CN104152868B - A kind of method utilizing technique for atomic layer deposition to make microchannel plate functional layer - Google Patents

A kind of method utilizing technique for atomic layer deposition to make microchannel plate functional layer Download PDF

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CN104152868B
CN104152868B CN201410363192.2A CN201410363192A CN104152868B CN 104152868 B CN104152868 B CN 104152868B CN 201410363192 A CN201410363192 A CN 201410363192A CN 104152868 B CN104152868 B CN 104152868B
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zinc
microchannel plate
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magnesium
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CN104152868A (en
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朱香平
邓国宝
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Dongguan Zhongke atomic precision manufacturing technology Co., Ltd
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XiAn Institute of Optics and Precision Mechanics of CAS
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Abstract

The present invention provides a kind of method utilizing technique for atomic layer deposition to make microchannel plate functional layer, to overcome microchannel plate to utilize tradition hydrogen reduction technology to prepare the inherent shortcoming of functional layer, solve microchannel plate functional layer and manufacture complexity, unstable properties, the difficult problems such as the life-span is not long, produce adhesive force is strong, smooth surface, thickness are uniform, constituent purity is high resistive layer and emission layer, improve the stability of microchannel plate, extend its working life.

Description

A kind of method utilizing technique for atomic layer deposition to make microchannel plate functional layer
Technical field
The invention belongs to microelectronics nanotechnology and manufacture photoelectronic imaging device arts, particularly relate to Technique for atomic layer deposition makes the method for the functional layer such as microchannel plate resistive layer and emission layer.
Background technology
Microchannel plate (MCP) is a kind of excellent electron multiplier, volume is little, lightweight, gain is high, Noise is low, running voltage is low, response time is short, and spatial resolution and temporal resolution are high, and radioprotective Ability is strong, can under strong magnetic field circumstance the advantage such as normal work.It is mainly used as the core device of image intensifier Part.It is high that it has gain,.Microchannel plate in lll night vision, image intensifying equipment, detector as core Device, in scientific instrument, medical image, satellite map and scouting, law enforcement, military, anti-terrorism and civilian It is widely used Deng field tool.
One layer of semi-conducting material that can launch secondary electron is had to prepare on the inwall of each passage of microchannel plate Emission layer.After adding certain voltage between to microchannel plate upper/lower electrode, each passage produces A raw uniform electric field.After the electronics having certain primary power enters electric field, touch with conduit wall Hit and produce secondary electron, and secondary electron is accelerated under the effect of axial electric field, such secondary electrical Son impinges upon on the emission layer on wall, can produce again the newest secondary electron, then at microchannel plate Outfan will produce by a large amount of electric molecular electron clouds.Generally, emissive layer materials selects Magnesium oxide that secondary electron yield is higher or aluminium oxide, but its dielectric coefficient is higher, and resistance is non- Chang great, it is difficult to effectively supplement electronics to emission layer by additional power source, it is therefore desirable to meet suitable body electricity Resistance (100M Ω magnitude), it is achieved electronics continual multiplication.
So far on market, commercial microchannel plate product mainly contains lead silicate glass (LSG) microchannel plate, Its excellent performance is represented in fields such as scientific instrument, medical image, satellite map.Due to tradition lead silicon The functional layer manufacturing technology of silicate glass microchannel plate uses mixes lead and carries out hydrogen reduction technology.Hydrogen is also Former technology not only complex process, for containing lead silicate glass microchannel plate, it is difficult to accomplish at silicate Glass aperture inwall adulterates lead salt uniformly, and thickness is also difficult to accurately control, follow-up hydrogen reduction skill Although art can realize the lead on surface and near surface to be reduced into metallic state, but the oxidation that distance surface is deeper Lead is difficult to Restore All, and this will have a strong impact on the performance and used life of microchannel plate.At microelectronics The technique for atomic layer deposition that in nanotechnology, fast development is got up, can overcome the intrinsic of hydrogen reduction technology to lack Fall into, prepare thickness uniform, smooth surface, the functional layer that adhesive force is strong.Last at inner wall surface conductance Layer is with electron emission layer preparation process, and its performance reproducibility is poor and easily causes microchannel plate and has wide model The gain enclosed and bulk resistor, directly result in the performance difference between plate bigger.Along with the development of society, to micro- The performance of channel plate is had higher requirement, but tradition lead silicate glass microchannel plate itself and merit The intrinsic defect of ergosphere manufacturing technology makes its spatial resolution, temporal resolution, signal to noise ratio, high counting Rates etc. are already close to its theoretical limit, and repeatability, stability and life-span are also restrained.
