CN112795899B - Preparation device and preparation process of electronic thin-film material - Google Patents
Preparation device and preparation process of electronic thin-film material Download PDFInfo
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- CN112795899B CN112795899B CN202011613749.5A CN202011613749A CN112795899B CN 112795899 B CN112795899 B CN 112795899B CN 202011613749 A CN202011613749 A CN 202011613749A CN 112795899 B CN112795899 B CN 112795899B
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
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- 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
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
- C23C16/4582—Rigid and flat substrates, e.g. plates or discs
- C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
- C23C16/4585—Devices at or outside the perimeter of the substrate support, e.g. clamping rings, shrouds
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
- C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
- C23C16/5096—Flat-bed apparatus
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation device and a preparation process of an electronic thin film material, wherein the preparation device comprises an RF reactor and N 2 Source, O 2 The preparation process comprises the following steps: s1, cleaning and drying a substrate; s2, fixing the substrate, vacuumizing the deposition chamber, and filling N 2 To standard atmospheric pressure; s3, depositing Ga on the surface of the substrate 2 O 3 A film; s4 Ga deposited in step S3 2 O 3 Depositing Cu-doped Ga on surface of film 2 O 3 A film; s5, cu-doped Ga deposited in step S4 2 O 3 Ga is continuously deposited on the surface of the film 2 O 3 A film is obtained, and a film with a three-layer structure is obtained; s6, taking out the film and annealing. The preparation device can promote the precursor to be deposited on the surface of the substrate under the action of the electrode, and improve the speed and the uniformity of the deposition of the precursor.
Description
Technical Field
The invention relates to the field of electronic thin films, in particular to a preparation device and a preparation process of an electronic thin film material.
Background
The 21 st century is the era of new materials, and energy, material and information science is the leader and the pillar of new technical revolution. Electronic film materials, as films of materials with special forms, have become the material basis of new development and development subjects such as microelectronics, optoelectronics, magnetoelectronics, cutter super-hardening, sensors, solar energy utilization and the like, and widely permeate into various fields of modern science and technology.
Ga 2 O 3 The semiconductor material is a wide-bandgap semiconductor material with direct band gap, has the maximum forbidden band width of-4.9 eV (-250 nm), has the characteristics of high ultraviolet and visible light transmittance, strong breakdown field (-8 MV/cm), low energy loss and the like, shows huge application prospect in devices such as transparent conductive electrodes, solar blind ultraviolet detectors, field effect transistors, gas sensors and the like, and is a multifunctional photoelectric material with great application potential. High quality Ga 2 O 3 The film plays an important role in researching photoelectric semiconductor devices, and the quality of the film is often determined by preparation methods and process parameters. Conventional Ga 2 O 3 The preparation method of the film has the problems of high energy consumption, low film forming efficiency and non-uniform film forming, and simultaneously the existing Ga 2 O 3 The film preparation method is not easy to realize in preparing the film containing the doping.
Disclosure of Invention
In order to solve the above-mentioned drawbacks of the prior art, the present invention provides an apparatus and a process for preparing an electronic thin film material. The preparation device can accurately control the distance between the two polar plates, the substrate is firmly fixed, and the special gas inlet and outlet design can promote the precursor to be deposited on the surface of the substrate under the action of the electrode and improve the speed and the uniformity of the precursor deposition. The preparation process of the invention adopts the atmospheric pressure RF-DBD plasma auxiliary pulse chemical vapor deposition, the prepared electronic film has good compactness and high growth rate, and meanwhile, the process at the normal temperature and the normal pressure saves more energy and is preparedPrepared Cu doped gamma-Ga 2 O 3 The three-layer structure of the film ensures that the dopant is stably bonded in the high-temperature annealing process, the adsorption effect is good, and the problem of outward diffusion is avoided.
