CN111243922A - Fluorescent film screen, preparation method thereof and application thereof in microchannel plate image intensifier - Google Patents

Fluorescent film screen, preparation method thereof and application thereof in microchannel plate image intensifier Download PDF

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CN111243922A
CN111243922A CN202010045735.1A CN202010045735A CN111243922A CN 111243922 A CN111243922 A CN 111243922A CN 202010045735 A CN202010045735 A CN 202010045735A CN 111243922 A CN111243922 A CN 111243922A
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fluorescent
layer
film layer
film
screen
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CN111243922B (en
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周东站
刘辉
蔡华
王辰
刘畅
廉姣
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China Building Materials Academy CBMA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J31/00—Cathode ray tubes; Electron beam tubes
    • H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
    • H01J31/10—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes
    • H01J31/12—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes with luminescent screen
    • H01J31/123—Flat display tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J31/00—Cathode ray tubes; Electron beam tubes
    • H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
    • H01J31/50—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output
    • H01J31/506—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output tubes using secondary emission effect
    • H01J31/507—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output tubes using secondary emission effect using a large number of channels, e.g. microchannel plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/20—Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel
    • H01J9/22—Applying luminescent coatings
    • H01J9/221—Applying luminescent coatings in continuous layers
    • H01J9/224—Applying luminescent coatings in continuous layers by precipitation

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
  • Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)

Abstract

The invention relates to a fluorescent film screen, a preparation method thereof and application thereof in a microchannel plate image intensifier. The fluorescent film layer is a light-emitting functional layer of the fluorescent screen and determines the performances of the fluorescent screen such as light-emitting spectrum, fluorescent life and the like; the fluorescence enhancement layer is a functional layer for enhancing the luminescence of the fluorescent layer, and can obviously improve the luminescence intensity of the fluorescent screen; the isolation film layer is a transparent insulating layer positioned between the fluorescent layer and the fluorescence enhancement layer; the conductive layer is a film layer which can smoothly conduct the negative charges of the fluorescent screen out, and has the functions of reflecting fluorescence and protecting the fluorescent layer.

Description

Fluorescent film screen, preparation method thereof and application thereof in microchannel plate image intensifier
Technical Field
The invention belongs to the technical field of display of a microchannel plate image intensifier, and particularly relates to a fluorescent film screen, a preparation method of the fluorescent film screen and application of the fluorescent film screen in the microchannel plate image intensifier.
Background
An MCP (micro channel plate) image intensifier is an important imaging device preferentially selected in weak signal detection and widely applied to the fields of low-light night vision, ultraviolet early warning, particle detection and the like. The phosphor screen, which is a key component of the MCP image intensifier, serves to convert the MCP multiplied electronic signals into optical signals and output the optical signals for viewing and recording. It follows that the quality of the phosphor screen directly affects the performance quality and lifetime of the MCP image intensifier.
At present, a fluorescent screen for an MCP image enhancer uses fluorescent powder as a fluorescent material, that is, fluorescent powder particles for a CRT are uniformly coated on a transparent substrate 1 ' with the aid of an adhesive to obtain a fluorescent powder layer 8 ', a smooth and flat organic film is coated on the fluorescent powder layer 8 ', an aluminum film layer is coated on the basis of the organic film to obtain a conductive film layer 6 ', the organic film is removed by high-temperature baking, and an aluminum-sealed fluorescent screen is finally formed, and can emit visible light when excited by a high-speed electron beam 7 ', and the structure of the aluminum-sealed fluorescent screen is shown in fig. 1.
However, the traditional phosphor screen has a complex manufacturing process and its own defects, which are very unfavorable for the use of the high-performance MCP image intensifier, and mainly reflected in the following aspects: first, the phosphor particles need to be bonded to the substrate by an adhesive, but the bonding force is poor, and the particle gap is increased, which results in poor resolution of the phosphor layer, large outgassing rate, poor thermal conductivity, and is not conducive to improving the performance of the MCP image intensifier. Secondly, because the organic film material has unstable chemical property, dangerous operation and strict coating requirement, the surface must be smooth and flat without pinholes; the manufacturing process is long in period, complex in operation and low in yield, and the production cost is not reduced and the production efficiency is improved. Thirdly, the fluorescent powder particles have large particle size, and the small particle size is generally 2-3 microns (micrometers), so that the surface roughness of the fluorescent powder layer is large, the close-to quality of the MCP image intensifier is affected, and the product performance and the service life of the MCP image intensifier are not favorably improved.
With the increasingly perfect and rapid development of thin film preparation technology, the thinning of various materials becomes the development trend of material application, more and more traditional materials are prepared into various functional thin films, such as conductive thin films, insulating thin films, semiconductor thin films, piezoelectric thin films, photoelectric thin films, passivation protective thin films and the like, which have unique advantages in the aspects of device miniaturization, integration and the like and are widely applied to various aspects of scientific research and production and daily life.
Meanwhile, the fluorescent film is usually polycrystalline or even amorphous, so that more structural defects exist inside the fluorescent film, and the luminous efficiency of the fluorescent film is reduced; because the refractive index of the fluorescent film is higher, except for the part of the light which has a smaller included angle with the normal line of the interface, the light can be emitted, and most of other fluorescent light is totally reflected on the interface and is consumed in the film; these two factors result in poor luminance of the fluorescent film.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a fluorescent thin film screen, a method for manufacturing the same, and an application of the fluorescent thin film screen in a microchannel plate image intensifier, so as to improve the production efficiency and product performance of the fluorescent screen for MCP image intensifier.