In order to overcome the technical bottleneck of microchannel plate, with Galileo company of the U.S., CirCom-ACMI company, Each scientific research institution that Litton company, ITT Corp., Photonis company of France etc. are representative puts into a large amount of people Power and material resources are devoted to explore substitution material and the improvement technology of tradition lead silicate glass microchannel plate, first After have developed long-life microchannel plate, bending channel microchannel plate, high export technique microchannel plate, body Electro-conductive glass microchannel plate, novel microsphere microchannel plate, semiconductor microactuator channel plate, silicon microchannel plate (Si-MCP).Long-life microchannel plate, bending channel microchannel plate, the merit of high export technique microchannel plate Ergosphere preparation is also based on mixing lead and carrying out the improvement of hydrogen reduction technology, although its performance is to a certain extent It is improved, but the bottleneck of this technology still exists, be difficult to improve further its performance.Body conducts electricity Glass micro channels plate, novel microsphere microchannel plate, semiconductor microactuator channel plate, silicon microchannel plate (Si-MCP) Semiconductor layer (conductive layer) and electron emission layer preparation selected respectively chemical vapour deposition technique (CVD), The methods such as liquid phase deposition process (LPD) are explored.
CVD technology is to use the chemical vapors of reactant to carry out chemical reaction in being constantly passed through vacuum chamber, Deposition oxide thin film on substrate, it is achieved prepared by microchannel plate functional layer.This deposition process is continuous print, And the deposition thickness of thin film and the uniformity of temperature, pressure, gas flow and flowing, time etc. multiple Factor is relevant.Liquid phase deposition process (LPD) is generation sull from the aqueous solution of metal fluoride Method, by adding water, boric acid or metallic aluminium make metal fluoride slowly hydrolyze, make metal-oxide It is deposited on matrix surface, completes microchannel plate functional layer and prepare.This method requires hydrolysis and solution Degree of supersaturation well control.
In view of chemical vapour deposition technique (CVD) deposition process is continuous print, it is impossible to enough accurately control thin The uniformity of film, step coverage rate and thickness.Liquid phase deposition (LPD) prepares sull technique Carrying out in reactant liquor, this method is it is difficult to ensure that at microchannel plate aperture inwall deposited oxide equably Thing thin film, also reactant liquor likely corrodes microchannel plate aperture inwall, and then changes microchannel plate aperture Arrangement.Therefore can employing chemical vapour deposition technique and liquid phase deposition deposition of thick on inner walls of deep holes surface The continuous film that degree is uniform and composition is consistent with physical and chemical performance is under suspicion, and this directly affects, and silicon is micro-to be led to The stability of guidance tape performance, the technology of preparing exploring novel micropore inner wall surface functional layer also will be to realize The practical problem that must solve of silicon microchannel plate.
Technique for atomic layer deposition (ALD) is a kind of advanced thin films deposition technique fast-developing in recent years, There is splendid uniformity, step coverage, conformality, repeatability and accurately control at atomic scale The outstanding advantages such as thickness.Utilize technique for atomic layer deposition to design synthesizing new function nano material, develop it Application in fields such as the energy, catalysis, environment, photoelectric devices is current study hotspot.
