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CN110981192B - Micro-channel plate leather glass with high stability and temperature resistance characteristics for low temperature and its preparation method and application - Google Patents

Micro-channel plate leather glass with high stability and temperature resistance characteristics for low temperature and its preparation method and application Download PDF

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Publication number
CN110981192B
CN110981192B CN201911267468.6A CN201911267468A CN110981192B CN 110981192 B CN110981192 B CN 110981192B CN 201911267468 A CN201911267468 A CN 201911267468A CN 110981192 B CN110981192 B CN 110981192B
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glass
temperature
microchannel plate
plate
low temperature
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CN110981192A (en
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蔡华
刘辉
周东站
贾金升
李庆
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China Building Materials Academy CBMA
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China Building Materials Academy CBMA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/04—Forming tubes or rods by drawing from stationary or rotating tools or from forming nozzles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/20—Uniting glass pieces by fusing without substantial reshaping
    • C03B23/207—Uniting glass rods, glass tubes, or hollow glassware
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J43/00—Secondary-emission tubes; Electron-multiplier tubes
    • H01J43/04—Electron multipliers
    • H01J43/06—Electrode arrangements
    • H01J43/10—Dynodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J43/00—Secondary-emission tubes; Electron-multiplier tubes
    • H01J43/04—Electron multipliers
    • H01J43/06—Electrode arrangements
    • H01J43/18—Electrode arrangements using essentially more than one dynode
    • H01J43/24—Dynodes having potential gradient along their surfaces
    • H01J43/246—Microchannel plates [MCP]
    • 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
    • H01J9/02—Manufacture of electrodes or electrode systems
    • 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

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  • Engineering & Computer Science (AREA)
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Abstract

本发明涉及一种低温用高稳定温阻特性的微通道板皮料玻璃及其制备方法和应用。该微通道板皮料玻璃，以摩尔百分比计，包括：SiO2 50％～78％；Bi2O3 1.5％～8％；PbO 5.0％～15％；Na2O、K2O和Cs2O中的至少一种4.0％～25％；MgO、BaO和CaO中的至少一种1.0％～6％；Al2O3 0.1％～2.5％；RuO2 1.5％～12％本发明从微通道板的温阻特性改性角度出发，将特殊氧化物直接引入玻璃材料，以实现玻璃材料成分调控的微通道板的导电层结构，从而降低微通道板的超低温体电阻，极大地提高微通道板超低温信号超快速读取与响应的能力。

Figure 201911267468

The invention relates to a micro-channel plate leather glass with high stable temperature resistance characteristics for low temperature use, and a preparation method and application thereof. The microchannel plate skin glass, in molar percentage, comprises: SiO 2 50%-78%; Bi 2 O 3 1.5%-8%; PbO 5.0%-15%; Na 2 O, K 2 O and Cs 2 At least one of O is 4.0% to 25%; at least one of MgO, BaO and CaO is 1.0% to 6%; Al 2 O 3 0.1% to 2.5%; RuO 2 1.5% to 12% From the perspective of modifying the temperature resistance characteristics of the plate, special oxides are directly introduced into the glass material to realize the conductive layer structure of the microchannel plate controlled by the composition of the glass material, thereby reducing the ultra-low temperature bulk resistance of the microchannel plate and greatly improving the microchannel plate. Ultra-fast reading and response capability of ultra-low temperature signals.

Figure 201911267468

Description

Microchannel plate cladding glass with high-stability temperature resistance characteristic for low temperature and preparation method and application thereof
Technical Field
The invention belongs to the field of glass processing, particularly relates to microchannel plate leather glass and a preparation method and application thereof, and particularly relates to microchannel plate leather glass with high stable temperature resistance for low temperature and a preparation method and application thereof.
Background
The microchannel plate is a special device for parallel multiplication of charged particle flow distributed in two-dimensional spaceGlass materials and devices are provided. Due to the advantages of high time resolution, high spatial resolution, extremely high signal amplification factor, compact structure and the like, the microchannel plate becomes an important device with the most potential for reading out low-temperature quantum analog computation signals. The low-temperature quantum simulation calculation requires that the signal reading device has the signal reading time of not more than 10 under the condition that the temperature is not more than 30K-5s to meet ultra-fast read requirements.
The signal reading time of the microchannel plate under the ultralow temperature condition is mainly determined by the body resistance of the microchannel plate and is in direct proportion to the body resistance. After being processed by a special process, the inner wall of the micro-channel plate forms a secondary electron emission layer and an electron conduction layer, is a semiconductor-like structure and has obvious negative resistance temperature coefficient characteristics. The microchannel plate is usually used at room temperature, the conventional bulk resistance is 100-200M omega, but under the ultralow temperature condition of 20-30K, the bulk resistance can be raised to about 10 of the bulk resistance at room temperature5～106The corresponding signal reading time is prolonged to 10-2s-1 s, far from the reading of the ultra-fast quantum signals required by low-temperature quantum simulation calculation. Therefore, the high resistance under the ultralow temperature condition is a major bottleneck for the fast reading of quantum signals of the silicate glass microchannel plate.
For the ultra-low temperature low body resistance micro-channel plate, the body resistance of the micro-channel plate under the ultra-low temperature use condition is reduced by adjusting the composition of the micro-channel plate material and optimizing the physical and chemical treatment process according to the prior patents and documents at home and abroad. However, there is no related patent or literature report for reducing the resistance of the microchannel plate body under the ultra-low temperature condition directly from the viewpoint of the modification and stabilization of the temperature resistance characteristics of the glass material components of the microchannel plate.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a microchannel plate skin material glass with high stable temperature resistance for low temperature, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a microchannel plate skin glass with high stable temperature resistance for low temperature, which comprises, in mole percent:
Figure BDA0002313263950000021
preferably, the microchannel plate skin glass with high stable temperature resistance characteristic for low temperature further comprises 0.10 to 0.80 weight percent of Sb2O3And/or As2O3。
Preferably, the transition temperature of the microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature is TgNot less than 450 ℃ and a softening temperature Tf≥545℃。
Preferably, the microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature is used, wherein the thermal expansion coefficient of the microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature at 100 ℃ to 300 ℃ is (60-105) x 10-7/℃。
Preferably, the microchannel plate skin glass with high stable temperature resistance characteristic for low temperature has no crystallization at 500-950 ℃, and has good crystallization resistance.