In order to achieve the above object, the present invention provides a fluorescent thin film panel, which includes a transparent substrate, and a first fluorescent thin film layer, a fluorescent enhancement layer, a second fluorescent thin film layer and a conductive film layer sequentially deposited on the transparent substrate.
Preferably, the fluorescent film screen further comprises at least one of a first isolation layer, a second isolation layer and a third isolation layer; the first isolation layer is arranged between the first fluorescent thin film layer and the fluorescent enhancement layer; the second isolation layer is arranged between the fluorescence enhancement layer and the second fluorescence thin film layer; the third isolation layer is arranged between the second fluorescent thin film layer and the conductive film layer.
Preferably, in the fluorescent thin film screen, the first isolation layer, the second isolation layer and the third isolation layer are made of SiO2、TiO2、HfO2、MgO、ZrO2、Si3N4Or Al2O3The thickness of the film layer is 5 nm-40 nm.
Preferably, the material of the transparent substrate is selected from glass, quartz, fiber optic panels or organic glass.
Preferably, in the fluorescent thin film panel, the first fluorescent thin film layer and the second fluorescent thin film layer are made of inorganic fluorescent materials, the fluorescent light-emitting wavelength of the fluorescent thin film layer is in a visible light range of 380nm to 760nm, and the thickness of the fluorescent thin film layer is 50nm to 2000 nm.
Preferably, the fluorescent film screen, wherein the inorganic fluorescent material is selected from fluorescent materials for CRT; more preferably, the fluorescent material for CRT is selected from sulfide, oxide, sulfur oxide or silicate.
Preferably, in the fluorescent thin film screen, the material of the fluorescent enhancement layer is at least one selected from Au, Ag, Cu, Al, Pt, Zn, Cr and alloys thereof, the thickness of the film layer is 5nm to 50nm, and the enhancement effect is better if the film layer is generally distributed in island-like, cluster-like, grid-like, and other dot-like arrays; of these, Au and Ag are most commonly used.
Preferably, in the fluorescent thin film panel, the conductive film layer is made of at least one material selected from Al, Ag, Cr, Ni, Au, Cu, Zn metals and alloys thereof, and the thickness of the conductive film layer is 20nm to 200 nm.
In order to achieve the above object, the present invention further provides a method for preparing a fluorescent thin film screen, comprising the following steps:
depositing a first fluorescent thin film layer on a transparent substrate by at least physical vapor deposition, chemical vapor deposition or wet chemical deposition;
depositing a fluorescence enhancement layer on the first fluorescent thin film layer at least by a sputtering method and a thermal evaporation method;
depositing a second fluorescent thin film layer on the fluorescence enhancement layer at least by physical vapor deposition, chemical vapor deposition or wet chemical deposition;
and depositing a conductive film layer on the second fluorescent film layer at least by a sputtering method and a thermal evaporation method.
Preferably, the method for preparing the fluorescent film screen further comprises
And arranging a first isolation layer between the first fluorescent thin film layer and the fluorescent enhancement layer.
Preferably, the method for preparing the fluorescent film screen further comprises
And a step of disposing a second spacer layer between the fluorescence enhancing layer and the second fluorescent thin film layer.
Preferably, the method for preparing the fluorescent film screen further comprises
And arranging a third isolating layer between the second fluorescent thin film layer and the conductive film layer.
In order to achieve the above object, the present invention further provides a microchannel plate image intensifier comprising the above fluorescent film screen.
The fluorescent film layer is a light-emitting functional layer of the fluorescent screen and determines the performances of the fluorescent screen such as light-emitting spectrum, fluorescent life and the like; the fluorescence enhancement layer is a functional layer for enhancing the luminescence of the fluorescent layer, and can obviously improve the luminescence intensity of the fluorescent screen; the isolation film layer is a transparent insulating layer positioned between the fluorescent layer and the fluorescence enhancement layer; the conducting layer is a film layer which can smoothly conduct the negative charges of the fluorescent screen out, and has the functions of reflecting fluorescence and protecting the fluorescent layer.
By the technical scheme, the invention at least has the following advantages:
the invention utilizes the interaction of the metal surface plasma effect and the fluorescent film layer, namely introduces the fluorescent enhancement layer to improve the luminous brightness of the fluorescent film. Meanwhile, in order to better exert the enhancement effect of the fluorescence enhancement layer, an isolation layer is introduced between the fluorescence thin film layer and the fluorescence enhancement layer. The invention finally realizes the high-performance fluorescent film screen for the MCP image intensifier by the thinning of the fluorescent material and the introduction of the fluorescent enhancement layer and the isolation layer.
The fluorescent material is plated into the fluorescent layer (namely the fluorescent film layer) in the form of a film, and the luminous intensity of the fluorescent film screen is improved through the interaction with the fluorescent enhancement layer, so that the fluorescent film screen has the following advantages:
firstly, due to the characteristics of high density, uniform thickness, smooth surface and the like of the fluorescent film, the plated fluorescent layer has low outgassing rate, good thermal conductivity and uniform luminous brightness, is beneficial to MCP close-up of the MCP image intensifier, and has high resolution.