The purpose of the invention can be realized by the following technical scheme:
the preparation device of the electronic thin film material comprises an RF reactor, an N2 source, an O2 source, a Ga source, a Cu source, a PC end and a vacuum pump, wherein the gas inlet end of the RF reactor is respectively connected with the N through electromagnetic valves Y1 and Y2 2 Source and O 2 The gas outlet end of the source RF reactor is connected with the gas inlet end of an electromagnetic valve Y1 through a three-way valve K, N 2 One gas outlet end of the source is respectively connected with the Ga source and the Cu source through electromagnetic valves Y3 and Y4, the gas outlet ends of the Ga source and the Cu source are respectively connected with a three-way valve K through electromagnetic valves Y5 and Y6, and N is 2 A flowmeter V1, O is arranged between the source and the electromagnetic valve Y1 2 A flowmeter V2, N is arranged between the source and the electromagnetic valve Y2 2 A flowmeter V3 and a one-way valve M are arranged between the source and the electromagnetic valves Y3 and Y4, the RF reactor is electrically connected with the PC end, and the PF reactor is connected with the output end of the vacuum pump through an electromagnetic valve Y7.
The RF reactor comprises a deposition chamber, a fixed mounting and fixing mechanism is arranged in the middle of the bottom of the deposition chamber, the fixed mounting and fixing mechanism comprises an annular cover, a sample support is arranged in the annular cover, a lower polar plate is fixedly mounted at the top of the sample support, a sealing cover is fixedly mounted at the top of the deposition chamber, a connecting rod is arranged in the middle of the sealing cover in a penetrating mode, the connecting rod is connected with the sealing cover in a sliding mode, the top end of the connecting rod is connected with an electric push rod, an upper polar plate is fixedly mounted at the bottom of the connecting rod, a quartz partition plate is fixedly mounted at the bottom of the upper polar plate, a barometer is fixedly mounted on the surface of the sealing cover, a plurality of air inlets are arranged in an annular array at the bottom of the deposition chamber, the air inlets are connected with a gas distributor, a first air outlet is arranged in the middle of the bottom of the deposition chamber, a second air outlet is connected with an external air pump, and a plurality of mounting plates are fixed in the annular array at the outer wall of the deposition chamber.
Further preferably, the upper polar plate and the lower polar plate are electrically connected with the RF power supply, the lower polar plate is connected with the ground wire, the upper polar plate is a copper plate, and the lower polar plate is a graphite plate.
Further preferably, a plurality of supporting rods are fixedly mounted at the top of the annular cover, one ends of the supporting rods are hinged to the top of the annular cover, torsional springs are arranged at the hinged shafts of the supporting rods, clamping blocks are fixedly mounted at the other ends of the supporting rods, and the bottoms of the clamping blocks are arc-shaped surfaces.
Further preferably, the sample holder comprises a fixing plate, a gap of 10-30mm is formed between the fixing plate and the annular cover, an annular boss extending downwards is arranged at the edge of the bottom of the fixing plate, a plurality of air outlets are formed in the annular boss and are arranged in an annular array, a first air outlet is formed in the annular boss, a plurality of heating wires are fixedly mounted inside the fixing plate, and the heating wires are arranged in the fixing plate in a surrounding mode.
A preparation process of an electronic thin film material specifically comprises the following steps:
s1, immersing a substrate into acetone, absolute ethyl alcohol and deionized water in sequence, ultrasonically cleaning for 5-10min, taking out, washing with deionized water, and finally washing with dry N 2 Air drying for later use;
s2, fixing the substrate on the sample support, closing the cover plate of the deposition chamber, vacuumizing the deposition chamber to 5-10Pa by an air pump, and filling N into the deposition chamber 2 Starting a substrate heating device to heat the substrate to 80-90 ℃ when the pressure is up to the standard atmospheric pressure;
s3, controlling the distance between the electrode plates, starting a radio frequency power supply, and adopting a pulse mode to mix an organic gallium precursor and O 2 Introducing into a deposition chamber, controlling the deposition period to be 50-100cycles, and depositing Ga on the surface of the substrate 2 O 3 A film;
s4, heating the substrate to 100-110 ℃ through a substrate heating device, and then adopting a pulse mode to heat an organic gallium precursor, an organic copper precursor and O 2 Introducing into a deposition chamber, controlling the deposition period to be 300-400cycles, and depositing Ga in the step S3 2 O 3 Deposition of Cu-doped Ga on film surface 2 O 3 A film;
s5, adopting a pulse mode to mix an organic gallium precursor and O 2 Introducing into a deposition chamber, controlling the deposition period to be 50-100cycles, and depositing Cu-doped Ga in step S4 2 O 3 Ga is continuously deposited on the surface of the film 2 O 3 A film of a material selected from the group consisting of,thereby obtaining a film having a three-layer structure;
s6, taking out the film obtained in the step S5 and putting the film in a container with N 2 Annealing in a tube furnace for 8-10h to obtain the electronic film, wherein the annealing temperature is 700-900 ℃.
