CN111785597A - Silicon channel plate for photomultiplier and preparation method thereof - Google Patents
Silicon channel plate for photomultiplier and preparation method thereof Download PDFInfo
- Publication number
- CN111785597A CN111785597A CN202010718865.7A CN202010718865A CN111785597A CN 111785597 A CN111785597 A CN 111785597A CN 202010718865 A CN202010718865 A CN 202010718865A CN 111785597 A CN111785597 A CN 111785597A
- Authority
- CN
- China
- Prior art keywords
- silicon
- silicon wafer
- solution
- photoresist
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 102
- 239000010703 silicon Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000005530 etching Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000010970 precious metal Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 238000001465 metallisation Methods 0.000 claims description 7
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 238000009279 wet oxidation reaction Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 3
- 239000002106 nanomesh Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000000861 blow drying Methods 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 229920001486 SU-8 photoresist Polymers 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- 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
- H01J9/12—Manufacture of electrodes or electrode systems of photo-emissive cathodes; of secondary-emission electrodes
- H01J9/125—Manufacture of electrodes or electrode systems of photo-emissive cathodes; of secondary-emission electrodes of secondary emission electrodes
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Weting (AREA)
Abstract
The invention provides a silicon channel plate for a photomultiplier and a preparation method thereof, wherein the preparation method comprises the following steps: acid washing and blow drying are carried out on the silicon wafer; uniformly coating photoresist on the surface of the blow-dried silicon wafer, covering a mask plate, irradiating for several minutes by adopting ultraviolet light, washing the photoresist on the surface by using a developing solution, and obtaining a pattern which is the same as or opposite to the pattern of the mask plate on the surface of the silicon wafer; depositing noble metal on the surface of the silicon wafer to obtain a noble metal layer, wherein the noble metal layer forms a nano-network structure on the surface of the silicon wafer; placing the silicon chip with the surface deposited with noble metal into the prepared HF-H2O2Soaking in the solution for several minutes to etch the surface of the substrate to obtain a microporous structure with corresponding depth; then taking out the etched silicon wafer, removing the deposited metal layer, and then cleaning and drying; and oxidizing the cleaned and dried silicon microchannel plate at high temperature to obtain a silicon oxide thin layer. The invention improves the gain consistency of the microchannel plate by improving the structure of the microchannel plateAnd the energy resolution of the photomultiplier tube.
Description
Technical Field
The invention relates to the technical field of photomultiplier tubes, in particular to a silicon channel plate for a photomultiplier tube and a preparation method thereof, and the preparation of a silicon microchannel plate with designable micropore size and distribution with high gain uniformity and high energy resolution is realized.
Background
The photomultiplier is a vacuum electronic device which converts weak optical signals into electric signals and multiplies and amplifies the electric signals, can effectively detect the extremely weak light, is widely applied to the research fields of extremely weak light detection, photon detection, chemiluminescence, bioluminescence and the like, and has the characteristics of high detection efficiency, high time resolution and the like. The photomultiplier mainly comprises a photocathode, a focusing electrode, an electron multiplier and other components, and is divided into two basic types, namely a microchannel plate type and a dynode type according to the electron multiplier.
The microchannel plate is a commonly used electron multiplier and is widely applied to a micro-optical image intensifier and a photomultiplier. Generally, a microchannel plate is made of glass, and a single piece of the microchannel plate can be prepared by the processes of drawing → arranging a screen → melting and pressing → slicing → corroding → hydrogen reducing → plating an electrode and the like.
To be provided withCan detect single photoelectrons, and has the electron gain of 107In the above, a method of stacking two microchannel plates is generally used for this purpose. Although the gain can be improved by the method, the obtained gain is poor in consistency, and the main reason is that the outgoing electron angles are dispersed after incident electrons are multiplied by the first microchannel plate, and many electrons with larger outgoing angles cannot enter the second microchannel plate. In addition, when the multiplied electrons emitted from the same micro-hole enter the next micro-channel plate, the multiplied electrons are difficult to enter the same micro-hole, which also causes the gain uniformity of the micro-channel plate to be poor. The gain consistency of the microchannel plate is directly related to the energy resolution of the photomultiplier, and the poor gain consistency can reduce the energy resolution of the photomultiplier.