Secondly, because the fluorescent film has strong bonding force with the substrate, the plated fluorescent layer can be firmly attached to the substrate without a binder, the risk of falling off of the fluorescent layer is greatly reduced, and the adverse effect of the binder on the fluorescent layer is also avoided, so that the brightness uniformity and the resolution of the fluorescent screen are improved, and the service performance and the quality of the fluorescent screen are ensured.
Thirdly, due to the characteristics of high density and smooth surface of the fluorescent film, other films can be directly plated on the surface of the fluorescent film, the organic film coating procedure in the traditional fluorescent powder screen manufacturing is omitted, the product defects of pinholes, aluminum penetration and the like of the traditional fluorescent powder screen are eliminated, the manufacturing period is shortened, the product percent of pass is improved, and the production cost is reduced.
Drawings
FIG. 1 is a schematic view of a conventional phosphor screen;
FIG. 2 is a schematic structural diagram of a fluorescent film panel according to the present invention;
wherein:
transparent substrate-1 ', fluorescent powder layer-8', conductive film layer-6 ', electron beam-7';
the fluorescent film comprises a transparent substrate-1, a first fluorescent film layer-2, a first isolation layer-31, a second isolation layer-32, a third isolation layer-33, a fluorescent enhancement layer-4, a second fluorescent film layer-5, a metal film layer-6 and an electron beam-7.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the fluorescent thin film screen, the preparation method thereof and the application thereof in the MCP image intensifier according to the present invention with reference to the accompanying drawings and the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
As shown in fig. 2, the present invention provides a fluorescent thin film screen, which comprises a transparent substrate 1, and a first fluorescent thin film layer 2, a fluorescent enhancement layer 4, a second fluorescent thin film layer 5 and a conductive film layer 6 sequentially deposited on the transparent substrate 1; at least one of the first separation layer 31, the second separation layer 32, and the third separation layer 33 may be further included: the first isolation layer 31 is arranged between the first fluorescent thin film layer 2 and the fluorescent enhancement layer 4; the second isolation layer 32 is arranged between the fluorescence enhancement layer 4 and the second fluorescence thin film layer 5; the third isolation layer 33 is disposed between the second fluorescent thin film layer 5 and the conductive film layer 6.
In specific implementation, the transparent substrate 1 is made of glass, quartz, an optical fiber panel or other transparent materials meeting the use requirements, and has the characteristics of transparency, insulation, high temperature resistance, corrosion resistance, etching resistance and the like when being used as an optical signal output window of a fluorescent screen.
In specific implementation, the first fluorescent thin film layer 2 and the second fluorescent thin film layer 5 may be made of inorganic fluorescent materials or organic fluorescent materials, the fluorescent light-emitting wavelength of the fluorescent thin film layer is generally in the visible light range of 380nm to 760nm, and the thickness of the fluorescent thin film layer is generally 50nm to 2000 nm; the inorganic fluorescent material is selected from fluorescent materials for CRT, which can be sulfide, oxide, oxysulfide or silicate, etc.; the fluorescent screen is a luminescent functional layer of the fluorescent screen, can emit visible light under the excitation of high-speed electron beam current 7, directly determines the basic performances of the fluorescent screen such as luminescent spectrum, fluorescent service life and the like, and has the characteristics of film type, high temperature resistance, electron bombardment resistance, smooth surface and the like. The fluorescent thin film layer 5 and the fluorescent thin film layer 2 may be different, and if they are different, they are different in at least one aspect including material composition, preparation method, film thickness, etc. In general, the fluorescent thin film layer 5 is made of a material having a better electron bombardment resistance than the fluorescent thin film layer 2, and thus the fluorescent thin film panel has a longer service life.
In specific implementation, the material of the fluorescence enhancement layer 4 can be at least one selected from Au, Ag, Cu, Al, Pt, Zn, Cr and alloys thereof, the thickness of the film layer is within the range of 5nm to 50nm, and the fluorescence enhancement effect is better if the film layer is generally distributed in island-like, cluster-like, grid-like and other lattice-like shapes; the luminescent auxiliary layer is spaced from the fluorescent thin film layer by a certain distance (namely, the thickness of the isolating layer is 5 nm-40 nm), the luminescent intensity of the fluorescent screen can be obviously improved, and the enhancement layer realizes the effect of enhancing fluorescence through the interaction of a metal surface plasma effect and the fluorescent layer.
In specific implementation, the material of the conductive film layer 6 is selected from metals of Al, Ag, Cr, Ni, Au, Cu, Zn and alloys thereof, and the thickness of the film layer is 20 nm-200 nm; the film layer positioned on the outermost surface of the fluorescent film screen has the functions of conducting electricity, reflecting fluorescence, protecting the inner film layer and the like, and has the characteristics of smoothness, flatness, good conductivity, high reflectivity and the like.
