizes the accurate regulation and control of the nonstoichiometric ratio of the wide-range AlO x material. Through the regulation of nonstoichiometric ratio, the regulation of the optical, electrical and other performances of the AlO x material is realized, and the deposition rate is high and can be up to 50-400 nm/min.
Description
Technical Field
The invention relates to the technical field of ceramic material preparation, in particular to a non-stoichiometric aluminum oxide material and a preparation method thereof.
Background
Alumina has good visible light transmission characteristics and dielectric breakdown characteristics, and is widely used as an optical protection and electronic insulation material. In the optical aspect, the material can be used in the fields of 3C product cover plate protection, communication optical fiber anti-reflection, decorative glass reflection and the like, and can be used as an electronic material in the aspects of circuit packaging insulation, liquid display screen ion blocking, grid insulation and the like. In addition, the alumina material (AlO x) with non-stoichiometric ratio has adjustable optical and electrical functional characteristics, is widely paid attention to society, and is expected to obtain new potential application in the fields of quantum, dimming, varistors, memory storage and the like.
The high-quality alumina is generally prepared by a vacuum magnetron sputtering method, and the magnetron sputtering technology is an efficient film deposition technology which has the hottest research, the fastest development and the widest application in recent years, and is characterized in that: the magnetic field effect can effectively enhance the energy and yield of sputtered particles and improve the ionization rate, and high-energy particles/ions can effectively bombard the surface of the base material to form strong film base combination, so that the prepared film has the advantages of high purity, good compactness and the like. However, since Al metal is too active, once oxygen is passed through the reactive gas during sputtering, an alumina layer is easily formed on the target surface by chemical combination, thereby affecting the continuous progress of discharge and resulting in "target poisoning". Researchers and industry propose to use voltage-current curve, spectrum and mass spectrum to control gas flow in feedback, although stable discharge can be obtained, the deposition rate of alumina is extremely low, generally only 10nm/min, even if the radio frequency method is used for directly sputtering the alumina target, the deposition rate is not obviously improved, so that the deposition of alumina material with certain thickness is extremely high in time cost. In addition, because the process window for reactive sputtering by aluminum target discharge is very narrow, the control is relatively difficult, the stoichiometric ratio for preparing aluminum oxide cannot be regulated and controlled by controlling the flow of the reaction gas, and an intermediate film with a non-stoichiometric ratio cannot be prepared, so that the application of the method in the richer industrial fields is limited.
Accordingly, there is a need for improvement and development in the art.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a series of non-stoichiometric alumina materials and a preparation method thereof, and aims to solve the problems of narrow process window and uncontrollable stoichiometric ratio in the existing alumina preparation process.
The technical scheme of the invention is as follows:
A non-stoichiometric alumina material, which is a series of compound materials composed of O element and Al element together, the chemical formula of which can be expressed as AlO x, wherein 0< x <2, and x +.3/2.
Further, the optical and electrical properties of the non-stoichiometric aluminum oxide material are between that of metallic aluminum and stoichiometric aluminum oxide (Al 2O3), and continuous adjustability of the optical and electrical properties can be achieved by adjusting the aluminum-to-oxygen ratio (x).
The continuous adjustable optical performance refers to continuous adjustment of color from metallic color of aluminum to black and then to transparency (transmittance > 99%), and corresponding changes of optical reflectivity, refractive index, absorptivity, transmittance and other parameters occur.
The continuous adjustment of the electrical property means that the electrical conductivity can be continuously adjusted from the resistivity (10 e-8Ω·mm) of the metallic aluminum to the resistivity (10 e16 Ω·mm) of the aluminum oxide conforming to the stoichiometric ratio.
A method for preparing a non-stoichiometric alumina material, the specific steps of the preparation method comprising:
Placing a substrate in a chamber, and vacuumizing the chamber;
After the vacuumizing, carrying out surface treatment on the base material;
And (3) performing high-power discharge on the aluminum target and sputtering by adopting a continuous high-power magnetron sputtering technology, and simultaneously introducing an oxygen-containing reaction gas to deposit an aluminum oxide material with a non-stoichiometric ratio on the substrate.
Alternatively, by controlling the flow of the oxygen-containing reactive gas, different non-stoichiometric aluminum oxide materials are deposited on the substrate.
Optionally, a vacuum pumping system is used to pump vacuum to below 5×10 -3 Pa.