From the principle, technique for atomic layer deposition is to obtain product thin film on substrate by chemical reaction, But in the quality of deposition reaction principle, the requirement of deposition reaction condition and sedimentary all with traditional chemistry Vapour deposition process is different, and in conventional chemical vapor sedimentation technical process, chemical vapors is constantly passed through very Empty indoor, therefore this deposition process is continuous print, the thickness of deposition thin film and temperature, pressure, gas stream The many factors such as amount and the uniformity of flowing, time are relevant.Technique for atomic layer deposition is by by gas phase Presoma pulse be alternately passed through reactor and on matrix chemisorbed and react formed deposition thin film one The method of kind.Technique for atomic layer deposition can control composition and the thickness of thin film, prepared thin film well Have that conformality is good, purity is high, uniformity good, thickness and precision reaches the advantages such as Ethylmercurichlorendimide level, the most by extensively General is applied to produce high-quality thin-film material, and development is swift and violent, is the thin film system of great market potential Standby technology.Technique for atomic layer deposition is compared with chemical vapour deposition technique, it can be ensured that strictly protect in gas phase Hold presoma to be isolated from each other, the uniformity of thin film, step coverage rate and thickness can be accurately controlled. The self-limiting growth mechanism of technique for atomic layer deposition makes thin film with a list in the process window of non-constant width Layer is unit repeated growth, and deposition parameter is highly controllable, and uniformity is good, do not have pin hole, and to thin film figure The conformality of shape is fabulous, can control the precision of film thickness and reach atomic level and to realize large area uniform Growth, completes have the microchannel plate aperture inner wall surface uniform coated of very big L/D ratio, solves tradition The difficult problem that cannot realize of film plating process.Therefore use technique for atomic layer deposition, can perfectly solve micro- The preparation of the functional layers such as channel plate resistive layer and emission layer, improves conventional microchannel plate processing technology, greatly Ground improves the performance of microchannel plate.
Summary of the invention
The present invention provide a kind of utilize technique for atomic layer deposition make microchannel plate functional layer method, with gram Taking microchannel plate utilizes tradition hydrogen reduction technology to prepare the inherent shortcoming of functional layer, solves microchannel plate function Layer manufactures complexity, unstable properties, the difficult problems such as the life-span is long, produce that adhesive force is strong, smooth surface, Thickness uniformly, the high resistive layer of constituent purity and emission layer, improve the stability of microchannel plate, Extend its working life.
The concrete technical solution of the present invention is as follows:
This method utilizing technique for atomic layer deposition to make microchannel plate functional layer comprises the following steps:
1] raw material is chosen
Choosing the material being suitable to prepare microchannel plate as substrate, it is zinc that gaseous state diethyl zinc makees (DEZ) Source, gaseous state trimethyl aluminium (TMA) is as aluminum source, gaseous state dicyclo penta 2 cyclopentadienyl magnesium (MgCP2) as magnesium Source, gaseous state deionized water is as oxygen source, and high pure nitrogen is as cleaning gas;
2] resistive layer is prepared
2.1] in vacuum environment, it is passed through cleaning gas, and makes the cleaning gas concentration in this vacuum environment reach Stop after criteria threshold being passed through;
2.2] according to zinc source, the exposure time in aluminum source, circulate in vacuum environment under the conditions of 200 DEG C and be passed through Zinc source, aluminum source, oxygen source carry out aluminum Zinc form and mix technique, make each aperture in the substrate in vacuum environment The aluminum uniformly generating 40-100nm thickness on inwall mixes zinc-oxide film;
Or
According to zinc source, the exposure time in magnesium source, under the conditions of 200 DEG C in vacuum environment circulation be passed through zinc source, Magnesium source, oxygen source carry out magnesium Zinc form and mix technique, make in the substrate in vacuum environment on the inwall of each aperture The magnesium uniformly generating 40-100nm thickness mixes zinc-oxide film;
3] emission layer is prepared
3.1] discharge the foreign gas that step 2 produces in vacuum environment, be again passed through clear in vacuum environment Clean gas, and make the cleaning gas concentration in this vacuum environment stop being passed through after reaching criteria threshold;
3.2] according to the exposure time in magnesium source, under the conditions of 95 DEG C, in vacuum environment, circulation is passed through magnesium source, clear Clean gas, oxygen source carry out magnesia film growth technique, and the aluminum making step 2 generate mixes zinc-oxide film Or magnesium mixes the magnesia film uniformly generating 80-100nm thickness on zinc-oxide film;
Or the exposure time according to aluminum source, under the conditions of 95 DEG C, in vacuum environment, circulation is passed through aluminum source, clear Clean gas, oxygen source carry out magnesia film growth technique, and the aluminum making step 2 generate mixes zinc-oxide film Or magnesium mixes the aluminum oxide film uniformly generating 80-100nm thickness on zinc-oxide film.