In specific implementation, the first isolation layer 31, the second isolation layer 32 and the third isolation layer 33 are made of SiO2、TiO2、HfO2、MgO、ZrO2、Si3N4Or Al2O3The thickness of the film layer is 5 nm-40 nm. The first isolation layer 31 is located between the first fluorescent thin film layer 2 and the fluorescent enhancement layer 3 or between the first fluorescent thin film layer 5 and the conductive film layer 6, and plays a role in isolating the first fluorescent thin film layer from the conductive film layer 6, so that the distance between the first fluorescent thin film layer and the fluorescent enhancement layer is controlled within a proper range, the fluorescent enhancement layer 3 (or the conductive film layer 6) is assisted to achieve the effect of enhancing fluorescence, and the fluorescent enhancement layer has the characteristics of transparency, insulation, high temperature resistance and the like.
When the fluorescent film screen is used specifically, electron beam current 7 is needed for bombardment; the electron beam 7 is a high-density electron beam working under a certain accelerating voltage, and has the function of realizing the conversion from an electron signal to an optical signal by bombarding the fluorescent layer by the electron beam. The source of the electrons is generally microchannel plate or dynode multiplied electrons, electrons emitted by a hot cathode, electrons emitted by a cold cathode, or the like.
The invention also provides a preparation method of the fluorescent film screen, which comprises the following steps:
depositing a first fluorescent thin film layer 2 on a transparent substrate 1 by at least physical vapor deposition, chemical vapor deposition or wet chemical deposition;
depositing a fluorescence enhancement layer 4 on the first fluorescent thin film layer 2 at least by a sputtering method and a thermal evaporation method;
depositing a second fluorescent thin film layer 5 on the fluorescence enhancing layer 4 by at least physical vapor deposition, chemical vapor deposition or wet chemical deposition;
and depositing a conductive film layer 6 on the second fluorescent film layer 5 at least by a sputtering method and a thermal evaporation method.
In specific implementation, the preparation method further comprises the following steps:
a step of disposing a first spacer layer 31 between the first fluorescent thin film layer 2 and the fluorescence-enhancing layer 4.
In specific implementation, the preparation method further comprises the following steps:
a step of disposing a second spacer layer 32 between the fluorescence enhancing layer 4 and the second fluorescent thin film layer 5.
It should be noted that the three separation layers are not necessarily required to be present at the same time, but if they are present at the same time, the fluorescence enhancement effect is more excellent.
In specific implementation, the preparation method further comprises the following steps:
and a step of disposing a third isolation layer 33 between the second fluorescent thin film layer 5 and the conductive film layer 6.
In specific implementation, the preparation method of the fluorescent film screen specifically comprises the following steps:
1) selecting a substrate: and selecting a transparent substrate with a smooth and flat surface, and cleaning the substrate to achieve the purposes of cleaning the surface, removing oil stains, removing dust and impurities, and the like. Taking a glass substrate as an example, the cleaning process can be ultrasonic cleaning in the sequence of acetone, absolute ethyl alcohol and deionized water, or repeated ultrasonic cleaning (generally cleaning for 2 times; if the surface of the substrate is found to be dirty by a microscope, the cleaning needs to be repeated continuously, and finally the substrate with a clean and pollution-free surface is obtained), and finally the substrate with a clean and pollution-free surface is obtained.
2) Preparing a fluorescent film: the required fluorescent raw material excited by electron beam to emit light is selected, the fluorescent light-emitting wavelength of the fluorescent raw material is generally in the visible light range of 380 nm-760 nm, and the fluorescent raw material is plated on a substrate by using a proper film preparation technology and process. Taking vacuum plating of traditional CRT fluorescent material (fluorescent material for CRT display screen) as an example, the preparation process of the fluorescent film can be carried out when the equipment reaches proper vacuum degree (better than 1 × 10)-3Pa), introducing working gas or reaction gas, and depositing the required fluorescent film material on a substrate heated (generally 100-300 ℃), wherein the thickness of the film layer is generally in the range of 50-2000 nm. The fluorescent film layer can be a single layer or a plurality of layers of fluorescent materials, and also can be one or more fluorescent material components.
3) Preparing an isolation layer: this fabrication process is not required, but if a spacer layer is present, the desired spacer layer material can be selected to enhance the fluorescence enhancement effect (generally, a suitable spacer layer can enhance the fluorescence enhancement effect by a factor of 10% to 200%, etc.), with SiO being commonly used2、TiO2、MgO、HfO2And the like, and is plated on the fluorescent film layer by using a proper film preparation technology and process. SiO vacuum plating2For example, the material can be prepared by a process that when the device reaches a suitable vacuum degree (better than 5X 10)-3Pa), introducing working gas or reaction gas, and depositing the required SiO on the heated (generally 100-300 ℃) fluorescent film2The thickness of the film layer is generally in the range of 5nm to 40 nm.
4) Preparing a fluorescence enhancement layer: the required fluorescence enhancing material, commonly used metals such as Au, Ag, Cu, Al, Pt, Zn, Cr and the like, is plated on the isolation film layer by a proper film preparation technology and process. Take vacuum sputtering Au material as an exampleThe preparation process can be carried out when the equipment reaches a proper vacuum degree (better than 1X 10)-3Pa), working gas (generally argon gas, or other inert gas) is introduced, a required Au thin film is deposited on an unheated isolation film layer, the thickness of the film layer is generally in the range of 5nm to 50nm, the film layer morphology generally presents island-shaped, particle-shaped, or grid-shaped distribution, and the fluorescence enhancement effect is better (the size of each point of the island-shaped, particle-shaped, or grid-shaped is in the nanometer level, for example, the Au thin film is considered to be formed by a zero-dimensional Au lattice, when a substance is gradually transited from a three-dimensional material to a lower-dimensional material, the energy state density of electrons is gradually reduced, and finally, a quasi-continuous energy level is changed into a discrete energy level (when quantum dots). In addition, the zero-dimensional material has many unique and novel physical properties due to the characteristics of small size and large specific surface area).