In order to achieve the above object, the present invention further provides a method for preparing a microchannel plate skin material glass with high stable temperature resistance characteristic for low temperature, comprising the following steps:
1) mixing quartz sand, lead oxide, bismuth oxide, barium salt, sodium carbonate, cesium carbonate, potassium salt, basic magnesium carbonate, calcium carbonate, aluminum hydroxide and ruthenium compound to obtain a batch mixture, and adding a clarifying agent accounting for 0.10-0.80 wt% of the total weight of the batch mixture;
2) adding the batch containing the clarifying agent into a crucible at 1300-1550 ℃ for one or more times for melting, wherein the time interval between each time of feeding is 15-90 minutes;
3) after the feeding is finished, heating to 1400-1550 ℃ for clarification for 2-12 hours;
4) cooling to 1200-;
5) drawing and forming the glass liquid into a glass tube material at 1200-1350 ℃ after homogenization;
6) and (3) preserving the heat of the formed glass tube material for 2-6 hours at the temperature of 550-650 ℃, then cutting off the power and annealing to room temperature and discharging to obtain the microchannel plate cladding material glass.
Preferably, the method for preparing the microchannel plate skin glass with high stable temperature resistance characteristic for low temperature comprises the following steps:
Figure BDA0002313263950000031
preferably, in the method for preparing the microchannel plate skin material glass with high stable temperature resistance characteristic for low temperature, the lead oxide is red lead or yellow lead; the barium salt is barium nitrate or barium carbonate; the potassium salt is potassium carbonate or potassium nitrate; the ruthenium compound is ruthenium trichloride, ruthenium trichloride hydrate, ruthenium dioxide or ruthenium dioxide hydrate.
Preferably, in the method for preparing the microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature, the refining agent is Sb2O3And/or As2O3。
In order to achieve the above object, the present invention further provides a microchannel plate with high stable temperature resistance for low temperature, which comprises a substrate and electrodes disposed on the upper and lower surfaces of the substrate, wherein the substrate comprises a frit glass with independent hollow channels and a cladding glass covering the outside of a hollow channel array composed of the frit glass, and the frit glass is the frit glass of the microchannel plate according to any one of claims 1 to 3.
In order to achieve the above object, the present invention further provides a method for preparing a microchannel plate with high stable temperature resistance for low temperature, comprising the following steps:
s1, drawing and forming a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate;
s2, preparing a core material glass rod;
s3, nesting the core material glass rod into the leather material glass tube and drawing the core material glass rod into a monofilament;
s4, combining a plurality of monofilaments and then drawing the monofilaments into multifilaments;
s5, regularly arranging multifilaments, and then melting and pressing the multifilaments into blank sections;
s6, slicing, chamfering, grinding and polishing the blank sections to obtain a blank plate;
and S7, corroding the blank plate with acid liquor to remove cores, reducing the blank plate with high-temperature hydrogen, and plating a metal electrode to obtain the micro-channel plate with high stable temperature resistance for low temperature.
Preferably, the method for preparing a microchannel plate having a high stable temperature resistance characteristic for low temperature as described above, wherein,
step S6 specifically includes: slicing, chamfering, grinding and polishing the blank sections to obtain a micro-channel plate blank plate with high stable temperature resistance for low temperature;
step S7 specifically includes: the method comprises the steps of corroding and coring a blank plate by acid liquor to obtain an independent hollow channel structure with millions of micron-sized apertures, reducing the structure by high-temperature hydrogen to grow a conducting layer and a silicon dioxide secondary electron emission layer with high stable temperature resistance characteristics in situ on the surface of the inner wall of the hollow channel, and then evaporating metal electrodes on the upper surface and the lower surface of the conducting layer and the silicon dioxide secondary electron emission layer to obtain the micro-channel plate with high stable temperature resistance characteristics for low temperature.
Preferably, the method for preparing a microchannel plate having a high stable temperature resistance characteristic for low temperature as described above, wherein,
in the step S1, the drawing forming temperature of the leather glass tube is 1200-1350 ℃;
in step S7, the acid solution is at least one of nitric acid and hydrochloric acid, the solubility of the acid solution is 0.1mol% -30 mol%, the corrosion time of the acid solution is 10 min-600 min, and the corrosion temperature of the acid solution is 30-90 ℃;
in step S7, the temperature of the high-temperature hydrogen reduction is 350-520 ℃, the time of the high-temperature hydrogen reduction is 20-600 min, and the flow rate of the hydrogen is 0.005-10L/min;
in step S7, the metal electrode is a Ti, Cr, Au, or Ni/Cr surface electrode; the sheet resistance of the metal electrode is not higher than 300 Ω.
In order to achieve the above object, the present invention also provides an ALD (atomic layer deposition) modified microchannel plate, which comprises a substrate having a single or multiple layers of modified thin films deposited on an inner wall surface thereof.
Preferably, the ALD-modified microchannel plate is a microchannel plate having a high stable temperature resistance characteristic for low temperature as described above.
In order to achieve the above object, the present invention further provides a method for preparing an ALD modified microchannel plate, comprising the following steps:
and (3) taking the low-temperature high-stability temperature-resistance microchannel plate as a substrate, and preparing a single-layer or multi-layer modified film on the surface of the inner wall of the channel of the microchannel plate by using an atomic layer deposition method to obtain the ALD modified microchannel plate.
The invention starts from the aspect of modifying the temperature resistance characteristic of the microchannel plate, and directly introduces special oxide into the glass material to realize the conductive layer structure of the microchannel plate for regulating and controlling the components of the glass material, thereby reducing the ultralow temperature bulk resistance of the microchannel plate, greatly improving the capacity of the ultralow temperature signal of the microchannel plate for reading and responding at an ultralow speed, and promoting the further application of the microchannel plate in the fields of ultralow temperature quantum analog computation and the like.
By the technical scheme, the invention at least has the following advantages:
according to the invention, the ruthenium-containing oxide with resistance temperature characteristic modification is directly introduced into the microchannel plate cladding glass material, and a conducting layer structure with high stable temperature resistance characteristic is formed on the glass surface by in-situ growth after high-temperature hydrogen reduction, so that the obvious negative resistance temperature characteristic modification of the microchannel plate for low temperature can be realized, and the resistance temperature coefficient can be adjusted.