Further preferably, the substrate is one of a PET film, a silicon wafer, a potassium bromide tablet and an alumina ceramic wafer, and the organic copper precursor is Cu (acac) 2 、Cu(hfac) 2 、Cu(thd) 2 、[Cu(O-t-Bu)] 4 Wherein the organic gallium precursor is Ga (CH) 3 ) 3 、Ga(C 2 H 5 ) 3 、Ga(N(CH 3 ) 2 ) 3 、C 9 H 21 GaO 3 To (3) is provided.
Further preferably, in the steps S3-S5, the radio frequency is 300-1000KHz, the radio frequency power is 50-200W, and the distance between the upper and lower polar plates is 5-10mm.
Further preferably, the organic gallium precursor, the organic copper precursor and O in steps S3-S5 2 Are all passing through N 2 For carrying the carrier into the deposition chamber, N 2 The flow rate of the organic gallium precursor, the organic copper precursor and O is 600-700sccm 2 The flow rate of (2) is 200-300sccm.
Further preferably, one deposition cycle in steps S3 and S5 includes introducing the organic gallium precursor and N 2 Purging organic gallium precursor, and introducing O 2 And N 2 Purging O 2 The introduction time of the Ga precursor in the steps S3 and S5 is 0.4-0.6S 2 The time for purging the organic gallium precursor is 50-70s 2 The introduction time of (A) is 4 to 6s 2 Purging O 2 The time of (a) is 30-50s;
in the step S4, a deposition period comprises the introduction of a mixture of an organic gallium precursor and an organic copper precursor, and N 2 Purging the organic precursor mixture, introducing O 2 And N 2 Purging O 2 Four steps, the leading-in time of the organic precursor mixture in the step S4 is 0.4-0.6S 2 The time for purging the organic precursor mixture is 60-80s 2 The introduction time of (2) is 5-8s 2 Blowing O 2 The time of (a) is 40-60s.
Further preferably, the volume ratio of the organic gallium precursor to the organic copper precursor introduced in the step S4 is 10-15:1.
the invention has the beneficial effects that:
1. the upper polar plate of the preparation device of the electronic film material is connected with an electric push-pull rod through a connecting rod, the distance between the two polar plates can be accurately controlled through an electric push rod, a plurality of clamping rods are fixedly arranged at the top of the annular cover, clamping blocks are fixedly arranged at the other ends of the clamping rods, a substrate can be effectively fixed through the clamping blocks to prevent the substrate from sliding, a plurality of air inlets are arranged at the bottom of the deposition chamber in an annular array mode and connected with a gas distributor, and a precursor and N swept through the gas distributor 2 Evenly let in the deposit room, first gas outlet sets up in annular boss, and the air current is discharged by in the annular boss after rising along the deposit room inner wall, can promote predecessor and deposit on the base plate surface through the effect of electrode, improves the sedimentary speed of predecessor and uniform degree.