5) Preparing an isolation layer: the same as the step 3).
6) Preparing other film layers: if the product needs to be plated with other fluorescent thin film layers, the processes of the steps 2) and 3) can be repeated on the basis of the isolating layer of the step 5), or the processes of the steps 2), 3), 4) and 5) can be repeated.
7) Preparing a conductive film layer: the required conductive material is selected on the outermost surface of each functional film layer of the fluorescent screen, the common metals such as Al, Ag, Cr, Ni and the like and the alloy thereof are used, the most common is Al, the Al has low price, good conductivity, high light reflection rate and good electron transmission effect, therefore, the most common is Al, the thickness of the film layer is generally in the range of 20 nm-200 nm, and the purpose is to provide a conductive protective layer which has the functions of smoothness, good conductivity, high fluorescence reflection rate, internal film layer protection and the like.
8) Annealing treatment: this fabrication process is not necessarily required, but if the functional layers are properly annealed, the performance quality of the phosphor screen can be improved. However, when the annealing treatment of the fluorescent material is not appropriate, the composition of the material changes due to oxidation, decomposition, or the like, and in the severe case, the phenomena of quenching of the emission luminance, change in emission color, or the like may occur. Therefore, the annealing treatment is generally performed in a protective atmosphere at a suitable temperature.
The present invention is further illustrated by the following specific examples.
Example 1
The embodiment provides a preparation method of a fluorescent film screen, which comprises the following steps:
1) the method comprises the steps of taking glass as a transparent substrate 1, sequentially performing ultrasonic treatment on the glass for 5 minutes by using acetone, absolute ethyl alcohol and deionized water respectively to clean the glass substrate, and then putting the glass substrate into a clean drying box to be dried for 10 minutes at 50 ℃, so as to finally obtain the glass substrate with a clean and pollution-free surface.
2) Preparing a first fluorescent thin film layer 2 by using a sulfide fluorescent material ZnS: Cu, Al (copper-aluminum doped zinc sulfide, wherein Cu/Al is 10 mol% -100 mol%, and Cu/Zn is 0.001 mol% -5 mol%) as a raw material: the ZnS: Cu, Al fluorescent film is prepared by PLD laser deposition method, wherein the vacuum degree of the cavity is better than 1 x 10-3Pa, substrate temperature of 200-300 ℃, laser energy of 10-20J/cm2The distance between the substrate and the film material is 3-8 cm, the deposition time is 5-30 minutes, and the first fluorescent film layer 2 with the thickness of 50-2000 nm is obtained.
3) With SiO2Preparing the first separation layer 31 as a raw material: preparation of SiO by electron beam evaporation2Film layer, wherein the vacuum degree of the chamber is better than 1 x 10-3Pa, the substrate temperature is 200-300 ℃, the electron beam high voltage is 5-10 kV, the beam current is 50-300 mA, the distance between the substrate and the membrane material is 10-50 cm, and the deposition time is 1-10 minutes, so that the first isolation membrane layer 31 with the thickness of 5-40 nm is obtained.
4) Preparing a fluorescence enhancement layer 4 by taking Au as a raw material: using ion sputtering to evaporate Au film layer, wherein the vacuum degree of the chamber is 7 multiplied by 10-1Pa, sputtering current of 5-100 mA, space between the substrate and the film material of 2-8 cm, deposition time of 0.5-5 minutes, and obtaining the fluorescence enhancement film layer 4 with thickness of 5-50 nm.
5) Repeating the steps 2) and 3) to obtain ZnS, Cu, Al/SiO2/Au/SiO2The sandwich-type multi-layer film structure of/ZnS, Cu and Al respectively obtains a second fluorescent film layer 5 with the thickness of 50 nm-2000 nm and a second isolating layer 32 with the thickness of 5 nm-40 nm.
6) And repeating the step 3) to obtain a third isolating layer 33 with the thickness of 5 nm-40 nm.
7) Preparing a conductive film layer 6 by using Al as a raw material: preparing Al film layer by electron beam evaporation method, wherein the vacuum degree of the chamber is better than 1 × 10-3Pa, heating the substrate, setting the high voltage of an electron beam to be 5-10 kV, setting the beam current to be 300-500 mA, setting the distance between the substrate and the film material to be 10-50 cm, and setting the deposition time to be 1-10 minutes to obtain a conductive film layer 6 with the thickness of 20-200 nm;
through the steps, the Au-film-reinforced ZnS: Cu, Al/Au/ZnS: Cu and Al fluorescent thin-film screen (wherein Cu/Al is 10-100 mol%, and Cu/Zn is 0.001-5 mol%) is obtained.