The invention can modify the intrinsic negative resistance temperature characteristic of the microchannel plate, reduce the change rate of exponential increase of the body resistance of the microchannel plate along with temperature reduction under the ultralow temperature condition, is beneficial to improving the temperature resistance coefficient stability of the microchannel plate under the ultralow temperature condition, and can reduce the ultralow temperature body resistance of the microchannel plate, thereby realizing the ultra-fast signal reading and response under the lower temperature condition.
Compared with the prior art which adopts various means and only reduces the resistivity of the conducting layer of the microchannel plate and the resistance of the normal temperature body, the invention utilizes the ruthenium-containing oxide directly introduced into the glass material to regulate and control the resistance temperature characteristic of the glass material of the microchannel plate, and slows down the trend that the resistance of the microchannel plate body increases rapidly along with the temperature under the ultralow temperature condition from the aspect of the modification of the resistance-temperature coefficient of the microchannel plate body, thereby realizing the high stable temperature resistance characteristic of the microchannel plate under the ultralow temperature condition, reducing the resistance of the microchannel plate under the ultralow temperature condition, aiming at the ultralow temperature section range applied by devices, the composition proportion of the ruthenium-containing oxide and the high-temperature hydrogen reduction treatment process can be adjusted and optimized to obtain the micro-channel plate suitable for the body resistance and the resistance temperature characteristic, so that the micro-channel plate has quicker signal reading and response in the required application ultralow temperature section.
Drawings
FIG. 1 is a schematic diagram of a micro-channel plate blank with high stable temperature resistance for low temperature use according to the present invention;
FIG. 2 is a schematic diagram of the structure of a microchannel plate blank with high stable temperature resistance for low temperature use according to the present invention;
FIG. 3 is a schematic structural view of a microchannel plate with high stable temperature resistance for low temperature use according to the present invention;
FIG. 4 is a schematic view showing the structure of the inner wall of the channel in embodiment 4 of the present invention;
FIG. 5 is a schematic view showing the structure of a microchannel plate and the inner wall of a channel in comparative example 4 of the present invention;
FIG. 6 is a schematic structural view of a microchannel plate and an inner wall of a channel in comparative example 3 of the present invention;
wherein: 1-skin glass, 2-core glass, 3-edge glass, 4-substrate, 5-channel inner wall, 6-electrode, 7-conducting layer and emission layer with high stable temperature resistance, 8-atom layer deposition microchannel plate film modification layer, 9-conventional substrate, 10-channel inner wall of conventional microchannel plate, and 11-conventional conducting layer and emission layer.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects of the microchannel plate cladding glass with high stable temperature resistance for low temperature and the preparation method and application thereof according to the present invention are provided with the accompanying drawings and 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.
The invention provides a microchannel plate cladding glass with high stable temperature resistance characteristic for low temperature, which comprises the following components in percentage by mole:
Figure BDA0002313263950000061
wherein, SiO2Is a glass former oxide, is a basic skeleton of a glass structure, is a main component of a clad glass, and when the content exceeds 78 mol%, the glass contains a large amount of [ SiO ]2]The planar structure is not beneficial to the chemical stability of the glass, the viscosity of the glass is also reduced, the thermal expansion coefficient is improved, and the compatibility with the micro-channel plate core glass with high stable temperature resistance for low temperature is deteriorated; when the content is less than 50 mol%, the glass stability may be deteriorated.
Bi2O3Is the oxide of the network outer body of the glass, is the fluxing agent of the glass, and proper Bi is added into the glass2O3The material property of glass forming can be improved, the thermal processing property of glass is improved, the high-temperature melting viscosity of the glass is reduced, and a conductive metal phase in a conductive layer can be formed after the high-temperature hydrogen reduction, but the content of the conductive metal phase exceeds 8 mol%, the phase splitting phenomenon is easy to occur, and the resistance property of the reduced glass is unstable; when the concentration is less than 1.5 mol%, the resistance of the prepared microchannel plate is unstable.
Na2O，K2O and Cs2O is the network external oxide of the glass, the alkali metal ions are easy to move and diffuse in the glass body, and the viscosity of the glass melted at high temperature can be reducedThe glass is easy to melt, is a good fluxing agent, can increase the thermal expansion coefficient of the glass, reduces the chemical stability and mechanical strength of the glass, and is not suitable to be introduced too much; na in micro-channel plate core material glass with high stable temperature resistance characteristic for low temperature2O，K2O and Cs2Adjusting the content of O, and introducing one or more of the O and the O to reduce the diffusion degree of the core skin in the fiber drawing and high-temperature hot pressing processes; if Na2O，K2O and Cs2When the total content of O is less than 4%, the glass forming property is poor; however, if the total content thereof is more than 25 mol%, the swelling is too high and the glass stability is poor.
MgO, BaO and CaO are network external oxides of the glass, are alkaline earth metal oxides, are beneficial to improving the anti-devitrification capability of the glass, adjusting the material property of the glass and improving the thermal processing performance of the glass, but the performance of the glass is unstable due to excessive addition, and the phase separation phenomenon occurs. If the total content of MgO, BaO and CaO is less than 1mol%, the hot workability of the glass is poor; however, if the total content is more than 6 mol%, the phase of the glass tends to be easily separated.
Al2O3The content of the oxide is the glass structure adjusting oxide, and the thermal expansion coefficient and the chemical and thermal stability of the glass are influenced. However, when the content is more than 2.5 mol%, the refractive index and dispersion of the glass are increased; when the amount is less than 0.1mol%, the thermal stability of the glass is poor.
RuO2The material is a glass conductive phase and a conductive phase precursor phase, is also a temperature resistance characteristic adjusting modified oxide of a conductive layer formed by in-situ growth of a microchannel plate, can form a novel ruthenium and ruthenium-based conductive metal phase after being reduced by high-temperature hydrogen, but is easy to generate crystallization and phase splitting phenomena after the content of the ruthenium and ruthenium-based conductive metal phase exceeds 12 mol%, and the stability of the resistance performance of the reduced glass is reduced; when the amount is less than 1.5 mol%, high resistance temperature stability cannot be satisfied.