2. The preparation process of the electronic film material successfully prepares the Cu-doped gamma-Ga by depositing the electronic film with a three-layer structure on the surface of a substrate through the atmospheric pressure RF-DBD plasma assisted pulse chemical vapor deposition 2 O 3 The three-layer structure of the film ensures that the dopant is stably bonded in the high-temperature annealing process, the adsorption effect is good, and the problem of outward diffusion is avoided.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a schematic view of a frame of an apparatus for producing an electronic thin film material of the present invention;
FIG. 2 is a schematic diagram of an RF reactor of an apparatus for preparing an electronic thin film material according to the present invention;
FIG. 3 is a schematic view of the overall structure of an RF reactor of the apparatus for preparing an electronic thin film material according to the present invention;
FIG. 4 is a schematic view of the internal structure of an RF reactor of the apparatus for preparing an electronic thin film material according to the present invention;
FIG. 5 is a disassembled schematic view of an RF reactor of the apparatus for preparing an electronic thin film material of the present invention;
FIG. 6 is a schematic view showing the structure of a sealing cover of an RF reactor used in an apparatus for manufacturing an electronic thin film material according to the present invention;
FIG. 7 is a schematic structural view of a deposition chamber of an RF reactor of an apparatus for preparing an electronic thin film material according to the present invention;
FIG. 8 is a sectional view of an RF reactor fixing mechanism of the apparatus for preparing an electronic thin film material according to the present invention;
FIG. 9 is a schematic view showing the structure of a gas distributor of an RF reactor of an apparatus for producing an electronic thin film material according to the present invention;
fig. 10 is an SEM image of the electron thin film prepared in example 1 of the present invention.
In the figure:
1-a deposition chamber, 2-a fixing mechanism, 3-an annular cover, 4-a sample holder, 5-a lower polar plate, 6-a sealing cover, 7-a connecting rod, 8-an electric push rod, 9-a higher-level plate, 10-a quartz clapboard, 11-a gas pressure meter, 12-a gas inlet, 13-a gas distributor, 14-a first gas outlet, 15-a second gas outlet, 16-a mounting plate, 17-a clamping rod, 18-a clamping block, 19-a fixing plate, 20-an annular boss, 21-a gas outlet and 22-a heating wire.
Detailed Description
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, 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 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.
In the description of the present invention, it is to be understood that the terms "opening," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like are used in an orientation or positional relationship merely to facilitate description of the invention and to simplify the description, and are not intended to indicate or imply that the referenced components or elements must be in a particular orientation, constructed and operative in a particular orientation, and are not to be construed as limiting the invention.
As shown in FIGS. 1-9, an apparatus for preparing an electronic thin film material comprises an RF reactor, an N2 source, an O2 source, a Ga source, a Cu source, a PC terminal and a vacuum pump, wherein the gas inlet of the RF reactor is connected to N via electromagnetic valves Y1 and Y2 2 Source and O 2 The gas outlet end of the source RF reactor is connected with the gas inlet end of an electromagnetic valve Y1 through a three-way valve K, N 2 One gas outlet end of the source is respectively connected with the Ga source and the Cu source through electromagnetic valves Y3 and Y4, the gas outlet ends of the Ga source and the Cu source are respectively connected with a three-way valve K through electromagnetic valves Y5 and Y6, and N is 2 A flowmeter V1, O is arranged between the source and the electromagnetic valve Y1 2 A flowmeter V2, N is arranged between the source and the electromagnetic valve Y2 2 A flowmeter V3 and a one-way valve M are arranged between the source and the electromagnetic valves Y3 and Y4, the RF reactor is electrically connected with the PC end, and the PF reactor is connected with the output end of the vacuum pump through an electromagnetic valve Y7.
The RF reactor includes deposition chamber 1, fixed mounting fixed establishment 2 in the middle of the 1 bottom of deposition chamber, fixed establishment 2 includes annular cover 3, annular cover 3 is inside to be equipped with sample support 4, sample support 4 top fixed mounting lower polar plate 5, the sealed lid 6 of the 1 top fixed mounting of deposition chamber, it is equipped with connecting rod 7 to run through in the middle of the sealed lid 6, connecting rod 7 and sealed 6 sliding connection that covers, the 7 top of connecting rod is connected with electric putter 8, connecting rod 7 bottom fixed mounting upper polar plate 9, upper polar plate 9 bottom fixed mounting quartz baffle 10, sealed lid 6 fixed surface installation barometer 11, 1 bottom annular array of deposition chamber is equipped with a plurality of air inlets 12, air inlet 12 is connected with gas distributor 13, first gas outlet 14 has been seted up in the middle of the 1 bottom of deposition chamber, 1 lateral wall of deposition chamber is equipped with second gas outlet 15, the external air pump of second gas outlet 15, a plurality of fixed mounting panels 16 of the annular array of the 1 outer wall of deposition chamber.
