CN114686846A - High-resistance film preparation method and high-resistance film - Google Patents
High-resistance film preparation method and high-resistance film Download PDFInfo
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- CN114686846A CN114686846A CN202210194534.7A CN202210194534A CN114686846A CN 114686846 A CN114686846 A CN 114686846A CN 202210194534 A CN202210194534 A CN 202210194534A CN 114686846 A CN114686846 A CN 114686846A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000011221 initial treatment Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 15
- 230000001276 controlling effect Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 21
- 230000008021 deposition Effects 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical group CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- JZPXQBRKWFVPAE-UHFFFAOYSA-N cyclopentane;indium Chemical compound [In].[CH]1[CH][CH][CH][CH]1 JZPXQBRKWFVPAE-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012713 reactive precursor Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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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
- C23C16/22—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
- C23C16/40—Oxides
- C23C16/403—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
- 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
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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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
- C23C16/22—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
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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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
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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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
- C23C16/455—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
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
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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
- C23C16/56—After-treatment
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Abstract
The disclosure relates to a high-resistance film and a preparation method thereof. The method comprises the following steps: placing the pretreated microchannel plate in atomic layer deposition equipment for primary treatment; depositing a conducting layer on the preliminarily processed microchannel plate; preparing a composite laminated structure on the conductive layer, wherein the composite laminated structure comprises i circulation structures, and each circulation structure comprises n circulation high-resistance phases and m circulation low-resistance phases; depositing a secondary electron emission layer on the composite laminate structure; and crystallizing the microchannel plate deposited with the secondary electron emission layer. The composite material of the high-resistance material and the low-resistance material in a specific ratio is prepared through ALD, and the high-resistance film for the MCP with the controllable resistance can be obtained by regulating and controlling the circulation ratio of a conductive phase in the composite material.
Description
Technical Field
The disclosure relates to the field of photoelectric technology, and in particular, to a high-resistance thin film and a preparation method thereof.
Background
The microchannel plate (MCP) is formed by tightly and orderly arranging millions of independent channel electron multipliers, and has the advantages of excellent electron multiplication performance, excellent time resolution, excellent space resolution and the like; therefore, the method is widely applied to the aspects of low-light night vision technology, space detection technology, radiation detection technology and the like. However, with the continuous improvement of the detection imaging requirements, the traditional lead silicate glass-based MCP is difficult to meet the structural and performance requirements due to the limitation of the processing performance.
Disclosure of Invention
In order to overcome the problems in the related art, embodiments of the present disclosure provide a method for manufacturing a high-resistance thin film and a high-resistance thin film. The technical scheme is as follows:
according to a first aspect of the embodiments of the present disclosure, there is provided a method for preparing a high-resistance thin film, including:
placing the pretreated microchannel plate in atomic layer deposition equipment for primary treatment;
depositing a conducting layer on the preliminarily processed microchannel plate;
preparing a composite laminated structure on the conductive layer, wherein the composite laminated structure comprises i circulation structures, and each circulation structure comprises n circulation high-resistance phases and m circulation low-resistance phases;
depositing a secondary electron emission layer on the composite laminate structure;
and crystallizing the microchannel plate on which the secondary electron emission layer is deposited.
The technical scheme provided by the embodiment of the disclosure can have the following beneficial effects: the embodiment of the disclosure provides a preparation method of a high-resistance film, which comprises the following steps: placing the pretreated microchannel plate in atomic layer deposition equipment for primary treatment; depositing a conducting layer on the preliminarily processed microchannel plate; preparing a composite laminated structure on the conductive layer, wherein the composite laminated structure comprises i circulation structures, and each circulation structure comprises n circulation high-resistance phases and m circulation low-resistance phases; depositing a secondary electron emission layer on the composite laminate structure; and crystallizing the microchannel plate on which the secondary electron emission layer is deposited. The composite material of the high-resistance material and the low-resistance material in a specific ratio is prepared by ALD, and the high-resistance film for the MCP with the controllable resistance can be obtained by regulating and controlling the circulation ratio of the conductive phase in the composite material.