The preparation methods of the micro-channel plate cladding glass with high stable temperature resistance characteristic for low temperature of the embodiment 1-4 and the cladding glass of the comparative example 1-2 comprise the following steps:
mixing quartz sand, lead oxide (red lead or yellow lead), bismuth oxide, and bariumMixing salt (barium nitrate or barium carbonate), sodium carbonate, cesium carbonate, potassium salt (potassium carbonate or potassium nitrate), basic magnesium carbonate, calcium carbonate, aluminum hydroxide and ruthenium compound (ruthenium trichloride or ruthenium trichloride hydrate or ruthenium dioxide hydrate) to obtain a batch, and adding a clarifying agent Sb (Sb) accounting for 0.10-0.80 wt% of the total weight of the batch2O3And/or As2O3；
Adding the batch mixture containing the clarifying agent into a crucible at 1300-1550 ℃ for one or more times for melting, wherein the time interval between each time of feeding is 15-90 minutes; after the feeding is finished, heating to 1400-1550 ℃ for clarification for 2-12 hours and 5-10 hours; cooling to 1200 and 1350 ℃ after the clarification is finished, and preserving the heat for 1-5 hours for homogenization; drawing and forming the glass liquid into a glass tube material at 1200-1350 ℃ after homogenization; and (3) preserving the heat of the formed glass tube material for 2-6 hours at the temperature of 550-650 ℃, then cutting off the power and annealing to room temperature and discharging to obtain the microchannel plate cladding material glass.
The method for preparing the conventional microchannel plate skin glass of comparative examples 3 to 4 of the present invention comprises the steps of:
mixing quartz sand, lead oxide (red lead or yellow lead), bismuth oxide, barium salt (barium nitrate or barium carbonate), sodium carbonate, cesium carbonate, potassium salt (potassium carbonate or potassium nitrate), basic magnesium carbonate, calcium carbonate and aluminum hydroxide to obtain a batch mixture, and adding a clarifying agent Sb accounting for 0.10-0.80 wt% of the total weight of the batch mixture2O3And/or As2O3；
Adding the batch mixture containing the clarifying agent into a crucible at 1300-1550 ℃ for one or more times for melting, wherein the time interval between each time of feeding is 15-90 minutes; after the feeding is finished, heating to 1400-1550 ℃ for clarification for 2-12 hours and 5-10 hours; cooling to 1200 and 1350 ℃ after the clarification is finished, and preserving the heat for 1-5 hours for homogenization; drawing and forming the glass liquid into a glass tube material at 1200-1350 ℃ after homogenization; the formed glass tube material is insulated for 2-6 hours at the temperature of 550-650 ℃, and then is cut off and annealed to room temperature to be discharged, thus obtaining the conventional microchannel plate cladding material glass described in the comparative examples 3-4.
The cladding glass of comparative example 1 of the present invention has poor glass forming characteristics and poor crystallization performance, and therefore, a microchannel plate with high stable temperature resistance characteristics for low temperature cannot be prepared, and the practicability of the cladding glass required for preparing the microchannel plate is not provided.
The preparation methods of the microchannel plate with high stable temperature resistance for low temperature in examples 1-3 and the microchannel plate in comparative example 2 of the invention adopt the cladding glass described in the above examples 1-3 and comparative example 2 as the cladding glass of the microchannel plate, and the preparation process mainly comprises the following steps:
pulling down at 1200-1350 ℃ to form a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate; preparing a core glass rod, nesting the core glass rod into the cladding glass tube, drawing the core glass rod into a single filament, combining a plurality of single filaments, and drawing the combined single filaments into a multifilament; the multifilaments are arranged regularly and then are melted and pressed into blank sections; then, the blank plate is obtained through slicing, chamfering, grinding and polishing, and the structure of the blank plate is shown in figure 1 and comprises the following components: the glass comprises skin glass 1, core glass 2 arranged in the skin glass 1 and edge-covered glass 3 coated outside a hollow channel array formed by the skin glass 1 (a core material rod, a skin material pipe and the edge-covered glass all undergo multiple heat effects together, and the skin material pipe, the core material rod, the skin material pipe and the edge-covered glass are fused and diffused with components). Removing core glass 2 from the blank plate by acid liquor corrosion (the acid liquor is at least one of nitric acid and hydrochloric acid, the solubility of the acid liquor is 0.1mol% -30 mol%, the time of the acid liquor corrosion is 10 min-600 min, the temperature of the acid liquor corrosion is 30-90 ℃), and forming the microchannel blank plate, wherein the microchannel blank plate has a structure shown in figure 2 and comprises: the hollow glass plate comprises a skin glass 1 with independent hollow channels and a coated glass 3 coated outside a hollow channel array formed by the skin glass 1. And then, carrying out high-temperature hydrogen reduction (the temperature is 350-520 ℃ for 20-600 min, the hydrogen flow is 0.005-10L/min) on the microchannel plate blank plate, plating a metal electrode to obtain the microchannel plate with the characteristics of 5-20 mu m of aperture, 0.20-0.80 mm of thickness and 10-50 mm of outer diameter phi and high stable temperature resistance for low temperature, wherein the structure of the microchannel plate is shown in figure 3, the microchannel plate comprises a base body 4 and electrodes 6 arranged on the upper surface and the lower surface of the base body 4, the base body 4 comprises cladding glass 1 with independent hollow channels and cladding glass 3 cladding the outside of a hollow channel array consisting of the cladding glass 1, and the cladding glass 1 comprises a base material and a channel inner wall 5 connected with the base material. The inner wall 5 of the channel is a high-stability temperature resistance conductive layer and an emission layer 7 generated in situ or as shown in fig. 4, and the inner wall 5 of the channel comprises the high-stability temperature resistance conductive layer and the emission layer 7 generated in situ and an atomic layer deposition microchannel plate film modification layer 8 attached to the high-stability temperature resistance conductive layer and the emission layer 7.