The upper polar plate 9 and the lower polar plate 5 are electrically connected with an RF power supply, the lower polar plate 5 is connected with a ground wire, the upper polar plate 9 is a copper plate, and the lower polar plate 5 is a graphite plate.
A plurality of supporting rods 17 of 3 top fixed mounting of annular cover, supporting rod 17 one end is articulated with 3 tops of annular cover, and the articulated shaft department of supporting rod 17 is equipped with the torsional spring, and supporting rod 17 other end fixed mounting grip block 18, grip block 18 bottom are the arcwall face.
The sample support 4 comprises a fixing plate 19, a gap of 10-30mm is formed between the fixing plate 19 and the annular cover 3, an annular boss 20 extending downwards is arranged at the edge of the bottom of the fixing plate 19, a plurality of air outlets 21 are formed in the annular boss 20, the air outlets 21 are arranged in an annular array, the first air outlet 14 is arranged in the annular boss 20, a plurality of heating wires 22 are fixedly installed inside the fixing plate 19, and the heating wires 22 are arranged in the fixing plate 19 in a surrounding mode.
Example 1
A preparation process of an electronic thin film material specifically comprises the following steps:
s1, sequentially immersing a silicon wafer substrate into acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 8min, taking out, washing with the deionized water, and finally washing with dry N 2 Air drying for later use;
s2, fixing the silicon wafer substrate on the sample support, closing a deposition chamber cover plate, vacuumizing the deposition chamber by an air pump until the vacuum degree is 5Pa, and filling N into the deposition chamber 2 Starting a substrate heating device to heat the substrate to 85 ℃ when the pressure is up to the standard atmospheric pressure;
s3, controlling the distance between the electrode plates to be 7mm, starting a radio frequency power supply, wherein the radio frequency is 450KHz, the power of the radio frequency is 100W, and the radio frequency passes through N 2 Organic gallium precursor Ga (CH) is used as a carrier 3 ) 3 Into a deposition chamber, an organic gallium precursor Ga (CH) 3 ) 3 The introduction time is 0.6s, and N is introduced 2 Purge 60s by N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 5s, and N is introduced again 2 Purging for 40s, and circulating for 60cycles to deposit Ga on the surface of the substrate 2 O 3 A film;
s4, heating the substrate to 100 ℃ by a substrate heating device, and then passing N 2 An organic gallium precursor and an organic copper precursor Cu (hfac) are used as carriers 2 Is carried into the deposition chamber and then is carried into the deposition chamber,the volume ratio of the organic gallium precursor to the organic copper precursor is 12:1, the introduction time of the organic gallium precursor and the organic copper precursor is 0.5s, and N is introduced 2 Purge 70s, through N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 8s, and N is introduced again 2 Purging for 50S, thus cycling through 300-400cycles, ga deposited in step S3 2 O 3 Depositing Cu-doped Ga on surface of film 2 O 3 A film;
s5, passing through N 2 Carrying an organic gallium precursor into the deposition chamber for the carrier, introducing the organic gallium precursor for 0.6s, and introducing N 2 Purge 60s by N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 5s, and N is introduced again 2 Purging 40S, thus cycling 60cycles, the Cu doped Ga deposited in step S4 2 O 3 Ga is continuously deposited on the surface of the film 2 O 3 A film, thereby obtaining a film having a three-layer structure;
s6, taking out the film obtained in the step S5 and putting the film in a container with N 2 Annealing for 8-10h in a tube furnace to obtain the electronic film, wherein the annealing temperature is 800 ℃.
FIG. 1 is an SEM image of an electronic film, and it can be seen from FIG. 1 that the electronic film prepared by the present invention has high density, and the deposited film is flat on the surface of the substrate.