In order to further improve the gain consistency and the energy resolution, a method of applying a reverse voltage between two microchannel plates is usually adopted, so that electrons with a larger emergent angle cannot enter a second microchannel plate, and further the gain consistency is improved, or a method of adjusting the partial pressure of the channel plates is adopted, so that the gain saturation degree of the second microchannel plate is increased, and the gain saturation is achieved as far as possible, and thus the higher energy resolution is obtained.
The above methods are all to adjust the electric field distribution at the electron multiplier from the aspect of electronics, so as to improve the gain consistency of the microchannel plate and the energy resolution of the photomultiplier, and have certain limitations.
Disclosure of Invention
The invention aims to provide a silicon channel plate for a photomultiplier and a preparation method thereof, which realize the improvement of the structure of the microchannel plate through novel photoetching and etching processes, and improve the gain consistency of the microchannel plate and the energy resolution of the photomultiplier.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a silicon channel plate for a photomultiplier tube, comprising the steps of:
step 1, acid cleaning is carried out on a silicon wafer, and H is contained at 100-120 DEG C2O2And H2SO4Soaking the mixed solution in the solution for 10 to 20 minutes, wherein H in the mixed solution2O2And H2SO4The volume ratio of (A) to (B) is 1: 1-1: 3; then soaking in 0.5-1% HF solution for 10-30 min to remove surface oxide, then cleaning with deionized water and drying with nitrogen;
step 2, uniformly coating photoresist on the surface of the blow-dried silicon wafer, covering a mask plate above the photoresist, irradiating for several minutes by adopting ultraviolet light, washing the surface photoresist by using a developing solution, and obtaining a pattern which is the same as or opposite to the pattern of the mask plate on the surface of the silicon wafer;
step 3, performing precious metal deposition on the surface of the silicon wafer with the surface photoresist pattern to obtain a precious metal layer with the thickness of 10-20nm, wherein the precious metal layer forms a nano-mesh structure on the surface of the silicon wafer;
step 4, putting the silicon chip with the noble metal deposited on the surface into the prepared HF-H2O2Soaking in the solution for several minutes to etch the surface of the substrate to obtain a microporous structure with corresponding depth; then taking out the etched silicon wafer, removing the deposited metal layer, cleaning with deionized water, and drying with nitrogen;
and 5, oxidizing the cleaned and dried silicon microchannel plate at high temperature to obtain a silicon oxide thin layer with the thickness of 10-500 nm.
Further, the solubility of the HF solution in the step 1 is 0.5-1%.
Further, in the step 2, the thickness of the coated photoresist is 10-20 μm, and after a mask plate is covered on the photoresist, ultraviolet light is adopted for irradiating for 1-30 minutes.
Further, in the step 3, the noble metal is one of gold, silver and platinum, a PVD deposition method is adopted, and the metal deposition rate is
And depositing for 5-10 minutes to obtain a noble metal layer with the thickness of 10-20 nm.
Further, in the step 4, the HF-H2O2The concentration of HF in the solution is 0.9-1.8 mol/L, H2O2The concentration of the etching solution is 3 to 3.2mol/L, and the etching rate is 0.5 to 1.0 μm/min.
Further, in the step 4, the etched silicon wafer is soaked in a nitric acid solution or an iodine-potassium iodide solution to remove the deposited noble metal layer.
Further, in the step 5, dry oxidation is adopted, and specifically includes: heating to 900-3And/s, oxidizing for 20-60 minutes to form a silicon dioxide thin layer.
Further, in the step 5, wet oxidation is adopted, and specifically, the method includes: heating to 700-1000 ℃, introducing high-purity water vapor at the aeration speed of 1-5 cm3And/s, oxidizing for 20-60 minutes to obtain a silicon oxide thin layer with the thickness of 10-500 nm.
According to a second aspect of the present invention, there is also provided a silicon channel plate prepared according to the aforementioned method.