The preparation method of the microchannel plate with the high-temperature resistance and stability for low temperature in embodiment 4 of the present invention adopts the cladding glass described in embodiment 4 as the cladding glass of the microchannel plate, and the preparation process mainly includes:
pulling down at 1200-1350 ℃ to form a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate; preparing a core glass rod, nesting the core glass rod into the cladding glass tube, drawing the core glass rod into a single filament, combining a plurality of single filaments, and drawing the combined single filaments into a multifilament; the multifilaments are arranged regularly and then are melted and pressed into blank sections; then, the blank plate is obtained through slicing, chamfering, grinding and polishing, and the structure of the blank plate is shown in figure 1 and comprises the following components: the glass comprises skin glass 1, core glass 2 arranged in the skin glass 1 and edge glass 3 coated outside a hollow channel array formed by the skin glass 1. Removing core glass 2 from the blank plate by acid liquor corrosion (the acid liquor is at least one of nitric acid and hydrochloric acid, the solubility of the acid liquor is 0.1mol% -30 mol%, the time of the acid liquor corrosion is 10 min-600 min, the temperature of the acid liquor corrosion is 30-90 ℃), and forming the microchannel blank plate, wherein the microchannel blank plate has a structure shown in figure 2 and comprises: the hollow glass plate comprises a skin glass 1 with independent hollow channels and a coated glass 3 coated outside a hollow channel array formed by the skin glass 1. Then, the microchannel plate blank is subjected to high-temperature hydrogen reduction (the temperature is 350-520 ℃, the time is 20-600 min, the hydrogen flow is 0.005L/min-10L/min), metal electrode plating and resistance temperature characteristic modification layer plating by atomic layer deposition to prepare the microchannel plate with the aperture of 5-20 microns, the thickness of 0.20-0.80 mm and the outer diameter phi of 10-50 mm and with high stable temperature resistance characteristic for low temperature, and the structure of the microchannel plate is shown in figure 4, and the microchannel plate comprisesThe electrode structure comprises a base body 4 and electrodes 6 arranged on the upper surface and the lower surface of the base body 4, wherein the base body 4 comprises cladding glass 1 with independent hollow channels and edge-covered glass 3 covering the outside of a hollow channel array formed by the cladding glass 1, and the cladding glass 1 comprises a base material and a channel inner wall 5 connected with the base material. The inner wall 5 of the channel of the microchannel plate comprises a conducting layer and an emitting layer 7 with high stable temperature resistance characteristics generated in situ and an atomic layer deposition microchannel plate film modification layer 8 attached to the conducting layer and the emitting layer 7 with the high stable temperature resistance characteristics, wherein the atomic layer deposition microchannel plate film modification layer 8 is a barium strontium titanate composite film, the thickness of the film is 201-203 nm, and barium oxide (BaO) and titanium dioxide (TiO) which form a barium strontium titanate single-layer composite film material2) And strontium oxide (SrO) with the molar ratio of 11:25:10, and the barium strontium titanate multilayer composite film with the thickness of 201-203 nm is formed through 25 times of preparation and superposition of the barium strontium titanate single-layer composite film.
The preparation method of the conventional microchannel plate of comparative example 4 of the present invention adopts the conventional cladding glass of comparative example 4 as the cladding glass of the microchannel plate, and the preparation process mainly comprises:
pulling down at 1200-1350 ℃ to form a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate; preparing a core glass rod, nesting the core glass rod into the cladding glass tube, drawing the core glass rod into a single filament, combining a plurality of single filaments, and drawing the combined single filaments into a multifilament; the multifilaments are arranged regularly and then are melted and pressed into blank sections; then, the blank plate is obtained through slicing, chamfering, grinding and polishing, and the structure of the blank plate is shown in figure 1 and comprises the following components: the glass comprises skin glass 1, core glass 2 arranged in the skin glass 1 and edge glass 3 coated outside a hollow channel array formed by the skin glass 1. Removing core glass 2 from the blank plate by acid liquor corrosion (the acid liquor is at least one of nitric acid and hydrochloric acid, the solubility of the acid liquor is 0.1mol% -30 mol%, the time of the acid liquor corrosion is 10 min-600 min, the temperature of the acid liquor corrosion is 30-90 ℃), and forming the microchannel blank plate, wherein the microchannel blank plate has a structure shown in figure 2 and comprises: the hollow glass plate comprises a skin glass 1 with independent hollow channels and a coated glass 3 coated outside a hollow channel array formed by the skin glass 1. Followed byThe microchannel plate blank is subjected to high-temperature hydrogen reduction (the temperature is 350-520 ℃ for 20-600 min, the hydrogen flow is 0.005L/min-10L/min), metal electrode plating and atomic layer deposition plating of a resistance temperature characteristic modification layer to obtain the microchannel plate with the aperture of 5-20 microns, the thickness of 0.20-0.80 mm and the outer diameter phi of 10-50 mm, and the high-temperature-resistance characteristic for low temperature, the structure of the microchannel plate is shown in figure 5, the microchannel plate comprises a conventional base body 9 and electrodes 6 arranged on the upper surface and the lower surface of the base body 9, the base body 9 comprises cladding glass 1 with independent hollow channels and edge-covering glass 3 covering the outside of a hollow channel array formed by the cladding glass 1, and the cladding glass 1 comprises a base material and channel inner walls 10 connected with the base material. The inner wall 10 of the channel of the microchannel plate comprises a conventional conducting layer and an emitting layer 11 which are generated in situ and an atomic layer deposition microchannel plate film modification layer 8 attached to the conventional conducting layer and the emitting layer 11, wherein the atomic layer deposition microchannel plate film modification layer 8 is a barium strontium titanate composite film, the thickness of the film is 180nm, and barium oxide (BaO) and titanium dioxide (TiO) which form a barium strontium titanate single-layer composite film material2) And the mol ratio of strontium oxide (SrO) is 10:25:6, and the barium strontium titanate multilayer composite film with the thickness of 180nm is formed by preparing and overlapping the barium strontium titanate single-layer composite film for 25 times.
The preparation method of the microchannel plate of comparative example 3 of the present invention adopts the cladding glass of comparative example 3 as the cladding glass of the microchannel plate, and the preparation process mainly comprises:
pulling down at 1200-1350 ℃ to form a leather glass tube, wherein the leather glass tube is made of the leather glass of the microchannel plate; preparing a core glass rod, nesting the core glass rod into the cladding glass tube, drawing the core glass rod into a single filament, combining a plurality of single filaments, and drawing the combined single filaments into a multifilament; the multifilaments are arranged regularly and then are melted and pressed into blank sections; then, the blank plate is obtained through slicing, chamfering, grinding and polishing, and the structure of the blank plate is shown in figure 1 and comprises the following components: the glass comprises skin glass 1, core glass 2 arranged in the skin glass 1 and edge glass 3 coated outside a hollow channel array formed by the skin glass 1. Removing core glass 2 from the blank plate by acid liquor corrosion (the acid liquor is at least one of nitric acid and hydrochloric acid, the solubility of the acid liquor is 0.1mol% -30 mol%, the time of the acid liquor corrosion is 10 min-600 min, the temperature of the acid liquor corrosion is 30-90 ℃), and forming the microchannel blank plate, wherein the microchannel blank plate has a structure shown in figure 2 and comprises: the hollow glass plate comprises a skin glass 1 with independent hollow channels and a coated glass 3 coated outside a hollow channel array formed by the skin glass 1. And then, carrying out high-temperature hydrogen reduction (the temperature is 350-520 ℃ for 20-600 min, the hydrogen flow is 0.005-10L/min) on the microchannel plate blank plate, plating a metal electrode to obtain the microchannel plate with the aperture of 5-20 microns, the thickness of 0.20-0.80 mm and the outer diameter phi of 10-50 mm, wherein the microchannel plate has the structure shown in figure 6 and comprises a conventional base body 9 and electrodes 6 arranged on the upper surface and the lower surface of the base body 9, the base body 9 comprises cladding glass 1 with independent hollow channels and cladding glass 3 cladding the outside of a hollow channel array formed by the cladding glass 1, and the cladding glass 1 comprises a base material and a channel inner wall 10 connected with the base material. Wherein, the inner wall 10 of the channel is a conventional conductive layer and an emitting layer 11 generated in situ.