Optionally, the step of performing surface treatment on the substrate specifically includes: argon is filled, the air pressure is controlled to be in the range of 0.1-5.0 Pa, the bias voltage is started, the bias voltage is controlled to be in the range of 0-1000V, and the ion source is started to clean the substrate by plasma.
Optionally, before the step of depositing the alumina material to a non-stoichiometric ratio, the step of: depositing a transition material on the substrate to improve the bonding strength of the coating to the substrate;
Wherein the step of depositing a transition material on the substrate specifically comprises: argon is filled, the air pressure is controlled to be in the range of 0.1-5.0 Pa, bias voltage is started, the bias voltage is controlled to be in the range of 0-1000V, a continuous high-power magnetron sputtering cathode metal target or alloy target is adopted, the power density is controlled to be in the range of 10-200W/cm 2, oxygen-containing reaction gas is gradually filled, and metal oxide materials with gradually changed oxygen content are deposited on the base material.
Alternatively, the alloy target may be doped with a non-stoichiometric alumina material by adding other metallic elements to a pure metallic aluminum target, the doping elements may be any element of the periodic table that forms a solid target with aluminum metal.
Optionally, adjusting the deposited process parameters to obtain an alumina material with a desired morphology, structure, stoichiometric ratio and thickness; wherein the process parameters include one or more of aluminum target purity, discharge power density, target substrate distance, flow rate of oxygen-containing reactant gas, bias voltage, deposition temperature, and deposition time.
Optionally, the oxygen-containing reaction gas is one or more of oxygen, ozone, water vapor or hydrogen peroxide vapor and other oxygen-containing gases.
Optionally, the power density of the continuous high-power magnetron sputtering is 10-200W/cm 2, and the working gas is oxygen-containing reaction gas or mixed gas of the oxygen-containing reaction gas and inert gas, and meanwhile, the working gas pressure is ensured to be 0.1-5.0Pa.
The beneficial effects are that: the invention adopts the continuous high-power magnetron sputtering technology (C-HPMS), expands the oxygen-containing reactive gas flow quantitative active window in the Al-O reactive magnetron sputtering process by virtue of the high-efficiency sputtering yield characteristic, delays the poisoning phenomenon, and realizes the accurate control and high-speed deposition of the stoichiometric ratio of the AlO x material in a wide range. Through the regulation and control of the stoichiometric ratio, the regulation and control of the performances of the series of nonstoichiometric ratio AlO x materials in various aspects such as optics, electricity, mechanics, corrosion, heat insulation and the like are realized, and the deposition rate is high and can be as high as 50-400nm/min.
Drawings
Fig. 1 is a sample plot of non-stoichiometric alumina materials prepared in example 1 and example 2.
FIG. 2 is an optical property test of the non-stoichiometric alumina material prepared in example 1.
Fig. 3 is an electrical property test of the non-stoichiometric alumina material prepared in example 2.
Fig. 4 is a stoichiometric ratio test of the non-stoichiometric alumina material prepared in example 2.
Detailed Description
The invention provides an alumina material with non-stoichiometric ratio and a preparation method thereof, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a preparation method of an alumina material with non-stoichiometric ratio, which comprises the following steps:
S1, placing a substrate in a cavity, and vacuumizing the cavity;
S2, carrying out surface treatment on the base material after the vacuumizing;
S3, adopting a continuous high-power magnetron sputtering technology to perform high-power discharge on the aluminum target and generate sputtering, and simultaneously introducing an oxygen-containing reaction gas to deposit the aluminum oxide material with a non-stoichiometric ratio on the base material.
The embodiment provides a preparation method of an alumina material with a nonstoichiometric ratio, which adopts a continuous high-power magnetron sputtering technology (C-HPMS), and expands a flow chemical activity window of oxygen-containing reaction gas (such as O 2, ozone, water vapor or hydrogen peroxide vapor, and the like, and is exemplified by O 2 below) in the Al-O reaction magnetron sputtering process by means of the characteristic point of high-efficiency sputtering yield, thereby delaying poisoning phenomena and realizing accurate regulation and control of the nonstoichiometric ratio of the alumina material with a wide range. Through the regulation and control of non-stoichiometric ratio, the regulation and control of the properties of the alumina material in various aspects such as optics, electricity, mechanics, corrosion, heat insulation and the like are realized, and the deposition rate is high and can be up to 100nm/min. The preparation method of the embodiment is a novel method which is hopeful to replace an evaporation method and a conventional sputtering method, realizes high-efficiency preparation of the alumina material with non-stoichiometric ratio, and accurately regulates and controls the non-stoichiometric ratio and the functionality.