The novel silicon microchannel plate prepared by the invention has the characteristics of designable distribution of micropores, adjustable pore diameter of the micropores and large and small sizes of the micropores. The silicon dioxide thin layer formed by thermal oxidation is tightly combined with silicon, the process is simple and reliable, the controllability is strong, and the silicon dioxide thin layer has the insulating property and has the secondary electron emission capability. The method simplifies the preparation process of the original microchannel plate. By the micropore distribution and the pore size design, the microchannel plate which is adaptive to the performance requirement of the photomultiplier can be prepared.
Meanwhile, the diameter of the micropore of the prepared silicon microchannel plate has the characteristics of large top and small bottom, so that photoelectrons can be gradually focused while being multiplied in the silicon microchannel plate, the dispersion degree of the exit angle of the photoelectrons is reduced, the consistency of the electrons entering the next microchannel plate is improved, and the gain consistency and the energy resolution of the photomultiplier are further improved.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent. In addition, all combinations of claimed subject matter are considered a part of the presently disclosed subject matter.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 and FIG. 2 are schematic diagrams of the distribution and size of micropores of silicon microchannel plates with different pore sizes.
FIG. 3 is a schematic diagram of a silicon wafer lithography and metal deposition process.
FIG. 4 is a photograph of a silicon wafer surface plated with gold by a high resolution scanning electron microscope.
FIGS. 5 and 6 are scanning electron microscope pictures of silicon microchannel plates.
FIGS. 7 and 8 are high-resolution scanning electron microscope images of the noble metal layer obtained by the too short and too long gold plating deposition time on the surface of the silicon wafer.
Detailed Description
In order to better understand the technical content of the invention, specific embodiments are specifically illustrated in the following description in combination with the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways, as the disclosed concepts and embodiments are not limited to any one implementation. In addition, some aspects of the present disclosure may be used alone, or in any suitable combination with other aspects of the present disclosure.
The invention provides a novel silicon microchannel plate, which is characterized in that the distribution and the aperture size of micropores of the microchannel plate are controlled and optimally designed through a photoetching process, the micropores are etched by adopting a metal-assisted chemical etching method, a complete silicon dioxide thin layer is formed on the surface of the silicon microchannel plate by adopting a thermal oxidation method, and the silicon microchannel plate has both insulating property and secondary electron emission property, wherein the aperture of the micropores has the trend characteristic of large top and small bottom, so that photoelectrons can gradually focus while being multiplied in the silicon microchannel plate, the dispersion degree of the photoelectron emergent angle is reduced, the consistency of the electrons entering the next microchannel plate is improved, and the gain consistency and the energy resolution of a photomultiplier are improved.
Embodiments of various aspects of the present invention are described in more detail below with reference to the figures 1-5.
In general, the preparation of the silicon microchannel plate of the present invention comprises the steps of:
step 1, acid cleaning is carried out on a silicon wafer, and H is contained at 100-120 DEG C2O2And H2SO4Soaking the mixed solution in the solution for 10 to 20 minutes, wherein H in the mixed solution2O2And H2SO4The volume ratio of (A) to (B) is 1: 1-1: 3; then soaking in 0.5-1% HF solution for 10-30 min to remove surface oxide, then cleaning with deionized water and drying with nitrogen;
step 2, uniformly coating photoresist on the surface of the blow-dried silicon wafer, covering a mask plate above the photoresist, irradiating for several minutes by adopting ultraviolet light, washing the surface photoresist by using a developing solution, and obtaining a pattern which is the same as or opposite to the pattern of the mask plate on the surface of the silicon wafer;
step 3, performing precious metal deposition on the surface of the silicon wafer with the surface photoresist pattern to obtain a precious metal layer with the thickness of 10-20nm, wherein the precious metal layer forms a nano-mesh structure on the surface of the silicon wafer;
step 4, sinking the surfacePlacing the silicon chip with the noble metal into the prepared HF-H2O2Soaking in the solution for several minutes to etch the surface of the substrate to obtain a microporous structure with corresponding depth; then taking out the etched silicon wafer, removing the deposited metal layer, cleaning with deionized water, and drying with nitrogen;
and 5, oxidizing the cleaned and dried silicon microchannel plate at high temperature to obtain a silicon oxide thin layer with the thickness of 10-500 nm, wherein the microporous structure tends to be large at the top and small at the bottom.