In the microchannel plate and the preparation method thereof, except that the cladding glass is the high-temperature-resistance-property high-stability cladding glass for the microchannel plate for low temperature obtained by the invention, other raw materials and preparation processes adopt corresponding means in the prior art, so the details are not repeated herein.
The inner wall structures of the channels of the microchannel plates described in embodiments 1 to 3 are all as shown in fig. 3, that is, the inner wall structures of the channels of the microchannel plates are the in-situ generated conductive layer and the emission layer 7 with high stable temperature resistance.
The structure of the inner wall of the microchannel plate in embodiment 4 is as shown in fig. 4, that is, the inner wall of the microchannel plate includes a conductive layer and an emission layer 7 with a high stable temperature resistance generated in situ, and an atomic layer deposition microchannel plate thin film modification layer 8 attached to the conductive layer and the emission layer 7 with the high stable temperature resistance, where the atomic layer deposition microchannel plate thin film modification layer 8 is a barium strontium titanate composite thin film, and in embodiment 4, the thickness of the thin film is 201 to 203nm, and barium oxide (BaO) and titanium dioxide (TiO) constituting a barium strontium titanate single-layer composite thin film material are barium strontium titanate single-layer composite thin films2) And strontium oxideThe mol ratio of (SrO) is 11:25:10, the barium strontium titanate multilayer composite film with the thickness of 201-203 nm is formed by 25 times of preparation and superposition of the barium strontium titanate single-layer composite film, in the comparative example 4, the thickness of the barium strontium titanate composite film is 180nm, and barium oxide (BaO) and titanium dioxide (TiO) of the barium strontium titanate single-layer composite film material are formed2) And the mol ratio of strontium oxide (SrO) is 10:25:6, and the barium strontium titanate multilayer film with the thickness of 180nm is formed through 25 times of barium strontium titanate single-layer film preparation and superposition.
The clad glasses used in comparative examples 3 to 4 of the present invention are those of conventional microchannel plates, and the main difference between the glasses and examples 1 to 4 of the present invention is that the former clad glasses do not contain ruthenium oxide having a positive temperature resistance characteristic. A microchannel plate and a channel inner wall structure thereof as shown in fig. 5 in comparative example 4, where the microchannel plate includes a conventional substrate 9 of the microchannel plate made of a conventional glass material and electrodes 6 disposed on upper and lower surfaces of the conventional substrate 9, the conventional substrate 9 includes a channel inner wall 10 of the conventional microchannel plate, the channel inner wall 10 of the conventional microchannel plate includes a conventional conductive layer and an emission layer 11 generated in situ and an atomic layer deposition microchannel plate thin film modification layer 8 attached to the conventional conductive layer and the emission layer 11, the atomic layer deposition microchannel plate thin film modification layer 11 is a barium strontium titanate composite thin film, and in comparative example 4, the barium strontium titanate composite thin film has a thickness of 180nm, and barium oxide (BaO) and titanium dioxide (TiO) constituting a barium strontium titanate single-layer composite thin film material2) And the mol ratio of strontium oxide (SrO) is 10:25:6, and the barium strontium titanate multilayer film with the thickness of 180nm is formed through 25 times of barium strontium titanate single-layer film preparation and superposition.
As shown in Table 1 below, the clad glass material used in comparative example 4 was RuO removed from the clad glass material used in comparative example 22Preparing a micro-channel plate substrate from similar glass materials as in comparative example 2, and performing Atomic Layer Deposition (ALD) on a micro-channel plate thin film modification layer 8, wherein the thickness of the barium strontium titanate composite thin film is 180nm, and the molar ratio of the barium strontium titanate single-layer composite thin film material is BaO to TiO2SrO 10:25:6, prepared by 25 times of barium strontium titanate single-layer thin film forming to the thickness of180nm barium strontium titanate multilayer film. Comparative example 4 has a resistance of not more than 5G Ω at a temperature of 30K while substantially satisfying high resistance temperature stability at an ultra-low temperature, but the latter is significantly more excellent in resistance temperature stability than example 4.
TABLE 1 compositions and Performance tests of the skin glasses for microchannel plates having high stable temperature resistance characteristics for low temperature according to examples 1 to 4 of the present invention and comparative examples 1 to 4, and Performance tests of microchannel plates respectively prepared using the skin glasses of examples 1 to 4 and comparative examples 2 to 4 described above
Figure BDA0002313263950000131
Figure BDA0002313263950000141
As can be seen from table 1, the smaller the absolute value of the resistance temperature coefficient of example 4 is, the higher the resistance temperature stability of the cladding glass prepared in example 4 is, that is, by introducing the positive temperature resistance oxide into the glass material and introducing the ALD modified thin film layer with positive temperature resistance on the surface of the inner wall of the channel, the microchannel plate with high stable temperature resistance under the ultra-low temperature condition can be realized; the absolute value of the resistance temperature coefficient of the embodiments 2, 1 and 3 is the second order, namely, the micro-channel plate with high stable temperature resistance characteristic under the ultralow temperature condition can be realized by introducing the positive temperature resistance characteristic oxide into the glass material, and the bulk resistances of the embodiments 2, 1 and 3 under the 30K low temperature condition are all less than 5G omega, so that the ultra-fast reading response requirements under the ultralow temperature detection conditions such as ultralow temperature quantum simulation calculation and the like can be met; the absolute value of the resistance temperature coefficient of the comparative example 3 is small, but the volume resistance of the resistance temperature coefficient exceeds 5G omega under the low-temperature conditions of 35K and 30K, and the ultra-fast reading response requirement under the low-temperature detection conditions of ultralow-temperature quantum simulation calculation and the like cannot be met; RuO having Positive temperature resistance characteristic due to temperature resistance characteristic modification in comparative example 12Too much introduction, greatly reduced glass forming property of the cladding glass, poor devitrification resistance and incapability of meeting the requirement of a micro-channelThe crystallization resistance required by the preparation of the plate can not prepare the microchannel plate, and the practicability of the cladding glass required by the preparation of the microchannel plate is not realized.