Specifically, the continuous high-power magnetron sputtering technology (C-HPMS) is characterized in that the generated metal plasma ionization rate is higher, which is similar to high-power pulse magnetron sputtering (HiPIMS), but the deposition efficiency is high based on direct current discharge.
Specifically, the optical properties mainly refer to refractive index, absorptivity, reflectivity, light transmittance, dawn light coefficient, color, and the like.
Specifically, the electrical properties mainly refer to resistivity, conductivity, dielectric coefficient, dielectric loss, and the like.
Specifically, the mechanical properties mainly refer to hardness, strength, toughness, modulus, wear resistance (including friction coefficient and wear rate), and the like.
In this embodiment, the non-stoichiometric aluminum oxide material is a series of compound materials composed of O element and Al element, and its chemical formula may be expressed as AlO x, where 0< x <2, and x +.3/2, for example, x may be 1.33, 1.39, 1.49, 1.59, etc. The nonstoichiometric AlO x refers to AlO x materials with other nonstoichiometric ratios except the standard compound Al 2O3 according to the atomic stoichiometric ratio, the AlO x materials can have different nonstoichiometric ratios, x represents the atomic ratio of O to Al, x is a value larger than 0 and is generally smaller than 2.0, and x is not equal to 3/2.
Specifically, the nonstoichiometric ratio of AlO x material: when x is less than 1.5, the AlO x material is rich in Al and has a non-stoichiometric AlO x material structure in an amorphous state, and the existing Al-rich part is free atoms and ions; when x is more than 1.5, the AlO x material is rich in O and has an amorphous structure of AlO x material, and the existing O-rich part is free atoms and ions.
The optical and electrical properties of the nonstoichiometric AlO x material are between that of metallic aluminum and aluminum oxide (Al 2O3) conforming to the stoichiometric ratio, and the optical and electrical properties can be continuously adjusted by adjusting the aluminum-oxygen ratio (x).
The continuous adjustable optical performance refers to continuous adjustment of color from metallic color of aluminum to black and then to transparency (transmittance > 99%), and corresponding changes of optical reflectivity, refractive index, absorptivity, transmittance and other parameters occur.
The continuous adjustment of the electrical property means that the electrical conductivity can be continuously adjusted from the resistivity (10 e-8Ω·mm) of the metallic aluminum to the resistivity (10 e16 Ω·mm) of the aluminum oxide conforming to the stoichiometric ratio.
When the nonstoichiometric ratios of the AlO x materials are different, the AlO x materials show different optical and electrical functional characteristics. Specifically, the nonstoichiometric ratio of AlO x material: when the value of x is increased from 0 to 1.5, the functional characteristics of a conductor state, a resistance state and a semiconductor state can be respectively displayed; when the x value is continuously increased from 1.5, the semiconductor state and the insulating state can respectively show functional characteristics.
The preparation method of the embodiment adopts a continuous high-power magnetron sputtering technology (C-HPMS), and realizes continuous stable discharge of the cathode aluminum target in a high-power density state and improvement of ionization rate of Al and O 2 particles through magnetic and thermal management.
Specifically, the preparation method carries out simulation on magnetic field distribution, optimizes cathode structure and magnetic field arrangement, enhances magnetic field constraint, effectively improves the stability of the Al-O reaction magnetron sputtering discharge state with the high power density of more than 100W/cm 2 and the ionization rate of Al and O 2 particles of more than 70 percent; meanwhile, the heat flow field is simulated, the cathode channel structure is optimized, the cold-heat exchange is enhanced, and the control of the strong convection cooling water temperature is combined, so that the sustainability of the discharge process of the C-HPMS in a state with the high power density of more than 100W/cm 2 is effectively improved for more than 5 hours.
The preparation method of the embodiment adopts a continuous high-power magnetron sputtering technology (C-HPMS), improves the power density, increases the activities of Al and O 2 particles in the Al-O reaction magnetron sputtering process, and expands the chemical activity window of O 2 flow.