In one embodiment, the depositing a conductive layer on the microchannel plate comprises:
al for performing a first predetermined cycle on the microchannel plate2O3And (6) depositing.
In one embodiment, the high resistance phase comprises: al (Al)2O3(ii) a The low resistance phase includes: TiO 22Or In2O3。
In one embodiment, the composite laminate structure has a thickness of less than or equal to 200nm and greater than or equal to 100 nm.
In one embodiment, n is any integer less than or equal to 20 and greater than or equal to 8.
In one embodiment, m is any integer less than or equal to 15 and greater than or equal to 4.
In one embodiment, the secondary electron emission layer includes: al (Al)2O3Or, MgO, or, Al2O3A composite material with MgO.
In one embodiment, the placing the pretreated microchannel plate in an atomic layer deposition apparatus for preliminary treatment includes:
vacuumizing the atomic layer deposition equipment, starting heating and raising the temperature to a preset temperature; the preset temperature is less than or equal to 150 ℃ and greater than or equal to 60 ℃;
and keeping the preset time and then starting nitrogen purging.
In one embodiment, the crystallizing the microchannel plate on which the secondary electron emission layer is deposited includes:
and crystallizing the microchannel plate deposited with the secondary electron emission layer by a vacuum annealing furnace.
According to a second aspect of the embodiments of the present disclosure, there is provided a high-resistance film, which is prepared by the method for preparing a high-resistance film according to any one of the embodiments.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and together with the description, serve to explain the principles of the disclosure.
Fig. 1 is a flow chart illustrating a method of preparing a high resistance thin film according to an exemplary embodiment.
Fig. 2 is a flow chart illustrating a method of making a high resistance thin film according to an exemplary embodiment.
Fig. 3 is a flow chart illustrating a method of making a high resistance thin film according to an exemplary embodiment.
FIG. 4 is an illustration of a TiO according to an example embodiment2The relationship between the doping concentration and the MCP bulk resistance is shown schematically.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the exemplary embodiments below are not intended to represent all implementations consistent with the present disclosure. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the present disclosure, as detailed in the appended claims.
Fig. 1 is a flowchart illustrating a method for manufacturing a high-resistance thin film according to an exemplary embodiment, as shown in fig. 1, including the following steps S101 to S103:
in step S101, the pretreated microchannel plate is placed in an atomic layer deposition apparatus for preliminary treatment.
The Atomic Layer Deposition (ALD) technology is a self-limiting Atomic-level film deposition technology, the method for preparing the film has the characteristics of uniform and compact surface, good continuity, high replication, high film purity, capability of accurately controlling the thickness of the film and the like, and the preparation of MCP dynode by the ALD technology instead of the traditional lead reduction dynode is a novel MCP research hotspot at home and abroad at present.
Common MCP working resistance is generally 106～109Omega, the thickness of the conductive layer is 100-200 nm, and the calculated sheet resistivity of the MCP conductive layer film prepared by ALD is about 1012～1014About Ω · cm, and no resistivity in this range in natureThe materials need to be compounded by different materials so that the film resistivity of the materials meets the range. The conductive layer combination of MCP developed by ALD at present mainly comprises ZnO-Al2O3，W-Al2O3And Mo-Al2O3。
And the present disclosure employs atomic layer deposition technology to prepare novel ALD-MCP on a microchannel bare plate.
In one implementation, the step S101 includes the following sub-steps S1011 to S1012:
in step S1011, the atomic layer deposition apparatus is vacuumized and heated to a preset temperature; the preset temperature is less than or equal to 150 ℃ and greater than or equal to 60 ℃;
in step S1012, a nitrogen purge is turned on after a preset time period.
Specifically, the washed and dried MCP is placed in a clamp and placed in an ALD (atomic layer deposition) device, the ALD device is vacuumized, heated to 60-150 ℃ after being started, nitrogen purging is started after the temperature is kept for a period of time, and deposition of the composite film in the following steps is carried out after the pressure of the device is stable.
In step S102, depositing a conductive layer on the preliminarily processed microchannel plate;
in one implementation, the first predetermined cycle of Al is performed on the microchannel plate2O3And (6) depositing.