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 (13)

1.一种低温用高稳定温阻特性的微通道板皮料玻璃，其特征在于，以摩尔百分比计，其包括：1. a kind of microchannel plate leather glass with high stability temperature resistance characteristic at low temperature, it is characterized in that, in molar percentage, it comprises: SiO2 50%~78%；SiO 2 50%~78%; Bi2O3 1.5%~8%；Bi 2 O 3 1.5%~8%; PbO 5.0%~15%；PbO 5.0%~15%; Na2O、K2O和Cs2O中的至少一种 4.0%~25%；4.0%~25% of at least one of Na 2 O, K 2 O and Cs 2 O; MgO、BaO和CaO中的至少一种 1.0%~6%；1.0%~6% of at least one of MgO, BaO and CaO; Al2O3 0.1%~2.5%；Al 2 O 3 0.1%~2.5%; RuO2 1.5%~12%。RuO 2 1.5%~12%. 2.如权利要求1所述的微通道板皮料玻璃，其特征在于，所述低温用高稳定温阻特性的微通道板皮料玻璃按重量百分比计还包括0.10%~0.80%的Sb2O3和/或As2O3。2. The microchannel plate cover glass according to claim 1, characterized in that, the microchannel plate cover glass with high stable temperature resistance characteristics for low temperature further comprises 0.10%-0.80% by weight of Sb 2 O 3 and/or As 2 O 3 . 3.如权利要求1所述的微通道板皮料玻璃，其特征在于，所述低温用高稳定温阻特性的微通道板皮料玻璃的转变温度为Tg≥450℃，软化温度为Tf≥545℃，在100℃到300℃的热膨胀系数为(60~105)×10-7/℃，在500℃~950℃之间无析晶。3. The microchannel plate covering glass according to claim 1, wherein the transition temperature of the microchannel plate covering glass with high stable temperature resistance characteristics for low temperature is T g ≥ 450°C, and the softening temperature is T f ≥ 545°C, the thermal expansion coefficient is (60~105)×10 -7 /°C at 100°C to 300°C, and there is no devitrification between 500°C and 950°C. 4.一种权利要求1-3任一项所述的低温用高稳定温阻特性的微通道板皮料玻璃的制备方法，其特征在于，包括以下步骤：4. The preparation method of the microchannel plate skin glass with high stable temperature resistance characteristics for low temperature use according to any one of claims 1-3, characterized in that, comprising the following steps: 1）将石英砂、铅氧化物、氧化铋、钡盐、碳酸钠、碳酸铯、钾盐、碱式碳酸镁、碳酸钙、氢氧化铝及钌的化合物混合，得到配合料，并加入占该配合料总重量0.10wt%~0.80wt%的澄清剂；1) Mix the compounds of quartz sand, lead oxide, bismuth oxide, barium salt, sodium carbonate, cesium carbonate, potassium salt, basic magnesium carbonate, calcium carbonate, aluminum hydroxide and ruthenium to obtain batching materials, and add 0.10wt%~0.80wt% clarifying agent of the total weight of the batching material; 2）在1300~1550℃下将含有澄清剂配合料按一次或多次加入坩埚中进行熔制，每次加料间隔时间15分钟-90分钟；2) At 1300~1550℃, add the batching material containing the clarifying agent into the crucible one or more times for melting, and the interval between each feeding is 15 minutes to 90 minutes; 3）加料完成后升温至1400~1550℃进行澄清2-12小时；3) After the feeding is completed, the temperature is raised to 1400~1550℃ for clarification for 2-12 hours; 4）澄清结束后降温至1200-1350℃保温1-5小时进行均化；4) After clarification, the temperature is lowered to 1200-1350°C and kept for 1-5 hours for homogenization; 5）均化结束后将玻璃液在1200-1350℃拉制成型为玻璃管料；5) After the homogenization is completed, the glass liquid is drawn into a glass tube material at 1200-1350 ℃; 6）成型的玻璃管料在在550-650℃下保温2-6小时，然后断电退火至室温出炉，得到所述微通道板皮料玻璃。6) The formed glass tube material is kept at 550-650° C. for 2-6 hours, and then annealed to room temperature after power off to obtain the micro-channel plate skin glass. 5.如权利要求4所述的制备方法，其特征在于，所述熔制的过程中坩埚内保持弱氧化气氛，所述弱氧化气氛中氧气分压大于20kPa。5 . The preparation method according to claim 4 , wherein a weakly oxidizing atmosphere is maintained in the crucible during the melting process, and the partial pressure of oxygen in the weakly oxidizing atmosphere is greater than 20 kPa. 6 . 6.如权利要求4所述的制备方法，其特征在于，所述配合料以摩尔百分比计包括：6. preparation method as claimed in claim 4 is characterized in that, described batching material comprises in mole percent: 石英砂 50%~78%；Quartz sand 50%~78%; 氧化铋 1.5%~8%；Bismuth oxide 1.5%~8%; 铅氧化物 5.0%~15%；Lead oxide 5.0%~15%; 碳酸钠、钾盐和碳酸铯中的至少一种 4.0%~25%；At least one of sodium carbonate, potassium salt and cesium carbonate 4.0%~25%; 碱式碳酸镁、钡盐和碳酸钙中的至少一种 1.0%~6%；1.0%~6% of at least one of basic magnesium carbonate, barium salt and calcium carbonate; 氢氧化铝 0.1%~2.5%；Aluminum hydroxide 0.1%~2.5%; 钌的化合物 1.5%~12%。Ruthenium compound 1.5%~12%. 7.如权利要求6所述的制备方法，其特征在于，所述铅氧化物为红丹或黄丹；所述钡盐为硝酸钡或碳酸钡；所述钾盐为碳酸钾或硝酸钾；所述钌的化合物为三氯化钌、三氯化钌水合物、二氧化钌或二氧化钌水合物；所述澄清剂为Sb2O3和/或As2O3。7. preparation method as claimed in claim 6 is characterized in that, described lead oxide is red red or yellow red; Described barium salt is barium nitrate or barium carbonate; Described potassium salt is potassium carbonate or potassium nitrate; The ruthenium compound is ruthenium trichloride, ruthenium trichloride hydrate, ruthenium dioxide or ruthenium dioxide hydrate; the clarifying agent is Sb 2 O 3 and/or As 2 O 3 . 8.一种低温用高稳定温阻特性的微通道板，其特征在于，包括基体及设于所述基体上下表面的电极，所述基体包括具有独立的中空通道的皮料玻璃及包覆于所述皮料玻璃外表面的包边玻璃，所述皮料玻璃为权利要求 1-3任一项所述的微通道板皮料玻璃。