Example 2
A preparation process of an electronic thin film material specifically comprises the following steps:
s1, sequentially immersing a PET film substrate into acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 5min, taking out, washing with deionized water, and finally washing with dry N 2 Air drying for later use;
s2, fixing the PET film substrate on a sample support, closing a deposition chamber cover plate, vacuumizing the deposition chamber by an air pump until the vacuum degree is 8Pa, and filling N into the deposition chamber 2 Starting a substrate heating device to heat the substrate to 80 ℃ when the pressure is up to the standard atmospheric pressure;
s3, controlling the distance between the electrode plates to be 6mm, and starting a radio frequency power supply with the radio frequency of 800KHz, power at radio frequency 150W, through N 2 Organic gallium precursor Ga (C) is taken as a carrier 2 H 5 ) 3 Carried into a deposition chamber, an organic gallium precursor Ga (C) 2 H 5 ) 3 The introduction time is 0.5s, and N is introduced 2 Purge 60s by N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 5s, and N is introduced again 2 Purging for 40s, thus circulating 80cycles, and depositing Ga on the surface of the substrate 2 O 3 A film;
s4, heating the substrate to 105 ℃ through a substrate heating device, and then passing N 2 Organic gallium precursor and organic copper precursor [ Cu (O-t-Bu) are used as carriers] 4 And carrying into a deposition chamber, wherein the volume ratio of the organic gallium precursor to the organic copper precursor is 10:1, the introduction time of the organic gallium precursor and the organic copper precursor is 0.5s, and N is introduced 2 Purge 70s by N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 7s, and N is introduced again 2 Purging for 50S, thus cycling through 350cycles, ga deposited in step S3 2 O 3 Depositing Cu-doped Ga on surface of film 2 O 3 A film;
s5, passing through N 2 Organic gallium precursor Ga (C) is taken as a carrier 2 H 5 ) 3 Carried into a deposition chamber, an organic gallium precursor Ga (C) 2 H 5 ) 3 The introduction time is 0.5s, and N is introduced 2 Purge 60s by N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 5s, and N is introduced again 2 Purging 40S, thus cycling 80cycles, the Cu doped Ga deposited in step S4 2 O 3 Ga is continuously deposited on the surface of the film 2 O 3 A film, thereby obtaining a film having a three-layer structure;
s6, taking out the film obtained in the step S5, and putting the film into a container filled with N 2 Annealing for 10 hours in a tube furnace to obtain the electronic film, wherein the annealing temperature is 750 ℃.
Example 3
A preparation process of an electronic thin film material specifically comprises the following steps:
s1, sequentially immersing a potassium bromide tabletting substrate into acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 8min, taking out, washing with deionized water, and finally washing with dry N 2 Air drying for later use;
s2, fixing the potassium bromide tabletting substrate on the sample support, closing the cover plate of the deposition chamber, vacuumizing the deposition chamber by an air pump until the vacuum degree is 5Pa, and filling N into the deposition chamber 2 Starting a substrate heating device to heat the substrate to 90 ℃ when the pressure reaches the standard atmospheric pressure;
s3, controlling the distance between the electrode plates to be 7mm, starting a radio frequency power supply, wherein the radio frequency is 500KHz, the power of the radio frequency is 50W, and the radio frequency passes through N 2 Organic gallium precursor C as carrier 9 H 21 GaO 3 Carried into a deposition chamber, an organic gallium precursor C 9 H 21 GaO 3 The introduction time is 0.4s, and N is introduced 2 Purge 60s by N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 5s, and N is introduced again 2 Purging for 40s, and circulating for 100cycles to deposit Ga on the surface of the substrate 2 O 3 A film;
s4, heating the substrate to 100 ℃ by a substrate heating device, and then passing N 2 An organic gallium precursor and an organic copper precursor Cu (acac) are used as carriers 2 And carrying into a deposition chamber, wherein the volume ratio of the organic gallium precursor to the organic copper precursor is 15:1, the introduction time of the organic gallium precursor and the organic copper precursor is 0.5s, and N is introduced 2 Purge 70s, through N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 8s, and N is introduced again 2 Purging for 50S, thus cycling through 300cycles, ga deposited in step S3 2 O 3 Depositing Cu-doped Ga on surface of film 2 O 3 A film;
s5, passing through N 2 Carrying an organic gallium precursor into the deposition chamber for the carrier, introducing the organic gallium precursor for 0.4s, and introducing N 2 Purge 60s by N 2 Using O as a carrier 2 Carried into a deposition chamber and is filled with O 2 The time is 4-6s, and N is introduced again 2 Purge 40S, cycle 100cycles, at step S4Deposited Cu-doped Ga 2 O 3 Ga is continuously deposited on the surface of the film 2 O 3 A film, thereby obtaining a film having a three-layer structure;
s6, taking out the film obtained in the step S5, and putting the film into a container filled with N 2 Annealing for 8 hours in the tube furnace to obtain the electronic film, wherein the annealing temperature is 850 ℃.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed.