Specifically, the preparation method increases the power density of Al-O reaction magnetron sputtering step by step, when the activity of Al and O 2 particles is increased, the O 2 flow chemical activity window of the Al-O reaction magnetron sputtering step by step is expanded synchronously, when the power density is increased from 10W/cm 2 to 200W/cm 2, the O 2 flow chemical activity window of the Al-O reaction magnetron sputtering step is expanded from 0-40 Sccm to 0-215 Sccm; meanwhile, by combining effective magnetic and thermal field management, a better linear relation exists between the increase of the power density and the expansion of the O 2 flow chemical activity window, the stability of the discharge state under the low/high power density state of magnetron sputtering is improved, the poisoning phenomenon in Al-O reaction sputtering is effectively delayed, and the poisoning resistance is enhanced.
According to the preparation method of the embodiment, the O 2 flow chemical activity window is expanded, so that the control precision of the nonstoichiometric ratio in the preparation process of the alumina material is improved.
Specifically, the preparation method adopts C-HPMS, when the O 2 flow chemical activity window is expanded from 0-40 Sccm to 0-215 Sccm, and when the regulated gas flow is 1Sccm, the control precision of the gas flow is improved from 1/40 (0.025) to 1/215 (0.00465), and the O 2 flow control precision is improved by more than 5 times, so that the non-stoichiometric precise control of the alumina material is facilitated.
According to the preparation method of the embodiment, the non-stoichiometric ratio of the alumina material is accurately controlled, so that the regulation and control of the functional characteristics of the alumina material are facilitated.
Specifically, the preparation method adopts C-HPMS, and can realize the regulation and control of the conductor state, the resistance state, the semiconductor state and the insulating state functional characteristics of the alumina material by changing the flow rate of O 2 from small to large, so that the consistency of the specific functional (non-stoichiometric ratio) alumina material in the large-scale industrial preparation can be ensured.
The preparation method of the embodiment adopts the C-HPMS, and when parameters such as power density, target base distance, O 2 flow and the like are changed, the high-efficiency preparation of the alumina material can be realized when the functional characteristics (non-stoichiometric ratio) of the alumina material are ensured to be adjustable.
Specifically, during deposition of a non-stoichiometric alumina material, a single parameter is varied: as its power density increases, the non-stoichiometric alumina material deposition rate increases; such as when the target pitch increases, its deposition rate decreases; such as when its O 2 flow increases, its deposition rate is smaller; finally, when alumina materials with nonstoichiometric ratios are prepared at the same position, the conductive state is converted into the resistance state, then the semiconductor state is converted, and finally the deposition speed generally shows a decreasing trend in the process of converting the insulating state. Further, the deposition speed of the non-stoichiometric alumina material under the specific functional characteristics can be effectively regulated to be in the range of 50-400 nm/min by adjusting parameters such as power density, target base distance, O 2 flow and the like; for example, when the distance between the target and the substrate reaches 55cm, the power density is increased to 100W/cm 2, the flow rate of O 2 is controlled to 200Sccm, and the deposition speed of the AlO x material with high insulation property can still reach about 100nm/min.
The preparation method of the embodiment adopts C-HPMS, and the AlO x material with the required morphology, structure, nonstoichiometric ratio and thickness can be obtained by adjusting the deposited technological parameters; wherein the process parameters include one or more of aluminum target purity, discharge power density, target substrate distance, flow rate of oxygen-containing reactant gas, bias voltage, deposition temperature, deposition time, and the like.
Specifically, the structure of the AlO x material refers to density, crystallinity, grain size, stress state, distribution of oxygen and aluminum atoms in the film, and the like.
In step S1, in one embodiment, the chamber is evacuated to a vacuum of less than 5×10 -3 Pa using a vacuum pumping system.
In one embodiment, the specific flow of step S1 is as follows: preparing a substrate, selecting a material with certain temperature resistance (temperature resistance is more than 300 ℃) as the substrate, cleaning the substrate (such as ultrasonic cleaning) by using reagents such as alcohol or acetone, installing in a chamber after baking and drying, closing a chamber door, sequentially starting a mechanical pump and a molecular pump to vacuumize the chamber, starting a chamber heating resistance wire when the vacuum degree reaches below 8 x 10 -2 Pa, setting the heating temperature to be 200-300 ℃, closing the heating resistance wire when the vacuum degree reaches below 3 x 10 -2 Pa, and cooling the chamber to a normal temperature state, wherein the vacuum degree reaches below 5 x 10 -3 Pa.
In particular, the material of the substrate may include, but is not limited to, organic, inorganic materials. Further, a glass sheet, a 304 stainless steel sheet or a silicon wafer is preferable as the substrate.