In above-mentioned steps 2.2, the doping-sequence of zinc-aluminium doping circulation is DEZ/TMA/H2O, zinc-aluminium mixes ratio Example is 19:1, after i.e. carrying out 19 zinc oxide circulations, carries out 1 aluminum doping circulation;Exposure time is: DE Z/N2/H2O/N2=0.1s/3s/0.1s/4s, TMA/N2/H2O/N2=0.1s/3s/0.1s/4s, DEZ/N2/TMA/ N2/H2O/N2=0.1s/3s/0.1s/3s/0.1s/4s;The circulation sum of each sample is 400 times.
In above-mentioned steps 2.2, the doping-sequence of zinc-magnesium doping circulation is DEZ/MgCP2/H2O, zinc-magnesium is joined Miscellaneous ratio is 9:1, after i.e. carrying out 9 zinc oxide circulations, carries out 1 mg-doped circulation;Exposure time is: DEZ/N2/H2O/N2=0.2s/4s/0.15s/6s, MgCP2/N2/H2O/N2=0.2s/5s/0.2s/5s, DEZ/N2/ MgCP2/N2/H2O/N2=0.15s/4s/0.1s/4s/0.1s/6s;The circulation sum of each sample is 180 times.
In above-mentioned steps 3.2, the time of exposure of magnesia film growth technique: MgCP2//N2/H2O/N2=2 0ms/5s/20ms/5s。
In above-mentioned steps 3.2, the time of exposure of aluminum oxide film growth technique: TMA/N2/H2O/N2=0.1s /3s/0.1s/4s。
Above-mentioned steps 3 carries out step 4 after completing and processes:
4] using vacuum evaporation technology to prepare conductive electrode on upper and lower two surfaces of substrate, electrode material is Nichrome.
It is an advantage of the current invention that:
Technique for atomic layer deposition of the present invention makes microchannel plate resistive layer and emission layer, it is possible to achieve thickness reaches 0. The precision of 1nm, so the resistive layer of preparation tens nanometer thickness and emission layer, is fully able to meet surface accuracy The advantages such as requirement, also has compact structure, and adhesive force is strong.Ratio and thickness can also be mixed by control, Adjust resistance value accurately.
Resistive layer material selection aluminum-doped zinc oxide films or mg-doped zinc-oxide film, relatively conventional microchannel The leaded resistive layer of plate, hot property is more stable, and surface is evenly.
Emissive layer materials selects magnesium oxide or aluminium oxide, has both overcome traditional secondary electron emission layer material The problem of lead processing difficulties, also have that surface is more smooth, adhesive force is higher, secondary electron yield more Advantages of higher.
The present invention utilizes technique for atomic layer deposition to make microchannel plate resistive layer and emission layer, uses standard Microelectronics nanotechnology, compared with tradition hydrogen reduction technology, it is possible to achieve batch processing and scale metaplasia Produce, production cost will be reduced, improve production efficiency.
The present invention utilizes technique for atomic layer deposition can produce microchannel plate resistive layer evenly and transmitting Layer, improves the gain of microchannel plate, extends the life-span of microchannel plate, expands military, astronomical further The application in the fields such as, high-energy physics, chemistry, quantum electronics, Ultra-Weak Bioluminescence detection.
Accompanying drawing explanation
Fig. 1 is technique for atomic layer deposition device schematic diagram of the present invention;
Fig. 2 is the present invention uncoated microchannel plate generalized section;
Fig. 3 is the generalized section that the present invention completes resistive layer thin film;
Fig. 4 is the generalized section that the present invention completes emission layer thin film;
Fig. 5 is the generalized section that the present invention completes electrode evaporation.
Description of reference numerals:
1-valve, 2-cleans gas container, 3-diethyl zinc container, 4-trimethyl aluminium container, 5-dicyclo penta Two cyclopentadienyl magnesium containers, 6-deionized water container, 7-vacuum chamber, 8-prepares the substrate of microchannel plate, and 9-sample is put down Platform, 10-vacuum pump, 11-Tail gas measuring device, 12-control system, 13-microchannel plate aperture, 14-is micro-logical Road panel aperture inwall, 15-conductive layer, 16-secondary electron emission layer, 17-electrode, 18-power supply.