Further, the solubility of the HF solution in the step 1 is 0.5-1%.
Further, in the step 2, the thickness of the coated photoresist is 10-20 μm, and after a mask plate is covered on the photoresist, ultraviolet light is adopted for irradiating for 1-30 minutes.
Further, in the step 3, the noble metal is one of gold, silver and platinum, a PVD deposition method is adopted, and the metal deposition rate is
And depositing for 5-10 minutes to obtain a noble metal layer with the thickness of 10-20 nm.
Further, in the step 4, the HF-H2O2The concentration of HF in the solution is 0.9-1.8 mol/L, H2O2The concentration of the etching solution is 3 to 3.2mol/L, and the etching rate is 0.5 to 1.0 μm/min.
Further, in the step 4, the etched silicon wafer is soaked in a nitric acid solution or an iodine-potassium iodide solution to remove the deposited noble metal layer.
Further, in the step 5, dry oxidation is adopted, and specifically includes: heating to 900-3And/s, oxidizing for 20-60 minutes to form a silicon dioxide thin layer.
Further, in the step 5, wet oxidation is adopted, and specifically, the method includes: heating to 700-1000 ℃, introducing high-purity water vapor at the aeration speed of 1-5 cm3The oxidation time is 20-60 minutes, and the silicon oxide film with the thickness of 10-500 nm is obtainedAnd (3) a layer.
[ example 1 ]
Step 1, putting the silicon wafer into a solution containing 30% of H at 110 DEG C2O2And 96% H2SO4Soaking the silicon wafer in the mixed solution (in a volume ratio of 1:3) for 20 minutes, then soaking the silicon wafer in 0.5% HF solution for 30 minutes to remove the oxide on the surface of the silicon wafer, and then washing the silicon wafer with deionized water and drying the silicon wafer with nitrogen.
And 2, uniformly coating the photoresist SU-8 on the surface of the blow-dried silicon wafer by adopting a spin-coating method, wherein the thickness is 20 microns.
And 3, covering a pre-designed mask plate above the photoresist, irradiating the photoresist for 10 minutes by using ultraviolet light to denature the SU-8 photoresist, and then washing the surface photoresist by using a developing solution, wherein the pattern obtained on the surface of the silicon wafer is opposite to the pattern of the mask plate.
Step 4, depositing gold on the surface of the silicon wafer in a vacuum evaporation mode at the speed of
The evaporation time was 5 minutes, and a gold-plated layer having a thickness of 15nm was obtained.
Step 5, putting the silicon chip with gold plated surface into prepared HF-H2O2Soaking in the solution for several minutes to obtain micropores with corresponding depths. HF-H here2O2The concentration of HF in the solution may be 0.9mol/L, H2O2The solubility of (A) can be 3.2mol/L, the etching speed is about 0.6 mu m/min, and after 500 minutes of etching, a through hole array with the depth of 0.3mm can be obtained.
In order to ensure the etching uniformity and quality of the silicon microchannel plate, the solution is preferably stirred by a magnetic rotor at a rotation speed of 60 rpm during the etching process. And after etching, washing the silicon wafer by using deionized water, soaking the silicon wafer in an iodine-potassium iodide solution for 2 minutes to remove the deposited gold-plated layer, washing the silicon wafer by using the deionized water, and drying the silicon wafer by using nitrogen.
Step 6, oxidizing the blow-dried silicon microchannel plate at high temperature, adopting dry oxidation, putting the silicon wafer into a heating furnace, heating to 1000 ℃, introducing oxygen at the speed of 1cm3Ventilation time 20 minutes, thickness 100A thin layer of silicon oxide of about nm.