Specifically, the heating resistance wire of the chamber is started to accelerate vacuum extraction and adsorption gas discharge, so that heating can be omitted when a substrate with no temperature resistance is selected, and the vacuum extraction time can be prolonged to a vacuum degree of below 5 x 10 -3 Pa.
In one embodiment, the specific flow of step S2 is as follows: argon is filled, the air pressure is controlled to be in the range of 0.2-2.0 Pa, the bias voltage is started, the bias voltage is controlled to be in the range of 0-1000V, and the gas ion source is started to clean the substrate by plasma. In the embodiment, the gas ion source is used for treating the surface of the substrate, and the bias voltage is combined to accelerate ion bombardment so as to quickly clean the surface of the substrate.
Specifically, the gas ion source may be one of an anode layer ion source, a hall ion source, a kaufman source, and the like.
Specifically, the gas can be one or more of active gases such as nitrogen, oxygen, hydrogen, silane, hydrogen sulfide, hydrogen fluoride and the like.
Specifically, the time for the gas ion source to perform the surface treatment of the substrate is generally 5 to 60 minutes.
Specifically, the bias voltage may be selected from, but not limited to, one or more of DC, pulsed, and RF bias voltages.
In one embodiment, after step S2, before step S3, the method further comprises the steps of: depositing a transition material on the substrate, and depositing the non-stoichiometric aluminum oxide material on the transition material. By depositing a layer of transition material between the substrate and the non-stoichiometric alumina material, the bond strength between the non-stoichiometric alumina material and the substrate can be enhanced.
In one embodiment, the step of depositing the transition material on the substrate is performed by: argon is filled, the air pressure is controlled within the range of 0.2-2.0 Pa, the bias voltage is started, the bias voltage is controlled within the range of 0-1000V, a continuous high-power magnetron sputtering cathode metal target or alloy target is adopted, the power density is controlled within the range of 10-200W/cm 2, the deposition surface of a substrate is regulated to be opposite to the sputtering cathode metal target or alloy target (through rotating the substrate or a shielding plate), oxygen-containing reaction gas (such as O 2) is gradually filled, a layer of metal oxide material is deposited on the substrate and gradually transited to an alumina material with non-stoichiometric ratio, and the bonding strength between the alumina material with non-stoichiometric ratio and the substrate is enhanced.
Specifically, when the transition material is deposited, the O 2 flow rate is increased by taking 1Sccm as a measurement unit, the deposition time of the transition material is determined according to the deposition time required by the thickness required by the non-stoichiometric alumina material, and is generally 1/10-1/5 of the deposition time required by the non-stoichiometric alumina material, and in general, the deposition time of the transition material is 1-20 min.
Specifically, the bias voltage can be selected from one or more of direct current, pulse and radio frequency bias voltage, and preferably pulse bias voltage or radio frequency bias voltage is selected.
Specifically, the power density is controlled in the range of 10-200W/cm 2, and when the target base distance is increased in view of the distance between the base material and the target (metal target or alloy target), the power density can be increased synchronously.
Specifically, the transition material for gradually transitioning the deposited metal oxide material to the nonstoichiometric alumina material is set in view of the difference of thermal expansion coefficients between the substrate and the prepared nonstoichiometric alumina material, and when the selected substrate and nonstoichiometric alumina material have similar thermal expansion coefficients and the preparation of the nonstoichiometric alumina material with special requirements, the step can be shortened or omitted.
Specifically, the transition material is deposited, preferably an aluminum target, other targets such as a chromium target, a nickel target, a titanium target and other simple substance metal targets can be selected, and an alloy target can also be selected, wherein other metal elements (such as titanium, nickel, chromium and the like) can be added into a pure metal aluminum target, and the metal elements can be any element in the periodic table of elements which can form a solid target with aluminum metal.
In the step S3, a high-power magnetron sputtering power supply is started to supply power to a metal aluminum target arranged on a cathode, continuous high-intensity glow discharge is formed, ionized argon ions sputter the aluminum target, and a certain amount of oxygen-containing reaction gas is introduced to deposit aluminum oxide materials with non-stoichiometric ratio. In the deposition process, the technological parameters of the alumina material can be adjusted according to the requirements of the morphology, the structure, the nonstoichiometric ratio and the thickness of the alumina material.