Detailed description of the invention
Technique for atomic layer deposition makes microchannel plate resistive layer and emission layer, to every in preparation technology link Operation and parameter have high required precision.As it is shown in figure 1, according to the program arranged, control system is first First open cleaning gas appts valve, be passed through cleaning gas in vacuum chamber, open vacuum-pump line simultaneously Valve, despumation gas, carry out composition and Concentration Testing at tail gas simultaneously.When the cleaning in tail gas After gas concentration reaches to set threshold value, close vacuum-pump line valve, close cleaning gas appts valve afterwards Door.
Then according to doping-sequence DEZ/TMA/H2O, aluminum zinc mixes ratio 19:1, exposure time DEZ/N2/H2O/N2=0.1s/3s/0.1s/4s, TMA/N2/H2O/N2=0.1s/3s/0.1s/4s, DEZ/N2/TMA/N2/H2O/N2=0.1s/3s/0.1s/3s/0.1s/4s, carries out aluminum zinc at a temperature of 200 DEG C and follows Ring mixes technique, and control system is by each precursor container, cleaning gas container, vacuum-pump line valve The open and-shut mode of door and time, on the inwall in each aperture of substrate, such as Fig. 2, produce uniformly The aluminum of 40-100nm thickness mixes zinc-oxide film, such as Fig. 3.
Then technique for atomic layer deposition is utilized to manufacture emission layer.According to the program arranged, control system is first Open cleaning gas appts valve, be passed through cleaning gas in vacuum chamber, open vacuum-pump line valve simultaneously Door, the foreign gas that eliminating is remaining after preparing conductive layer, carry out composition and Concentration Testing at tail gas simultaneously. After the cleaning gas concentration in tail gas reaches to set threshold value, close vacuum-pump line valve, turn off clear Clean gas device valve.Then according to the time of exposure of magnesia film growth technique: MgCP2//N2/H2O/N2=20ms/5s/20ms/5s, carries out magnesia film growth work at a temperature of 95 DEG C Skill, mixes the magnesia film producing 80-100nm thickness on zinc-oxide film uniformly at aluminum, such as figure 4。
Then utilize vacuum evaporation technology in the substrate preparing microchannel plate after above-mentioned PROCESS FOR TREATMENT Lower two surfaces produce conductive electrode, as shown in Figure 5.
Use following doping-sequence: TMA/DEZ/H2O, and keep mixing ratio, exposure time condition not Becoming, obtained resistive layer and emission layer under equal conditions carry out performance test, and its surface accuracy is only 100nm magnitude, compared with the scheme that the present invention proposes, surface accuracy have dropped 1000 times.
Use remaining aluminum zinc to mix proportionality coefficient, as aluminum zinc mixes than for 20:1 or 18:1, and protect Demonstrate,proving remaining condition and keep constant, the electric conductivity of obtained microchannel plate resistive layer and emission layer changes relatively Greatly, it is impossible to meet the resistance characteristic of microchannel plate.
To sum up, above-mentioned parameter is the best parameter group preparing high performance MCP resistive layer and emission layer.

Claims (6)

1. one kind utilizes the method that technique for atomic layer deposition makes microchannel plate functional layer, it is characterised in that Comprise the following steps:
1] raw material is chosen
Choosing the material being suitable to prepare microchannel plate as substrate, it is zinc that gaseous state diethyl zinc makees (DEZ) Source, gaseous state trimethyl aluminium (TMA) is as aluminum source, gaseous state dicyclo penta 2 cyclopentadienyl magnesium (MgCP2) as magnesium Source, gaseous state deionized water is as oxygen source, and high pure nitrogen is as cleaning gas;
2] resistive layer is prepared
2.1] in vacuum environment, it is passed through cleaning gas, and makes the cleaning gas concentration in this vacuum environment reach Stop after criteria threshold being passed through;
2.2] according to zinc source, the exposure time in aluminum source, circulate in vacuum environment under the conditions of 200 DEG C and be passed through Zinc source, aluminum source, oxygen source carry out aluminum Zinc form and mix technique, make each aperture in the substrate in vacuum environment The aluminum uniformly generating 40-100nm thickness on inwall mixes zinc-oxide film;
Or
According to zinc source, the exposure time in magnesium source, under the conditions of 200 DEG C in vacuum environment circulation be passed through zinc source, Magnesium source, oxygen source carry out magnesium Zinc form and mix technique, make in the substrate in vacuum environment on the inwall of each aperture The magnesium uniformly generating 40-100nm thickness mixes zinc-oxide film;
3] emission layer is prepared
3.1] discharge the foreign gas that step 2 produces in vacuum environment, be again passed through clear in vacuum environment Clean gas, and make the cleaning gas concentration in this vacuum environment stop being passed through after reaching criteria threshold;
3.2] according to the exposure time in magnesium source, under the conditions of 95 DEG C, in vacuum environment, circulation is passed through magnesium source, clear Clean gas, oxygen source carry out magnesia film growth technique, and the aluminum making step 2 generate mixes zinc-oxide film Or magnesium mixes the magnesia film uniformly generating 80-100nm thickness on zinc-oxide film;
Or the exposure time according to aluminum source, under the conditions of 95 DEG C, in vacuum environment, circulation is passed through aluminum source, clear Clean gas, oxygen source carry out magnesia film growth technique, and the aluminum making step 2 generate mixes zinc-oxide film Or magnesium mixes the aluminum oxide film uniformly generating 80-100nm thickness on zinc-oxide film.