The phosphor screens of ZnS: Cu, Al/Au/ZnS: Cu, Al (wherein Cu/Al is 10 mol% to 100 mol%, and Cu/Zn is 0.001 mol% to 5 mol%) having the phosphor layers of 200nm to 2000nm prepared in example 1 and ZnS: Cu having the phosphor layers of 4 μm to 6 μm (μm) (the phosphor particle size is 2 to 3 μm) of comparative example 1 were subjected to performance tests under the same conditions, and the test results are shown in Table 1.
Testing the binding force of the fluorescent layer and the substrate: the adhesion of the film to the substrate was measured according to the tape method of astm d 3359-09 standard test methods at room temperature and the adhesion rating was given.
Outgassing rate testing of the phosphor layer: the vacuum chamber deflation rate is less than 1.5 x 10 under the room temperature condition-8(Pa·m3S), test initial vacuum degree better than 1X 10-4(Pa), test time interval 1 hour.
Testing the heat conductivity of the fluorescent layer: the vacuum degree is measured by a 3 omega method under the condition of room temperature, and is 1.33 multiplied by 10-2(Pa), and omega AC frequency of 200-1200 Hz.
Testing the brightness uniformity of the fluorescent screen: the vacuum degree is better than 5 multiplied by 10 under the condition of room temperature-4(Pa), the filament current is adjustable at 0-10A, and the incident electron energy is adjustable at 2-4 keV.
Surface roughness test of the fluorescent layer: AFM is adopted to test the film surface at room temperature, and the probe force is 10-8～10-6(N), measurement range 2 x 1 μm.
Testing the resolution ratio of the fluorescent screen: under the condition of room temperature, the adopted light source power is 25W, the light source color temperature is 2860K, and the standardQuasi-resolution target USAF1951, image brightness greater than 1cd/m2The viewing angle is greater than 10'.
TABLE 1
Figure BDA0002369330050000101
Example 2
The embodiment provides a preparation method of a fluorescent film screen, which comprises the following steps:
1) and (2) taking the optical fiber panel as a transparent substrate 1, sequentially performing ultrasonic treatment for 10 minutes by using acetone, absolute ethyl alcohol and deionized water to clean the glass substrate, and then putting the glass substrate into a clean drying box to be dried for 5 minutes at 90 ℃, so as to finally obtain the optical fiber panel substrate with a clean and pollution-free surface.
2) Preparing a first fluorescent thin film layer 2 by taking an oxide fluorescent material ZnO as a raw material: preparing ZnO fluorescent film by using atomic layer deposition method of wet chemical reaction, wherein the vacuum degree of a chamber is superior to 2 multiplied by 102Pa (the requirement on the vacuum degree of the equipment is not high), the substrate temperature is 150-250 ℃, nitrogen is used as a working carrier gas, diethyl zinc and water are used as reaction sources, the introduction proportion of the diethyl zinc and the water is 1.5s (second), the water is 1.5s (second) and the nitrogen is 10s (second) according to the time, the mixture is sequentially introduced into a chamber to be used as a cycle, the deposition time is 400-3500 cycles, and the first fluorescent thin film layer 2 with the thickness of 50-500 nm is obtained.
3) With HfO2Preparing the first separation layer 31 as a raw material: preparation of HfO using magnetron sputter deposition2Film layer, wherein the vacuum degree of the chamber is better than 3 x 10-3Pa, the substrate temperature is 200-300 ℃, the distance between the substrate and the film material is 3-8 cm, the working gas is Ar gas, the working power is 80-200W, and the deposition time is 1-10 minutes, so that the first isolation film layer 31 with the thickness of 5-40 nm is obtained.
4) Preparing a fluorescence enhancement layer 4 by using Al as a raw material: preparing Al film layer by thermal evaporation method, wherein the vacuum degree of the chamber is better than 1 × 10-3Pa, the substrate is not heated, the distance between the substrate and the film material is 10-50 cm, a tungsten boat is used for electrifying and heating to melt Al, the working current is 0.5-10A, and the deposition time is 0.5-5 minutes, so that the fluorescence enhancement layer 4 with the thickness of 5-50 nm is obtained.
5) And repeating the parameters of the step 3) to obtain a second isolation film layer 32 with the thickness of 5 nm-40 nm.
6) Preparing a second fluorescent thin film layer 5 by taking an oxide fluorescent material ZnO and Al (wherein Al/Zn is 0.5 mol% -10 mol%) as raw materials: the ZnO-Al fluorescent film is prepared by a magnetron sputtering deposition method, wherein the vacuum degree of a cavity is superior to 3 multiplied by 10-3Pa, keeping the substrate temperature at 200-300 ℃, keeping the distance between the substrate and the membrane material at 3-8 cm, using argon as working gas, working power at 80-200W, and depositing for 5-30 minutes to obtain a second fluorescent thin film layer 5 with the thickness of 50-500 nm.
7) Annealing at 400-700 ℃ for 0.5-1 h in an inert atmosphere to obtain ZnO/HfO2/Al/HfO2Al/ZnO in the structure of a multilayer film.
8) And repeating the step 3) to obtain a third isolation film layer 33 with the thickness of 5 nm-40 nm.
9) Preparing a conductive film layer 6 by taking Ag as a raw material: preparing Ag film layer by thermal evaporation method, wherein the vacuum degree of the chamber is better than 1 × 10-3Pa, the substrate is not heated, the distance between the substrate and the film material is 10-50 cm, a tungsten boat is electrified to heat and melt Ag, the working current is 0.5-10A, and the deposition time is 0.5-5 minutes, so that the conductive film layer 6 with the thickness of 20-200 nm is obtained.