In one embodiment, the specific flow of step S3 is as follows: and adopting a continuous high-power magnetron sputtering technology, carrying out glow discharge on an aluminum target and generating sputtering under the power density of 10-200W/cm 2, and simultaneously introducing an oxygen-containing reaction gas (such as O 2), setting the deposition time according to the thickness of the aluminum oxide material with the required nonstoichiometric ratio, so as to obtain the aluminum oxide material with the nonstoichiometric ratio.
Specifically, the power density of continuous high-power magnetron sputtering is adjusted, the power density is preferably 100W/cm 2 under the condition of high power density (more than 100W/cm 2), the wide-range O 2 flow rate adjustment requirement (O 2 flow rate chemical window reaches the range of 0-215 Sccm) can be met, the ionization rate of Al and O 2 particles is more than 70%, the non-stoichiometric ratio control of a more accurate alumina material is realized, and the high deposition speed of more than 100nm/min in the sputtering process is ensured.
Specifically, based on the target base distance, according to the nonstoichiometric ratio and thickness of the alumina material with the required functional characteristics, the flow of O 2 is regulated, the flow is controlled to be in the range of 0-215 Sccm, the deposition time is set, and the deposition time is controlled to be in the range of 1-120 min.
Specifically, the flow rate of O 2 is regulated to be controlled in the range of 0-215 Sccm, when the flow rate of O 2 is 0, a metal aluminum foil is deposited to be in a conductor state, and when the position of a substrate is fixed and the flow rate of O 2 is gradually increased, the deposited film is gradually transited to a resistance state, then to a semiconductor state and then to an insulation state.
Specifically, the multi-layer non-stoichiometric alumina material can be prepared, and the multi-layer non-stoichiometric alumina material with different functional characteristic combinations can be prepared by changing the flow of O 2 and setting corresponding deposition time, so that the characteristics of one-step preparation of the non-stoichiometric alumina material in a conductor state, a resistance state, a semiconductor state and an insulation state can be realized.
Specifically, the selected continuous high-power magnetron sputtering power density is 100W/cm 2, the corresponding O 2 flow chemical activity window is in the range of 0-215 Sccm, and when the power density is reduced or increased, the O 2 flow chemical activity window is correspondingly reduced or expanded, so that the alumina material with the same or similar functional characteristics and non-stoichiometric ratio can be prepared.
The invention is further illustrated by the following specific examples.
Example 1
S101: selecting a 304 stainless steel sheet with the length of 50mm, the width of 30mm and the thickness of 1.5mm and a high-transmittance quartz glass sheet with the length of 30mm, the width of 30mm and the thickness of 2.0mm, cleaning the surface layer of a substrate by ultrasonic waves for 15min, wiping the surface layer of the substrate by acetone, baking and drying, placing the substrate in a chamber at a position close to an anode gas ion source, enabling the deposition surface of the substrate to face an aluminum target, and setting the target base distance to be about 55cm;
S102: starting a mechanical pump to pump vacuum to below 10Pa, starting a molecular pump to pump vacuum to below 8 x 10 -2 Pa, starting a chamber heating resistance wire, setting the heating temperature to 300 ℃, and closing the heating resistance wire when the vacuum degree is below 3 x 10 -2 Pa;
S103: when the temperature of the chamber is cooled to a normal temperature state, the vacuum degree of the chamber reaches below 5 x 10 -3 Pa, argon is filled, the air pressure is controlled to be 0.8Pa, the direct current bias voltage is started, and the pressure is controlled to be 800V;
S104: starting an anode gas ion source, setting the voltage to be 800V and the current to be 0.44A, and adopting the anode gas ion source to carry out plasma cleaning on the substrate for 25min;
S105: setting the cathode water inlet temperature to 10 ℃, starting a continuous high-power magnetron sputtering cathode aluminum target, setting the power density of the sputtering aluminum target to 15W/cm 2, starting an O 2 flow controller, setting the O 2 flow to 5Sccm, removing a shielding plate, depositing for 1min, increasing the O 2 flow by 1Sccm every 30 seconds, and adjusting the O 2 flow to 25Sccm;
S106: the power density of the sputtering aluminum target is set to be 100W/cm 2,O2, the flow rate is synchronously and rapidly adjusted to 160 Sccm, a nonstoichiometric AlO x film is deposited for 8min, and the thickness of the film is about 1 mu m.