The prepared microchannel plate has a micropore structure with a trend of being large at the top and small at the bottom. The size of the micro-channel plate is 30mm in diameter, the shape of the micro-hole is circular, the diameter of the micro-hole is 0.5 mu m, the hole distance between adjacent micro-holes is 0.5 mu m, and the depth of the micro-hole is 0.3 mm.
[ example 2 ]
Step 1, putting the silicon wafer into a solution containing 30% of H and at 100 DEG C2O2And 96% H2SO4Soaking the silicon wafer in the mixed solution (in a volume ratio of 1:1) for 20 minutes, then soaking the silicon wafer in a 1.0% HF solution for 15 minutes to remove the oxide on the surface of the silicon wafer, and then washing the silicon wafer with deionized water and drying the silicon wafer with nitrogen.
Step 2, uniformly coating photoresist AZ-1350 with the thickness of 10 microns, 20 microns or 30 microns on the surface of the blow-dried silicon wafer by adopting a spin-coating method;
and 3, covering a pre-designed mask plate above the photoresist, irradiating the photoresist for 6 to 15 minutes by using ultraviolet light to denature the AZ-1350 photoresist, and then washing the surface photoresist by using a developing solution to obtain the same pattern on the surface of the silicon wafer as the pattern of the mask plate.
Step 4, depositing platinum on the surface of the silicon wafer in a vacuum electron beam sputtering mode at a speed of about
Evaporating for 10 minutes to obtain a platinum metal layer with the thickness of about 10-20 nm;
step 5, putting the silicon slice with platinum deposited on the surface into prepared HF-H2O2Soaking in the solution for several minutes to obtain micropores with corresponding depths.
HF-H here2O2The concentration of HF in the solution may be 1.8mol/L, H2O2The solubility of (A) may be 3.0mol/L, the etching rate may be about 1.0 μm/min, and after etching for 300 minutes, a via array of 0.3mm may be obtained.
In order to ensure the etching uniformity and quality of the silicon microchannel plate, a magnetic rotor is adopted to stir the solution in the etching process, and the rotating speed of the rotor is 60 revolutions per minute.
And after etching, washing the silicon wafer by using deionized water, soaking the silicon wafer in an iodine-potassium iodide solution for 2 minutes to remove the deposited platinum metal layer, washing the silicon wafer by using the deionized water, and drying the silicon wafer by using nitrogen.
Step 6, oxidizing the blow-dried silicon microchannel plate at high temperature, adopting wet oxidation, putting the silicon wafer into a heating furnace, heating to 800 ℃, introducing high-purity water vapor, and introducing 1cm of high-purity water vapor3And/s, ventilating for 20 minutes to obtain a thin silicon oxide layer of about 50 nm.
The prepared microchannel plate has a micropore structure with a trend of being large at the top and small at the bottom. The size of the micro-channel plate is 30mm in diameter, the shape of the micro-hole is circular, the size of the micro-hole is 1 mu m, the hole distance between adjacent micro-holes is 2 mu m, and the depth of the micro-hole is 0.3 mm.
In a preferred embodiment, the increase in photoresist thickness will affect the extension of the UV exposure time, the concentration of HF will affect the etch rate, and the increase in HF concentration will increase the etch rate, which can be selected and adjusted as desired.
Preferably, in the process for forming the noble metal layer, the thickness of the noble metal layer is 10-20nm, and as shown in fig. 4, the solution can pass through between the metal layers on the surface of the silicon wafer due to the existence of gaps. If the noble metal is deposited relatively thickly, the solution does not readily etch the wafer through the metal layer, and therefore the solution can only penetrate past the edges of the metal layer, resulting in non-uniform etching, as shown in FIG. 7. If the metal layer is too thin, the deposited metal is in the form of non-uniformly distributed islands and cannot form a nano-network structure, as shown in fig. 8.
Through tests, a secondary electron emission layer is formed on the surface of the micropore array of the traditional channel plate in an ALD (atomic layer deposition) coating mode, the secondary electron emission coefficient is about 3-4, and the secondary electron emission coefficient of the micropore array with the silicon dioxide thin layer prepared by the method is more than 3.2 and reaches a considerable level.