Through the steps, the ZnO/Al/ZnO/Al fluorescent film screen of the Al film reinforced fluorescent layer is obtained (wherein the Al/Zn is 0.5-10 mol%).
The phosphor layer prepared in example 2 was formed to have a thickness of 150nm to 1200nm, i.e., ZnO/Al/ZnO: Al (wherein Al/Zn is 0.5 mol% to 10 mol%). The performance of the fluorescent film screen and the ZnO/Al fluorescent powder screen of comparative example 2, in which the thickness of the fluorescent layer is 4-7 μm (the particle size of the fluorescent powder is 2-5 μm), were tested under the same conditions (the test conditions are the same as those of example 1), and the test results are shown in Table 2.
TABLE 2
Figure BDA0002369330050000111
Example 3:
the embodiment provides a preparation method of a fluorescent film screen, which comprises the following steps:
1) the method comprises the steps of taking quartz as a transparent substrate 1, sequentially performing ultrasonic treatment on the transparent substrate 1 for 10 minutes by using acetone, absolute ethyl alcohol and deionized water respectively to clean the glass substrate, and then drying the glass substrate in a clean drying box at 60 ℃ for 10 minutes to finally obtain the quartz substrate with a clean and pollution-free surface.
2) With sulfur oxide Gd2O2Tb (wherein Tb/Gd is 0.1 mol% -7 mol%) is used as raw material to prepare the first fluorescent thin film layer 2: preparation of Gd using magnetron sputtering deposition2O2Tb fluorescent film, in which the vacuum degree of its cavity is superior to 3X 10-3Pa, the substrate temperature is 200-300 ℃, the distance between the substrate and the membrane material is 3-8 cm, the working gas is argon, the working power is 80-200W, the deposition time is 5-30 minutes, a first fluorescent thin film layer 2 with the thickness of 50-2000 nm is obtained, and then H is put into the first fluorescent thin film layer2Annealing in an S atmosphere furnace at 600-800 ℃ for 0.5-2 hours.
3) With Si3N4Preparing the first separation layer 31 as a raw material: preparation of Si by magnetron sputtering deposition3N4Film layer, wherein the vacuum degree of the chamber is better than 3 x 10-3Pa, the substrate temperature is 200-300 ℃, the distance between the substrate and the film material is 3-8 cm, the working gas is Ar gas, the working power is 100-200W, and the deposition time is 1-10 minutes, so that the first isolation film layer 31 with the thickness of 5-40 nm is obtained.
4) Preparing a fluorescence enhancement layer 4 by taking Cr as a raw material: preparing Cr film layer by electron beam evaporation method, wherein the vacuum degree of the chamber is better than 1 × 10-3Pa, the substrate is not heated, the high voltage of the electron beam is 5-10 kV, the beam current is 250-350 mA, the distance between the substrate and the membrane material is 10-50 cm, the deposition time is 0.5-5 minutes, and the fluorescence enhancement layer 4 with the thickness of 5-50 nm is obtained.
5) And repeating the step 3) to obtain a second isolating layer 32 with the thickness of 5 nm-40 nm.
6) With aluminate Y3Al5O12The second fluorescent film layer 5 is prepared by taking Ce (wherein Ce/Y is 0.02 mol% -4 mol%) as a raw material: preparation of Y Using Electron Beam Evaporation3Al5O12Ce film layer, wherein the vacuum degree of the chamber is better than 1 x 10-3Pa, substrate temperature ofAnd (3) at the temperature of 200-300 ℃, the high voltage of the electron beam is 5-10 kV, the beam current is 100-200 mA, the distance between the substrate and the film material is 10-50 cm, the deposition time is 0.5-5 minutes, and the second fluorescent thin film layer 5 with the thickness of 50-2000 nm is obtained.
7) And repeating the step 3) to obtain a third isolating layer 33 with the thickness of 5 nm-40 nm.
8) Preparing a conductive film layer 6 by taking NiCr alloy as a raw material: the NiCr alloy film layer is prepared by an electron beam evaporation method, wherein the vacuum degree of a cavity is better than 1 x 10-3Pa, the substrate is not heated, the distance between the substrate and the film material is 10-50 cm, the electron beam high voltage is 5-10 kV, the beam current is 250-350 mA, and the deposition time is 1-10 minutes, so that the conductive film layer 6 with the thickness of 20-200 nm is obtained.
Through the steps, Gd of the Cr film reinforced double-layer fluorescent layer is obtained2O2S:Tb/Cr/Y3Al5O12Ce fluorescent film screen.
Gd with the thickness of the fluorescent layer prepared in example 3 being 200nm to 2000nm2O2S:Tb/Cr/Y3Al5O12The thickness of the fluorescent layer of the Ce fluorescent film screen and the fluorescent layer of the comparative example 3 is 4-6 mu m (the grain diameter of the fluorescent powder is 2-5 mu m)2O2S:Tb/Y3Al5O12The Ce phosphor screen was subjected to a performance test under the same conditions (the test conditions were the same as in example 1), and the test results are shown in Table 3.