Example 2
S201: selecting a 304 stainless steel sheet with the length of 50mm, the width of 30mm and the thickness of 1.5mm and a quartz glass sheet with the length of 30mm, the width of 30mm and the thickness of 2.0mm, cleaning the surface layer of a substrate by ultrasonic waves for 20min, wiping the surface layer of the substrate by alcohol, baking and drying, placing the substrate in a chamber, enabling the deposition surface of the substrate to face an anode gas ion source, and setting the target base distance to be about 30cm;
S202: starting a mechanical pump to pump vacuum to 10Pa or below, starting a molecular pump to pump vacuum to 8 x 10 -2 Pa or below, starting a chamber heating resistance wire, setting the heating temperature to 200 ℃, and closing the heating resistance wire when the vacuum degree reaches 2 x 10 -2 Pa or below;
S203: when the temperature of the chamber is cooled to a normal temperature state, the vacuum degree of the chamber reaches below 5 x 10 -3 Pa, argon is filled, the air pressure is controlled to be 0.6Pa, the direct current bias voltage is started, and the pressure is controlled to be 1000V;
s204: starting an anode gas ion source, setting the voltage to be 1000V and the current to be 0.44A, and cleaning the substrate by adopting the anode gas ion source for 40min;
S205: setting the cathode water inlet temperature to 10 ℃, starting a continuous high-power magnetron sputtering cathode aluminum target, setting the power density of the sputtering aluminum target to 10W/cm 2, starting an O 2 flow controller, setting the O 2 flow to 5Sccm, rotating a base station, enabling a substrate to face the aluminum target, and adjusting the O 2 flow to 20Sccm according to the speed of increasing the O 2 flow by 1Sccm every 20 seconds after depositing for 1min;
S206: the power density of the sputtering aluminum target is set to be 100W/cm 2,O2, the flow rate is synchronously and rapidly adjusted to 120 Sccm, a nonstoichiometric AlO x film is deposited for 30min, and the thickness of the film is about 16.8 mu m.
In addition, the following comparative experiments were performed:
Otherwise, the target pitches in step S201 are set to be about 40 cm and 50cm, respectively.
And (3) synchronously and rapidly adjusting the flow rate of the O 2 in the step S206 to 130Sccm, 140 Sccm, sccm Sccm and 160Sccm respectively without changing the flow rate.
Structural characterization and performance test results
FIG. 1 shows sample physical graphs of example 1 and example 2, and the exact control of the light transmittance and nonstoichiometric ratio can be realized by adjusting the oxygen flow rate or the target base distance, wherein the nonstoichiometric ratio AlO x film prepared in example 1 has good visible light transmittance, and the visible light transmittance changes in the range of 30-98% as shown in FIG. 2; the nonstoichiometric AlO x film prepared in example 2 has variable resistance characteristics and exhibits a semiconductor state, see FIG. 3, with a surface static resistance varying in the range of 5X 10 8～ 2×1012 Ω/≡; the non-stoichiometric ratios of AlO x films prepared in example 2 are shown in FIG. 4, and the corresponding O/Al ratios are 1.33, 1.39, 1.49, 1.59 when the O 2 flow rates are 120Sccm, 130Sccm, 140Sccm, 160Sccm, respectively. Wherein, the nonstoichiometric AlO x film prepared in example 2 presents a resistance state, and the resistance range increases in series with the increase of the target base distance; the deposition rate of the nonstoichiometric AlO x film prepared in example 2 was gradually decreased as the target base distance was increased, and was about 560 nm/min, 420nm/min, 330nm/min when the target base distances were 30cm, 40cm, and 50cm, respectively. The result shows that the non-stoichiometric AlO x film is deposited by adopting the C-HPMS, the precise control of the non-stoichiometric ratio can be realized, the adjustable optical and electrical functional characteristics of the prepared non-stoichiometric AlO x film can be realized, and the deposition speed of the AlO x film is high.