By combining the preparation process, the silicon microchannel plate with different micropore distributions and micropore sizes can be prepared by designing the mask, and the preparation requirements of different microchannel plates can be met; meanwhile, the preparation process of the original microchannel plate is simplified, the influence degree of manual operation on the process is reduced, the preparation process can be realized by adopting a machine, and the production efficiency and the yield are improved. Meanwhile, the micropores etched by the metal-assisted chemical etching method have the characteristics of large upper aperture and small lower aperture, and can control the electron emergent angle, so that the energy resolution is improved. The silicon dioxide thin layer which is completely covered and flat is directly obtained by a thermal oxidation method, the silicon dioxide thin layer has good bonding force with a silicon wafer, has insulating property and secondary electron emission property, and the step of depositing a secondary electron emission layer by an atomic layer on the original microchannel plate is omitted.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (10)
1. A method for preparing a silicon channel plate for a photomultiplier, comprising:
step 1, acid cleaning is carried out on a silicon wafer, and H is contained at 100-120 DEG C2O2And H2SO4Soaking the mixed solution in the solution for 10 to 20 minutes, wherein H in the mixed solution2O2And H2SO4The volume ratio of (A) to (B) is 1: 1-1: 3; then soaking in 0.5-1% HF solution for 10-30 min to remove surface oxide, then cleaning with deionized water and drying with nitrogen;
step 2, uniformly coating photoresist on the surface of the blow-dried silicon wafer, covering a mask plate above the photoresist, irradiating for several minutes by adopting ultraviolet light, washing the surface photoresist by using a developing solution, and obtaining a pattern which is the same as or opposite to the pattern of the mask plate on the surface of the silicon wafer;
step 3, performing precious metal deposition on the surface of the silicon wafer with the surface photoresist pattern to obtain a precious metal layer with the thickness of 10-20nm, wherein the precious metal layer forms a nano-mesh structure on the surface of the silicon wafer;
step 4, putting the silicon chip with the noble metal deposited on the surface into the prepared HF-H2O2Soaking in solution for several timesEtching the surface in minutes to obtain a micropore structure with corresponding depth; then taking out the etched silicon wafer, removing the deposited metal layer, cleaning with deionized water, and drying with nitrogen;
and 5, oxidizing the cleaned and dried silicon microchannel plate at high temperature to obtain a silicon oxide thin layer with the thickness of 10-500 nm.
2. The method for preparing a silicon channel plate for a photomultiplier according to claim 1, wherein the solubility of the HF solution in step 1 is 0.5 to 1%.
3. The method for preparing a silicon channel plate for a photomultiplier according to claim 1, wherein the step 2 is performed by coating a photoresist having a thickness of 10 to 20 μm, and irradiating the photoresist with ultraviolet light for 1 to 30 minutes after covering a mask over the photoresist.
4. The method as claimed in claim 1, wherein in step 3, the noble metal is one of gold, silver and platinum, and the metal deposition rate is PVD
And depositing for 5-10 minutes to obtain a noble metal layer with the thickness of 10-20 nm.
5. The method for producing a silicon channel plate for a photomultiplier according to claim 1, wherein in the step 4, the HF-H2O2The concentration of HF in the solution is 0.9-1.8 mol/L, H2O2The concentration of the etching solution is 3 to 3.2mol/L, and the etching rate is 0.5 to 1.0 μm/min.
6. The method of claim 1, wherein in step 4, the etched silicon wafer is immersed in a solution of nitric acid or iodine-potassium iodide to remove the deposited noble metal layer.
7. The method for preparing a silicon channel plate for a photomultiplier according to claim 1, wherein in the step 5, dry oxidation is used, and specifically comprises: heating to 900-3And/s, oxidizing for 20-60 minutes to form a silicon dioxide thin layer with the thickness of 10-500 nm.