Specifically, 50-100 cycles of Al can be preferentially deposited by ALD processes2O3As the bottom layer of the composite film layer.
In step S103, preparing a composite laminated structure on the conductive layer, the composite laminated structure including i cyclic structures, each cyclic structure including n cyclic high resistance phases and m cyclic low resistance phases;
wherein, the high resistant phase includes: al (Al)2O3(ii) a The low resistance phase includes: TiO 22Or In2O3。
The thickness of the composite laminated structure is less than or equal to 200nm and greater than or equal to 100 nm.
n is any integer less than or equal to 20 and greater than or equal to 8.
m is any integer of 15 or less and 4 or more.
In step S104, depositing a secondary electron emission layer on the composite laminated structure;
a secondary electron emission layer comprising: al (Al)2O3Or, MgO, or, Al2O3A composite material with MgO.
In step S105, the microchannel plate on which the secondary electron emission layer is deposited is subjected to crystallization treatment.
In one implementation, the crystallization process is performed on the microchannel plate on which the secondary electron emission layer is deposited by a vacuum annealing furnace.
Specifically, the ALD-MCP prepared in the step S104 is placed in a vacuum annealing furnace, and the vacuum annealing furnace is vacuumized to 10 degrees-1Pa, and raising the temperature to 250-500 ℃, and annealing the ALD-MCP for 4-10h, which aims to perform secondary crystallization on the low-resistance phase material prepared in the previous step and improve the conductivity of the low-resistance phase material.
In one implementation, the ALD carrier and purge gases are selected from nitrogen or argon; ALD reaction Chamber bottom pressure of 10-1Pa, the reaction pressure is 100-200 Pa.
The embodiment of the disclosure provides a preparation method of a high-resistance film, which comprises the following steps: placing the pretreated microchannel plate in atomic layer deposition equipment for primary treatment; depositing a conducting layer on the preliminarily processed microchannel plate; preparing a composite laminated structure on the conductive layer, wherein the composite laminated structure comprises i circulation structures, and each circulation structure comprises n circulation high-resistance phases and m circulation low-resistance phases; depositing a secondary electron emission layer on the composite laminate structure; and crystallizing the microchannel plate on which the secondary electron emission layer is deposited. The composite material of the high-resistance material and the low-resistance material in a specific ratio is prepared by ALD, and the high-resistance film for the MCP with the controllable resistance can be obtained by regulating and controlling the circulation ratio of the conductive phase in the composite material.
The implementation is described in detail below by way of several embodiments.
Example one
The purpose of the present disclosure is to prepare a high-resistance material Al with a specific ratio by low-temperature ALD2O3With low-resistance material TiO2(or In)2O3) The composite material is annealed at high temperature to make TiO2(or In)2O3) Recrystallization reduces the composite resistivity. The high-resistance film for MCP with controllable resistance is achieved by regulating and controlling the circulation ratio of the conductive phase in the composite material. The present disclosure provides a specific technical solution as follows:
s1, cleaning MCP;
s2, placing the washed and dried MCP in a clamp and in an ALD deposition device, vacuumizing, starting heating, raising the temperature to 60-150 ℃, keeping the temperature for a period of time, starting nitrogen purging, and depositing a composite film after the pressure of the device is stable:
s3 preferential deposition of 50-100 cycles of Al by ALD Process2O3As a composite film priming layer;
s4, preparing a high-resistance phase and low-resistance phase composite laminated structure by an ALD process, namely preparing a conductive layer;
wherein the high-resistance phase is Al2O3The low-resistance phase being TiO2Or In2O3；
The composite laminated structure comprises i cyclic structures, wherein each cyclic structure comprises n high-resistance phases of cycles and m low-resistance cyclic phases of cycles;
the total design thickness of the composite lamination is 100-200 nm;
n is any integer of 8-20, and m is any integer of 4-15;
s5, depositing a 50-100Cycle secondary electron emission layer by an ALD process;
wherein the secondary electron emission layer comprises Al2O3MgO or a composite thereof;
s6, placing the prepared ALD-MCP into a vacuum annealing furnace, and vacuumizing to 10 DEG-1Pa, and heating to 250-500 ℃;
s7, annealing by ALD-MCP for 4-10h, and the purpose is to perform secondary crystallization on the low-resistance phase material prepared in the previous step and improve the conductivity of the low-resistance phase material;
s8, obtaining the prepared ALD-MCP;
preferably, the ALD carrier gas and the purge gas are nitrogen or argon;
preferably, the ALD reaction chamber has a bottom pressure of 10-1Pa, the reaction pressure is 100-200 Pa;
compared with the prior art, the method has the following advantages:
1. the method adopts a low-temperature ALD preparation method, the process is simple and controllable, the resistivity of the conductive layer can be accurately controlled by controlling the circulation proportion of the conductive phase, and the prepared film has compact structure, smooth surface and uniform thickness;
2. the resistivity of the conducting layer is further improved by adopting secondary high-temperature annealing, and tests show that the conductivity of the MCP is improved after annealing, and the stability of the MCP is also obviously improved, namely the MCP bulk resistance after annealing can not obviously fluctuate along with the change of voltage and service temperature;
3. further, the disclosed ALD-MCP annealing step may be combined with a high temperature degassing step, simplifying the manufacturing process.