Claims (9)
1. A preparation process of an electronic thin film material is characterized in that,
the method specifically comprises the following steps:
s1, immersing a substrate into acetone, absolute ethyl alcohol and deionized water in sequence, ultrasonically cleaning for 5-10min, taking out, washing with deionized water, and finally washing with dry N 2 Air drying for later use;
s2, fixing the substrate on the sample holder, closing the cover plate of the deposition chamber, vacuumizing the deposition chamber to 5-10Pa by using an air pump, and filling N into the deposition chamber 2 Starting a substrate heating device to heat the substrate to 80-90 ℃ when the pressure is up to the standard atmospheric pressure;
s3, controlling the electrode plateThe radio frequency power supply is started, and the organic gallium precursor and O are added in a pulse mode 2 Introducing into a deposition chamber, controlling the deposition period to be 50-100cycles, and depositing Ga on the surface of the substrate 2 O 3 A film;
s4, heating the substrate to 100-110 ℃ through a substrate heating device, and then adopting a pulse mode to heat an organic gallium precursor, an organic copper precursor and O 2 Introducing into a deposition chamber, controlling the deposition period to be 300-400cycles, and depositing Ga in step S3 2 O 3 Deposition of Cu-doped Ga on film surface 2 O 3 A film;
s5, adopting a pulse mode to mix an organic gallium precursor and O 2 Introducing into a deposition chamber, controlling the deposition period to be 50-100cycles, and depositing Cu-doped Ga in step S4 2 O 3 Ga is continuously deposited on the surface of the film 2 O 3 A film, thereby obtaining a film having a three-layer structure;
s6, taking out the film obtained in the step S5 and putting the film in a container with N 2 Annealing for 8-10h in the tube furnace to obtain the electronic film, wherein the annealing temperature is 700-900 ℃;
the preparation device adopted by the preparation process of the electronic thin film material comprises an RF reactor and N 2 Source, O 2 The gas inlet end of the RF reactor is respectively connected with N through electromagnetic valves Y1 and Y2 2 Source and O 2 The gas outlet end of the RF reactor is connected with the gas inlet end of an electromagnetic valve Y1 through a three-way valve K, and the N is 2 One gas outlet end of the source is respectively connected with a Ga source and a Cu source through electromagnetic valves Y3 and Y4, the gas outlet ends of the Ga source and the Cu source are respectively connected with a three-way valve K through electromagnetic valves Y5 and Y6, and the N is 2 A flow meter V1 is arranged between the source and the electromagnetic valve Y1, O 2 A flowmeter V2 is arranged between the source and the electromagnetic valve Y2, N 2 A flowmeter V3 and a one-way valve M are arranged between the source and the electromagnetic valves Y3 and Y4, the RF reactor is electrically connected with the PC end, and the RF reactor is connected with the output end of the vacuum pump through an electromagnetic valve Y7;
the RF reactor comprises a deposition chamber (1), a fixed mounting fixing mechanism (2) is arranged in the middle of the bottom of the deposition chamber (1), the fixed mounting fixing mechanism (2) comprises an annular cover (3), a sample support (4) is arranged in the annular cover (3), a sample support (4) top fixed mounting lower polar plate (5) is arranged, a deposition chamber (1) top fixed mounting sealing cover (6), a connecting rod (7) penetrates through the middle of the sealing cover (6), the connecting rod (7) is connected with the sealing cover (6) in a sliding mode, the top end of the connecting rod (7) is connected with an electric push rod (8), a connecting rod (7) bottom fixed mounting upper polar plate (9) is arranged, a connecting plate (9) bottom fixed mounting quartz partition plate (10) is arranged, a sealing cover (6) surface fixed mounting air pressure gauge (11), an annular array is arranged at the bottom of the deposition chamber (1) and is provided with a plurality of air inlets (12), the air inlets (12) are connected with a gas distributor (13), a first air outlet (14) is arranged in the middle of the bottom of the deposition chamber (1), a side wall of the deposition chamber (1) is provided with a second air outlet (15), and an external annular array is arranged on the outer wall of the deposition chamber (16).