TABLE 3
Figure BDA0002369330050000131
As can be seen from the data in tables 1 to 3, the fluorescent thin film panels prepared in examples 1 to 3 of the present invention are significantly superior to the corresponding fluorescent powder panels of comparative examples 1 to 3 in terms of various properties, because the layers and the substrate of the fluorescent thin film panels prepared in examples 1 to 3 are physically and chemically bonded, and the film layer has high stacking density, the substrate-fluorescent layer-conductive layer has large bonding force and low outgassing rate, which is beneficial to heat dissipation by heat conduction; meanwhile, the film layer of the fluorescent film screen has uniform particles, uniform thickness and smooth surface, so the fluorescent film screen has good brightness uniformity, small surface roughness and high resolution, is beneficial to MCP close-up of the MCP image intensifier, and can effectively improve the product performance and prolong the service life of the MCP image intensifier.
The fluorescent screen for the high-performance MCP image intensifier is realized by adopting the fluorescent film as a fluorescent layer and simultaneously introducing the fluorescent enhancement layer and the isolation layer; the manufacturing method is to obtain various photoelectric functional layers such as a fluorescent thin film layer, an isolation layer, a fluorescent enhancement layer, a conductive film layer and the like by vacuum deposition or wet chemical deposition technology.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (11)

1. A fluorescent film screen is characterized by comprising a transparent substrate, and a first fluorescent film layer, a fluorescent enhancement layer, a second fluorescent film layer and a conductive film layer which are sequentially deposited on the transparent substrate.
2. The fluorescent film screen of claim 1, further comprising at least one of a first spacer layer, a second spacer layer, and a third spacer layer; the first isolation layer is arranged between the first fluorescent thin film layer and the fluorescent enhancement layer; the second isolation layer is arranged between the fluorescence enhancement layer and the second fluorescence thin film layer; the third isolation layer is arranged between the second fluorescent thin film layer and the conductive film layer.
3. The phosphor film screen of claim 2, wherein the first, second and third spacers are made of a material selected from the group consisting of SiO2、TiO2、HfO2、MgO、ZrO2、Si3N4Or Al2O3The thickness of the film layer is 5 nm-40 nm.
4. The fluorescent film screen of claim 1, wherein the transparent substrate is made of a material selected from the group consisting of glass, quartz, fiber optic faceplate, and plexiglass.
5. The fluorescent film screen according to claim 1, wherein the first fluorescent film layer and the second fluorescent film layer are made of inorganic fluorescent materials, the fluorescent light emission wavelength is in the visible light range of 380nm to 760nm, and the film thickness is 50nm to 2000 nm.
6. The fluorescent film screen of claim 5, wherein the inorganic fluorescent material is selected from the group consisting of fluorescent materials for CRT; the fluorescent material for CRT is selected from sulfide, oxide, oxysulfide or silicate.
7. The phosphor film screen of claim 1, wherein the phosphor-enhanced layer is made of at least one material selected from the group consisting of Au, Ag, Cu, Al, Pt, Zn, Cr and alloys thereof, and has a film thickness of 5nm to 50 nm.
8. The phosphor film panel of claim 1, wherein the conductive film layer is made of at least one material selected from the group consisting of Al, Ag, Cr, Ni, Au, Cu, Zn metals and alloys thereof, and has a film thickness of 20nm to 200 nm.
9. A method for manufacturing a fluorescent thin film screen according to any one of claims 1 to 8, comprising the steps of:
depositing a first fluorescent thin film layer on a transparent substrate by at least physical vapor deposition, chemical vapor deposition or wet chemical deposition;
depositing a fluorescence enhancement layer on the first fluorescent thin film layer at least by a sputtering method and a thermal evaporation method;
depositing a second fluorescent thin film layer on the fluorescence enhancement layer at least by physical vapor deposition, chemical vapor deposition or wet chemical deposition;
and depositing a conductive film layer on the second fluorescent film layer at least by a sputtering method and a thermal evaporation method.
10. The fluorescent film screen of claim 9, wherein the method of making further comprises at least one of the following steps:
a step of disposing a first spacer layer between the first fluorescent thin film layer and the fluorescent enhancement layer;
a step of disposing a second spacer layer between the fluorescence enhancing layer and the second fluorescent thin film layer; and
and arranging a third isolating layer between the second fluorescent thin film layer and the conductive film layer.
11. A microchannel plate image intensifier comprising the fluorescent film screen of any of claims 1 to 8.
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CN1708824A (en) * 2002-10-29 2005-12-14 株式会社东芝 Phosphor screen with metal back, method of forming the same and image display unit
CN101270468A (en) * 2008-05-05 2008-09-24 浙江大学 Method for reinforcing zinc oxide thin membrane luminescence
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Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3526527A (en) * 1967-04-28 1970-09-01 Sylvania Electric Prod Process of forming a cathodoluminescent screen
US4906892A (en) * 1987-11-13 1990-03-06 Thomson-Csf High luminance color screen for cathode ray tube and method for making a screen of this type
JP2000169842A (en) * 1998-12-07 2000-06-20 Hitachi Ltd TWO-LAYER FLUORESCENT FILM USING ZnS FLUOPHOR AND CATHODE RAY TUBE USING THE FILM
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JP2004055385A (en) * 2002-07-22 2004-02-19 Toshiba Corp Fluorescent screen with metal back and image display device
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