Example two
ALD of TiO2-Al2O3Conductive layer
Placing the cleaned microchannel plate in a fixture and an ALD deposition device, starting a vacuum pump to evacuate to 10 DEG-1Pa, opening the chamber, heating to 80 ℃, and heating to TiO 22The reaction precursor source is TDMAT [ tetra (dimethylamino) titanium]And H2O，Al2O3The reaction precursor source is TMA [ trimethyl aluminum ]]And H2O, setting the TDMAT heating temperature to be 60 ℃ and setting nitrogen N2The flow rates were 80sccm +80sccm, respectively. First, 50 cycles (English) of Al were carried out2O3Deposition of a bottom layer with a single Cycle of TMA/N2/H2O/N20.5s/8s/0.5s/10 s. Secondly, a conductive layer is deposited, firstly 12cycle Al2O3Deposition with a single Cycle of TMA/N2/H2O/N20.5s/8s/0.5s/10 s; then 6cycle TiO is carried out2Deposition, singulationCycle is TDMAT/N2/H2O/N20.5s/10s/0.5s/10 s. 12Cycle Al in this example2O3And 6Cycle TiO2And repeating the 70 cycles of the large Cycle for a large Cycle to complete the deposition of the conductive layer. Finally, 80Cycle Al is carried out2O3As the secondary electron emission layer, the single Cycle is TMA/N2/H2O/N20.5s/8s/0.5s/10 s. After the deposition is finished, the temperature is reduced and the sample is taken, the prepared ALD-MCP is placed in a vacuum annealing furnace, and the vacuum is pumped to 10 DEG-1Pa, heating to 450 ℃ and preserving the heat for 8 h. And taking out after cooling.
EXAMPLE III
ALD of TiO2-Al2O3Conductive layer
Placing the cleaned microchannel plate in a fixture and an ALD deposition device, starting a vacuum pump to evacuate to 10 DEG-1Pa, opening the chamber, heating to 100 ℃, and TiO2The source of the reactive precursor is TiCl4And H2O，Al2O3The reaction precursor source is TMA [ trimethyl aluminum ]]And H2O，N2The flow rates were 80sccm +80sccm, respectively. Wherein, TiO2The doping concentration versus MCP bulk resistance is shown in fig. 4.
First, 50Cycle Al was performed2O3Bottom layer deposition with single Cycle of TMA/N2/H2O/N20.5s/8s/0.5s/10 s. Secondly, a conductive layer is deposited, firstly 12cycle Al2O3Deposition with a single Cycle of TMA/N2/H2O/N20.5s/8s/0.5s/10 s; 4cycle TiO further2Deposition with a single Cycle of TiCl4/N2/H2O/N20.3s/10s/0.5s/10 s. 12Cycle Al in this example2O3And 4Cycle TiO2And repeating the above large Cycle of 75 cycles for a large Cycle to complete the deposition of the conductive layer. Finally, 80Cycle Al is carried out2O3As the secondary electron emission layer, the single Cycle is TMA/N2/H2O/N20.5s/8s/0.5s/10 s. After the deposition is finished, the temperature is reduced and the sample is taken, the prepared ALD-MCP is placed in a vacuum annealing furnace, and the vacuum is pumped to 10 DEG-1Pa, heating to 450 ℃ and preserving the heat for 8 h. And taking out after cooling.