8. The method for preparing a silicon channel plate for a photomultiplier according to claim 1, wherein in the step 5, wet oxidation is used, and specifically comprises: heating to 700-1000 ℃, introducing pure steam with the aeration speed of 1-5 cm3And/s, oxidizing for 20-60 minutes to obtain a silicon dioxide thin layer with the thickness of 10-500 nm.
9. A silicon channel plate prepared according to the method of any one of claims 1 to 8.
10. The silicon channel plate as claimed in claim 9, wherein the pore diameter of the micropores in the microporous structure tends to be large at the top and small at the bottom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010718865.7A CN111785597A (en) | 2020-07-23 | 2020-07-23 | Silicon channel plate for photomultiplier and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010718865.7A CN111785597A (en) | 2020-07-23 | 2020-07-23 | Silicon channel plate for photomultiplier and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111785597A true CN111785597A (en) | 2020-10-16 |
Family
ID=72764025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010718865.7A Pending CN111785597A (en) | 2020-07-23 | 2020-07-23 | Silicon channel plate for photomultiplier and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111785597A (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2090048A (en) * | 1980-12-19 | 1982-06-30 | Philips Electronic Associated | A channel plate electron multiplier structure having a large input multiplying area |
| US5569355A (en) * | 1995-01-11 | 1996-10-29 | Center For Advanced Fiberoptic Applications | Method for fabrication of microchannel electron multipliers |
| JPH10223162A (en) * | 1997-02-03 | 1998-08-21 | Hamamatsu Photonics Kk | Electron tube |
| US5997713A (en) * | 1997-05-08 | 1999-12-07 | Nanosciences Corporation | Silicon etching process for making microchannel plates |
| US6384519B1 (en) * | 1996-10-30 | 2002-05-07 | Nanosciences Corporation | Micro-dynode integrated electron multiplier |
| CN101022068A (en) * | 2007-03-29 | 2007-08-22 | 长春理工大学 | Producing method for continuous dynode in silicon micro channel |
| CN101054158A (en) * | 2007-03-09 | 2007-10-17 | 华东师范大学 | Self-separation manufacturing method for silicon micro-channel structure |
| US20100075445A1 (en) * | 2008-09-20 | 2010-03-25 | Arradiance, Inc. | Silicon Microchannel Plate Devices With Smooth Pores And Precise Dimensions |
| US20100248449A1 (en) * | 2009-03-31 | 2010-09-30 | Georgia Tech Research Corporation | Metal-Assisted Chemical Etching of Substrates |
| CN102956548A (en) * | 2012-11-09 | 2013-03-06 | 华中科技大学 | Electric field aided silicon through hole etching process |
| US20140264937A1 (en) * | 2013-03-15 | 2014-09-18 | Semprius, Inc. | Through-Silicon Vias and Interposers Formed by Metal-Catalyzed Wet Etching |
| CN104952628A (en) * | 2015-07-22 | 2015-09-30 | 齐齐哈尔大学 | High-performance electrochemical capacitor plate material and preparation method thereof |
| CN105668509A (en) * | 2016-01-28 | 2016-06-15 | 华东医药（杭州）基因科技有限公司 | Method for etching micron silicon through hole |
| CN107285618A (en) * | 2017-07-13 | 2017-10-24 | 广州宏晟光电科技有限公司 | A kind of solid light micro channel array panel and preparation method thereof |
-
2020
- 2020-07-23 CN CN202010718865.7A patent/CN111785597A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2090048A (en) * | 1980-12-19 | 1982-06-30 | Philips Electronic Associated | A channel plate electron multiplier structure having a large input multiplying area |
| US5569355A (en) * | 1995-01-11 | 1996-10-29 | Center For Advanced Fiberoptic Applications | Method for fabrication of microchannel electron multipliers |
| US6384519B1 (en) * | 1996-10-30 | 2002-05-07 | Nanosciences Corporation | Micro-dynode integrated electron multiplier |