2. The process for preparing the electronic thin film material according to claim 1, wherein the upper plate (9) and the lower plate (5) are electrically connected with an RF power supply, the lower plate (5) is connected with a ground wire, the upper plate (9) is a copper plate, and the lower plate (5) is a graphite plate.
3. The preparation process of the electronic film material as claimed in claim 1, wherein a plurality of clamping rods (17) are fixedly mounted at the top of the annular cover (3), one ends of the clamping rods (17) are hinged to the top of the annular cover (3), a torsion spring is arranged at a hinged shaft of each clamping rod (17), clamping blocks (18) are fixedly mounted at the other ends of the clamping rods (17), and the bottoms of the clamping blocks (18) are arc-shaped surfaces.
4. The preparation process of the electronic thin film material according to claim 1, wherein the sample holder (4) comprises a fixing plate (19), a gap of 10-30mm is formed between the fixing plate (19) and the annular cover (3), a downwardly extending annular boss (20) is arranged at the bottom edge of the fixing plate (19), a plurality of air outlets (21) are formed in the annular boss (20), the air outlets (21) are arranged in an annular array, the first air outlet (14) is arranged in the annular boss (20), a plurality of heating wires (22) are fixedly mounted in the fixing plate (19), and the heating wires (22) are arranged in the fixing plate (19) in a surrounding manner.
5. The process for preparing an electronic thin film material according to claim 1, wherein the substrate is one of a PET film, a silicon wafer, a potassium bromide tablet and an alumina ceramic wafer, and the organic copper precursor is Cu (acac) 2 、Cu(hfac) 2 、Cu(thd) 2 、[Cu(O-t-Bu)] 4 The organic gallium precursor is Ga (CH) 3 ) 3 、Ga(C 2 H 5 ) 3 、Ga(N(CH 3 ) 2 ) 3 、C 9 H 21 GaO 3 To (3) is provided.
6. The process for preparing an electronic thin film material according to claim 1, wherein in the steps S3-S5, the radio frequency is 300-1000KHz, the radio frequency power is 50-200W, and the distance between the upper and lower electrode plates is 5-10mm.
7. The process for preparing an electronic thin film material according to claim 1, wherein the organic gallium precursor, the organic copper precursor and O in steps S3-S5 2 All pass through N 2 For carrying the carrier into the deposition chamber, said N 2 The flow rate of the organic gallium precursor, the organic copper precursor and O is 600-700sccm 2 The flow rate of (2) is 200-300sccm.
8. The process of claim 1, wherein one deposition cycle of steps S3 and S5 includes introducing an organic gallium precursor, N 2 Purging organic gallium precursor, and introducing O 2 And N 2 Blowing O 2 The introduction time of the Ga precursor in the steps S3 and S5 is 0.4-0.6S 2 The time for purging the organic gallium precursor is 50-70s 2 Is passed for a period of 4 to 6s 2 Purging O 2 The time of (2) is 30-50s;
said step S4, in one deposition period, introducing a mixture of an organic gallium precursor and an organic copper precursor, and N 2 Purging the organic precursor mixture, introducing O 2 And N 2 Blowing O 2 Four steps, the leading-in time of the organic precursor mixture in the step S4 is 0.4-0.6S 2 The time for purging the organic precursor mixture is 60-80s 2 The introduction time of (2) is 5 to 8s 2 Blowing O 2 For a period of 40-60s.
9. The process for preparing an electronic thin film material according to claim 1, wherein the volume ratio of the organic gallium precursor to the organic copper precursor introduced in the step S4 is 10-15:1.
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