In summary, the invention provides a non-stoichiometric aluminum oxide film and a preparation method thereof. By adopting a continuous high-power magnetron sputtering technology (C-HPMS), the flow chemical activity window of oxygen-containing reaction gas (such as O 2, ozone and the like) in the Al-O reaction magnetron sputtering process is expanded by virtue of the high-efficiency sputtering yield characteristics, the poisoning phenomenon is delayed, and the precise regulation and control of the nonstoichiometric ratio of the wide-range AlO x material is realized. Through the regulation and control of non-stoichiometric ratio, the regulation and control of the performances of AlO x materials in various aspects such as optics, electricity, mechanics, corrosion, heat insulation and the like are realized, and the deposition rate is high and can be up to 400nm/min.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (1)
1. A method for preparing a non-stoichiometric alumina material, the method comprising the specific steps of:
S101: selecting a 304 stainless steel sheet with the length of 50mm, the width of 30mm and the thickness of 1.5mm and a high-transmittance quartz glass sheet with the length of 30mm, the width of 30mm and the thickness of 2.0mm, cleaning the surface layer of a substrate by ultrasonic waves for 15min, wiping the surface layer of the substrate by acetone, baking and drying, placing the substrate in a chamber at a position close to an anode gas ion source, enabling the deposition surface of the substrate to face an aluminum target, and setting the target base distance to be 55cm;
S102: starting a mechanical pump to pump vacuum to below 10Pa, starting a molecular pump to pump vacuum to below 8 x 10 -2 Pa, starting a chamber heating resistance wire, setting the heating temperature to 300 ℃, and closing the heating resistance wire when the vacuum degree is below 3 x 10 -2 Pa;
S103: when the temperature of the chamber is cooled to a normal temperature state, the vacuum degree of the chamber reaches below 5 x 10 -3 Pa, argon is filled, the air pressure is controlled to be 0.8Pa, the direct current bias voltage is started, and the pressure is controlled to be 800V;
s104: starting an anode gas ion source, setting the voltage to be 800V and the current to be 0.44A, and adopting the anode gas ion source to carry out plasma cleaning on the substrate for 25min;
S105: setting the cathode water inlet temperature to 10 ℃, starting a continuous high-power magnetron sputtering cathode aluminum target, setting the power density of the sputtering aluminum target to 15W/cm 2, starting an O 2 flow controller, setting the O 2 flow to 5sccm, removing a shielding plate, depositing for 1min, increasing the O 2 flow to 1sccm every 30 seconds, and adjusting the O 2 flow to 25sccm;
S106: setting the power density of a sputtering aluminum target to be 100W/cm 2,O2, synchronously and rapidly adjusting the flow to 160sccm, depositing an AlO x film with a nonstoichiometric ratio for 8min, and enabling the thickness of the film to be 1 mu m;
or the preparation method comprises the following specific steps:
S201: selecting a 304 stainless steel sheet with the length of 50mm, the width of 30mm and the thickness of 1.5mm and a quartz glass sheet with the length of 30mm, the width of 30mm and the thickness of 2.0mm, cleaning the surface layer of a substrate by ultrasonic waves for 20min, wiping the surface layer of the substrate by alcohol, baking and drying the substrate, placing the substrate in a cavity, enabling the deposition surface of the substrate to face an anode gas ion source, and setting the target base distance to be 30cm;
S202: starting a mechanical pump to pump vacuum to 10Pa or below, starting a molecular pump to pump vacuum to 8 x 10 -2 Pa or below, starting a chamber heating resistance wire, setting the heating temperature to 200 ℃, and closing the heating resistance wire when the vacuum degree reaches 2 x 10 -2 Pa or below;
S203: when the temperature of the chamber is cooled to a normal temperature state, the vacuum degree of the chamber reaches below 5 x 10 -3 Pa, argon is filled, the air pressure is controlled to be 0.6Pa, the direct current bias voltage is started, and the pressure is controlled to be 1000V;
s204: starting an anode gas ion source, setting the voltage to be 1000V and the current to be 0.44A, and adopting the anode gas ion source to carry out plasma cleaning on the substrate for 40min;
S205: setting the cathode water inlet temperature to 10 ℃, starting a continuous high-power magnetron sputtering cathode aluminum target, setting the power density of the sputtering aluminum target to 10W/cm 2, starting an O 2 flow controller, setting the O 2 flow to 5sccm, rotating a base station, enabling a substrate to face the aluminum target, and adjusting the O 2 flow to 20sccm according to the speed of increasing the O 2 flow by 1sccm every 20 seconds after depositing for 1 min;
S206: setting the power density of a sputtering aluminum target to be 100W/cm 2,O2, synchronously and rapidly adjusting the flow to 120sccm, depositing an AlO x film with a nonstoichiometric ratio for 30min, and forming a film thickness of 16.8 mu m;
Or else, the flow of O 2 in step S206 is synchronously and rapidly adjusted to 130sccm, 140sccm and 160sccm respectively.
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| CN115142033A (en) | 2022-10-04 |
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