8. A microchannel plate with high stable temperature resistance characteristics for low temperature use, characterized in that it comprises a base body and electrodes arranged on the upper and lower surfaces of the base body, and the base body comprises leather glass with independent hollow channels and coated on The edging glass on the outer surface of the leather glass is the micro-channel plate leather glass according to any one of claims 1-3. 9.一种低温用高稳定温阻特性的微通道板的制备方法，其特征在于，包括以下步骤：9. A preparation method of a microchannel plate with high stable temperature resistance characteristics at low temperature, characterized in that, comprising the following steps: S1．拉制成型皮料玻璃管，所述皮料玻璃管的材质为权利要求1-3任一项所述的微通道板皮料玻璃；S1. Drawing and forming a leather glass tube, the material of the leather glass tube is the micro-channel plate leather glass according to any one of claims 1-3; S2．制备芯料玻璃棒；S2. Preparation of core glass rods; S3．将所述芯料玻璃棒嵌套入所述皮料玻璃管中拉成单丝；S3. inserting the core glass rod into the leather glass tube and drawing it into a monofilament; S4．将多根单丝组合后拉成复丝；S4. After combining multiple monofilaments, they are drawn into multifilaments; S5．复丝规则排列后熔压成毛坯段；S5. The multifilaments are regularly arranged and then melted and pressed into a blank segment; S6．将毛坯段经切片、倒角、研磨抛光制得毛坯板；S6. The blank section is sliced, chamfered, ground and polished to obtain a blank plate; S7．将毛坯板经酸液腐蚀去芯、高温氢气还原、镀制金属电极后得到低温用高稳定温阻特性的微通道板。S7. A microchannel plate with high stable temperature resistance characteristics for low temperature is obtained after the blank plate is corroded by acid solution, de-cored, reduced by high temperature hydrogen gas, and plated with metal electrodes. 10.如权利要求9所述的制备方法，其特征在于，10. preparation method as claimed in claim 9, is characterized in that, 步骤S6具体包括：将毛坯段经切片、倒角、研磨抛光制得低温用高稳定温阻特性的微通道板毛坯板；Step S6 specifically includes: slicing, chamfering, grinding and polishing the blank segment to obtain a microchannel plate blank plate with high stable temperature resistance characteristics for low temperature; 步骤S7具体包括：将毛坯板先经酸液腐蚀去芯制得具有数百万根微米级孔径的独立中空通道结构，后经高温氢气还原，从而在其中空通道内壁表面原位生长形成高稳定温阻特性的导电层、二氧化硅二次电子发射层，之后在其上下双表面蒸镀金属电极，得到低温用高稳定温阻特性的微通道板。Step S7 specifically includes: first corroding the blank plate with acid solution to obtain an independent hollow channel structure with millions of micron-scale pore diameters, and then reducing it with high-temperature hydrogen, so as to grow in situ on the inner wall surface of the hollow channel to form a highly stable structure. A conductive layer with temperature resistance characteristics and a silicon dioxide secondary electron emission layer, and then metal electrodes are evaporated on the upper and lower surfaces to obtain a microchannel plate with high temperature resistance characteristics for low temperature use. 11.如权利要求10所述的制备方法，其特征在于，11. preparation method as claimed in claim 10, is characterized in that, 步骤S1中，所述皮料玻璃管的拉制成型温度为1200~1350℃；In step S1, the drawing temperature of the leather glass tube is 1200-1350°C; 步骤S7中，所述酸液为硝酸和盐酸中的至少一种，所述酸液的溶度为0.1mol%~30mol%，所述酸液腐蚀的时间为10min~600min，所述酸液腐蚀的温度为30℃~90℃；In step S7, the acid solution is at least one of nitric acid and hydrochloric acid, the solubility of the acid solution is 0.1mol%～30mol%, the acid solution corrosion time is 10min～600min, the acid solution corrosion The temperature is 30℃~90℃; 步骤S7中，所述高温氢气还原的温度为350℃~520℃，所述高温氢气还原的时间为20min~600min，所述氢气的流量为0.005L/min~10L/min；In step S7, the temperature of the high-temperature hydrogen reduction is 350°C to 520°C, the high-temperature hydrogen reduction time is 20min to 600min, and the flow rate of the hydrogen is 0.005L/min to 10L/min; 步骤S7中，所述金属电极为Ti，或Cr，或Au，或Ni/Cr表面电极；所述金属电极的面电阻为不高于300Ω。In step S7, the metal electrode is Ti, or Cr, or Au, or a Ni/Cr surface electrode; the sheet resistance of the metal electrode is not higher than 300Ω. 12.一种ALD改性微通道板，其特征在于，所述ALD改性微通道板包括基板，所述基板的内壁表面沉积有单层或多层改性薄膜；所述基板为权利要求8所述的低温用高稳定温阻特性的微通道板。12. An ALD-modified microchannel plate, characterized in that the ALD-modified microchannel plate comprises a substrate, and a single-layer or multi-layer modified film is deposited on the inner wall surface of the substrate; the substrate is claim 8 The microchannel plate with high stable temperature resistance characteristics for low temperature use. 13.一种权利要求12所述的ALD改性微通道板的制备方法，其特征在于，包括以下步骤：13. a preparation method of ALD modified microchannel plate according to claim 12, is characterized in that, comprises the following steps: 以权利要求8所述的低温用高稳定温阻特性的微通道板为基体，使用原子层沉积法在该微通道板的通道内壁表面制备单层或多层改性薄膜，以得到ALD改性微通道板。Taking the microchannel plate of claim 8 with high stable temperature resistance characteristics for low temperature as a substrate, using atomic layer deposition method to prepare a single-layer or multi-layer modified film on the inner wall surface of the channel of the microchannel plate, to obtain ALD modification Microchannel plate.
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