| JPH10223162A (en) * | 1997-02-03 | 1998-08-21 | Hamamatsu Photonics Kk | Electron tube |
| US5997713A (en) * | 1997-05-08 | 1999-12-07 | Nanosciences Corporation | Silicon etching process for making microchannel plates |
| CN101054158A (en) * | 2007-03-09 | 2007-10-17 | 华东师范大学 | Self-separation manufacturing method for silicon micro-channel structure |
| CN101022068A (en) * | 2007-03-29 | 2007-08-22 | 长春理工大学 | Producing method for continuous dynode in silicon micro channel |
| US20100075445A1 (en) * | 2008-09-20 | 2010-03-25 | Arradiance, Inc. | Silicon Microchannel Plate Devices With Smooth Pores And Precise Dimensions |
| US20100248449A1 (en) * | 2009-03-31 | 2010-09-30 | Georgia Tech Research Corporation | Metal-Assisted Chemical Etching of Substrates |
| CN102956548A (en) * | 2012-11-09 | 2013-03-06 | 华中科技大学 | Electric field aided silicon through hole etching process |
| US20140264937A1 (en) * | 2013-03-15 | 2014-09-18 | Semprius, Inc. | Through-Silicon Vias and Interposers Formed by Metal-Catalyzed Wet Etching |
| CN104952628A (en) * | 2015-07-22 | 2015-09-30 | 齐齐哈尔大学 | High-performance electrochemical capacitor plate material and preparation method thereof |
| CN105668509A (en) * | 2016-01-28 | 2016-06-15 | 华东医药（杭州）基因科技有限公司 | Method for etching micron silicon through hole |
| CN107285618A (en) * | 2017-07-13 | 2017-10-24 | 广州宏晟光电科技有限公司 | A kind of solid light micro channel array panel and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 向嵘等: "Si基体二维深通道微孔列阵刻蚀技术", 《微纳电子技术》 * |
| 张洋等: "微通道板用玻璃材料的研究进展", 《材料导报》 * |
| 牛丽红等: "硅微通道板电子倍增器的研制", 《光学技术》 * |
| 郭艳玲等: "Si-MCP连续打拿极的制备", 《长春理工大学学报(自然科学版)》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100521061C (en) | Field emitting display with carbon nano tube emitting polar and its making method | |
| US8987038B2 (en) | Method for forming solar cell with selective emitters | |
| JP2002117801A (en) | Multi-channel plate and its manufacturing method | |
| JP2010098232A (en) | Solar battery and method of manufacturing solar battery | |
| JPH11121438A (en) | Plasma etching method | |
| CN110010431B (en) | Preparation method of microchannel plate with ion feedback prevention film | |
| WO2011156560A1 (en) | Solar cell silicon wafer process | |
| JP2009088098A (en) | Method of patterning dielectric film | |
| JP2008282912A (en) | Manufacturing method for solar battery element | |
| JP2006156646A (en) | Solar cell manufacturing method | |
| CN111785597A (en) | Silicon channel plate for photomultiplier and preparation method thereof | |
| CN1011272B (en) | Iron-nickel alloy shadom mask for color cathode-ray tube | |
| KR20130021365A (en) | Method for doping a semiconductor substrate and solar cell having two-stage doping | |
| CN117239008A (en) | Photovoltaic cell side surface insulation method | |
| Ehara et al. | Planar Interconnection Technology for LSI Fabrication Utilizing Lift‐off Process | |
| CN114334582B (en) | Manufacturing method of field emission device structure and field emission device structure | |
| CN116288641A (en) | Electrochemical etching device and etching method thereof | |
| JP2012094739A (en) | Deposition method and method of manufacturing semiconductor device | |
| JP3226250B2 (en) | Transfer mask | |
| US7635625B2 (en) | Method for manufacturing image sensor | |
| JP2006040863A (en) | Field emission display equipped with carbon nanotube emitter, and its manufacturing method | |
| US20020102766A1 (en) | Solar cell and method of manufacturing same | |
| CN114252465B (en) | Preparation method of etched pit semiconductor sample for microscope | |
| JP2005116783A (en) | Manufacturing method of solar cell and solar cell manufactured thereby | |
| JP3330844B2 (en) | Electrode plate for color display device and color display device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201016 |