Example four
ALD deposition of In2O3-Al2O3Conductive layer
Placing the cleaned microchannel plate in a fixture and an ALD deposition device, starting a vacuum pump to evacuate to 10 DEG-1Pa, opening the chamber, heating to 100 deg.C, In2O3The sources of the reaction precursor are Incp (cyclopentadienyl indium) and H2O，Al2O3The reaction precursor source is TMA [ trimethyl aluminum ]]And H2O，N2The flow rates were 80sccm +80sccm, respectively. First, 50Cycle Al was performed2O3Deposition of a bottom layer with a single Cycle of TMA/N2/H2O/N20.5s/8s/0.5s/10 s. Secondly, a conductive layer is deposited, firstly 10cycle Al2O3Deposition with a single Cycle of TMA/N2/H2O/N20.5s/8s/0.5s/10 s; then 8 cycles of In were carried out2O3Deposition, single Cycle is Incp/N2/H2O/N20.3s/10s/0.5s/10 s. 10Cycle Al in this example2O3And 3Cycle Incp is a large Cycle, and the conductive layer deposition can be completed by repeating the large Cycle of 70 cycles. Finally, 80Cycle Al is carried out2O3As the secondary electron emission layer, the single Cycle is TMA/N2/H2O/N20.5s/8s/0.5s/10 s. After the deposition is finished, the temperature is reduced and the sample is taken, the prepared ALD-MCP is placed in a vacuum annealing furnace, and the vacuum is pumped to 10 DEG-1Pa, heating to 350 ℃ and keeping the temperature for 8 h. And taking out after cooling.
The disclosure also provides a high-resistance film, which is prepared by the preparation method of any one of the embodiments.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
It will be understood that the present disclosure is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the present disclosure is limited only by the appended claims.
Claims (10)
1. A preparation method of a high-resistance film is characterized by comprising the following steps:
placing the pretreated microchannel plate in atomic layer deposition equipment for primary treatment;
depositing a conducting layer on the preliminarily processed microchannel plate;
preparing a composite laminated structure on the conductive layer, wherein the composite laminated structure comprises i circulation structures, and each circulation structure comprises n circulation high-resistance phases and m circulation low-resistance phases;
depositing a secondary electron emission layer on the composite laminate structure;
and crystallizing the microchannel plate on which the secondary electron emission layer is deposited.
2. The method of claim 1, wherein the depositing a conductive layer on the microchannel plate comprises:
al for performing a first predetermined cycle on the microchannel plate2O3And (6) depositing.
3. The method of claim 1, wherein the high resistance phase comprises: al (Al)2O3(ii) a The low resistance phase includes: TiO 22Or In2O3。
4. The method of claim 1, wherein the composite laminate structure has a thickness of less than or equal to 200nm and greater than or equal to 100 nm.
5. The method of claim 1, wherein n is any integer less than or equal to 20 and greater than or equal to 8.
6. The method of claim 1, wherein m is any integer less than or equal to 15 and greater than or equal to 4.
7. The method of claim 1, wherein the secondary electron emission layer comprises: al (Al)2O3Or, MgO, or, Al2O3A composite material with MgO.
8. The method of claim 1, wherein the pre-treating the microchannel plate in the atomic layer deposition apparatus comprises:
vacuumizing the atomic layer deposition equipment, starting heating and raising the temperature to a preset temperature; the preset temperature is less than or equal to 150 ℃ and greater than or equal to 60 ℃;
and keeping the preset time and then starting nitrogen purging.
9. The method according to claim 1, wherein the crystallizing treatment of the microchannel plate on which the secondary electron emission layer is deposited comprises:
and crystallizing the microchannel plate deposited with the secondary electron emission layer by a vacuum annealing furnace.
10. A high-resistance film, which is prepared by the method of any one of claims 1 to 9.
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