The side utilizing technique for atomic layer deposition to make microchannel plate functional layer the most according to claim 1 Method, it is characterised in that: in described step 2.2, the doping-sequence of zinc-aluminium doping circulation is DEZ/TMA/H2 O, the zinc-aluminium ratio of mixing is 19:1, after i.e. carrying out 19 zinc oxide circulations, carries out 1 aluminum doping circulation; Exposure time is: DEZ/N2/H2O/N2=0.1s/3s/0.1s/4s, TMA/N2/H2O/N2=0.1s/3s/0.1s/4s, DEZ/N2/TMA/N2/H2O/N2=0.1s/3s/0.1s/3s/0.1s/4s;The circulation sum of each sample is 400 Secondary.
The side utilizing technique for atomic layer deposition to make microchannel plate functional layer the most according to claim 1 Method, it is characterised in that: in described step 2.2, the doping-sequence of zinc-magnesium doping circulation is DEZ/MgCP2/ H2O, the zinc-magnesium ratio of mixing is 9:1, after i.e. carrying out 9 zinc oxide circulations, carries out 1 mg-doped circulation; Exposure time is: DEZ/N2/H2O/N2=0.2s/4s/0.15s/6s, MgCP2/N2/H2O/N2=0.2s/5s/0.2s / 5s, DEZ/N2/MgCP2/N2/H2O/N2=0.15s/4s/0.1s/4s/0.1s/6s;The circulation sum of each sample It it is 180 times.
4. make microchannel plate function according to the arbitrary described technique for atomic layer deposition that utilizes of claims 1 to 3 The method of layer, it is characterised in that: in described step 3.2, the time of exposure of magnesia film growth technique: MgCP2//N2/H2O/N2=20ms/5s/20ms/5s.
5. make microchannel plate function according to the arbitrary described technique for atomic layer deposition that utilizes of claims 1 to 3 The method of layer, it is characterised in that: in described step 3.2, the time of exposure of aluminum oxide film growth technique: T MA/N2/H2O/N2=0.1s/3s/0.1s/4s.
The side utilizing technique for atomic layer deposition to make microchannel plate functional layer the most according to claim 1 Method, it is characterised in that: described step 3 carries out step 4 after completing and processes:
4] using vacuum evaporation technology to prepare conductive electrode on upper and lower two surfaces of substrate, electrode material is Nichrome.
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CN105502283A (en) * 2015-12-07 2016-04-20 华东师范大学 Method for depositing three-dimensional nano-film structure on side wall of microchannel plate by hydrothermal method
CN105448638B (en) * 2015-12-15 2017-09-22 中国科学院西安光学精密机械研究所 A kind of micro-channel type entrance window and preparation method thereof
LU93390B1 (en) * 2016-12-21 2018-07-24 Luxembourg Inst Science & Tech List Method for depositing alumina by atomic layer deposition
CN108493083B (en) * 2018-04-13 2019-11-12 中国建筑材料科学研究总院有限公司 Ultralow temperature stablizes the microchannel plate and preparation method thereof of temperature resistance characteristic
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CN111968898B (en) * 2020-07-24 2022-04-22 北方夜视技术股份有限公司 Method and apparatus for microchannel plate hydrogen reduction
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