CN215418100U - Microchannel plate - Google Patents
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- CN215418100U CN215418100U CN202121109628.7U CN202121109628U CN215418100U CN 215418100 U CN215418100 U CN 215418100U CN 202121109628 U CN202121109628 U CN 202121109628U CN 215418100 U CN215418100 U CN 215418100U
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Abstract
The disclosure relates to a microchannel plate, and belongs to the technical field of photoelectricity. The microchannel plate provided by the utility model comprises a microchannel plate body and a high-resistance film arranged on the inner wall of the microchannel plate body; the high-resistance film has a laminated structure composed of 1-M thin film layers, each thin film layer including a first material layer made by atomic layer deposition and a second material layer deposited on the first material layer by atomic layer deposition; the inner wall of the microchannel plate body is provided with a first material layer of a 1 st thin film layer, and the first material layer of the ith thin film layer is deposited on a second material layer of an i-1 th thin film layer; the thickness of the high-resistance film is within a preset thickness value range; wherein the first material is any one of a specified insulating material and a specified conducting material, and the second material is the other one of the specified insulating material and the specified conducting material; i 2, … M. The problem that its accessory substance of prior art is poisonous and harmful gas can be solved in this application.
Description
Technical Field
The present disclosure relates to the field of photovoltaic technologies, and in particular, to a microchannel plate.
Background
The traditional microchannel plate is prepared from lead-containing glass with higher secondary electron emission coefficient, and after complex process treatment, the roughness of the inner wall of the channel is deteriorated, so that the problems of gain reduction, noise increase and the like are caused, and the improvement of the performance of the traditional microchannel plate is limited. The atomic layer deposition technology has the capability of depositing a film in the high-aspect-ratio channel, and the performance of the microchannel plate can be improved by preparing the functional layer on the inner wall of the microchannel plate through the atomic layer deposition process.
At present, the mature commercial functional layer films of the microchannel plate prepared by adopting atomic layer deposition are W/Al2O3 and Mo/Al2O3, and the resistance of the functional layer films can meet the use requirement of the microchannel plate by adjusting the proportion of W/Mo and Al2O 3. It has several disadvantages: firstly, tungsten hexafluoride (WF6) and molybdenum hexafluoride (MoF6) have strong and extremely toxic gaseous precursors and are used in the ALD preparation of W, Mo thin films, the chemical properties of the precursors are unstable and difficult to store, and huge potential safety hazards exist in the preparation of the thin films; secondly, in the composite film of W/Al2O3 and Mo/Al2O3 prepared by ALD, residual impurities are still contained, wherein nearly 16.5% of F element can be detected, and the residual F, C element in the conductive layer can influence various performances of the MCP to a certain extent, particularly in terms of gain and service life; thirdly, byproducts such as AlF3, HF, CHFx and the like are generated in the ALD reaction process, and the fluorides corrode equipment and seriously damage the equipment; fourthly, when the ALD is used for preparing the W film, the growth rate of the W film is as high as
While the Al2O3 film prepared by ALD has a growth rate of
The growth rates of the two are greatly differentThis can result in the W film particles not being uniformly doped when coated with Al2O3 particles, and ultimately affecting the performance of the conductive layer and thus the MCP performance.
In order to solve the problem that when the existing microchannel plate uses W/Al2O3 or Mo/Al2O3, a toxic precursor source WF6 or MoF6 needs to be used, and the byproduct is toxic and harmful HF. The utility model provides a microchannel plate and a high-resistance film prepared by laminating conductive materials Ir, IrO2, Ru and RuO2 and an insulating material on the inner wall of the microchannel plate.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a microchannel plate, which is used for solving the problems that when W/Al2O3 or Mo/Al2O3 is used, a toxic precursor source WF6 or MoF6 is needed, and a byproduct of the toxic precursor source WF or MoF6 is toxic and harmful gas HF. The technical scheme provided by the utility model is as follows:
according to a first aspect of the embodiments of the present disclosure, a microchannel plate is provided, which includes a microchannel plate body and a high resistance film disposed on an inner wall of the microchannel plate body; the high-resistance film has a laminated structure composed of 1-M thin film layers, each thin film layer including a first material layer made by atomic layer deposition and a second material layer deposited on the first material layer by atomic layer deposition; the inner wall of the microchannel plate body is provided with a first material layer of a 1 st thin film layer, and the first material layer of the ith thin film layer is deposited on a second material layer of an i-1 th thin film layer; the thickness of the high-resistance film is within a preset thickness value range;
wherein the first material is any one of a specified insulating material and a specified conducting material, and the second material is the other one of the specified insulating material and the specified conducting material; i 2, … M.
In one embodiment, the first material layer is obtained by cycling the first material by atomic layer deposition n, and the second material layer is obtained by cycling the second material by atomic layer deposition m; n is a natural number, and m is a natural number.
In one embodiment, the first material is a designated insulating material and the second material is the designated conductive material.
In one embodiment, n is any integer between 5 and 15, and m is any integer between 1 and 5.
In one embodiment, the deposition temperature for atomic layer deposition is any temperature between 100 ℃ and 400 ℃.
In one embodiment, the specified conductive material includes, but is not limited to, Ir, IrO2、Ru、RuO2One kind of (1).
In one embodiment, the specified insulating material includes, but is not limited to, YSZ, HfO2、Ta2O5、Pr2O3One kind of (1).
In one embodiment, the predetermined thickness range is 100-200 nm.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 is a flow chart of a method for manufacturing a microchannel plate according to the present invention;
fig. 2 is a schematic structural diagram of a microchannel plate according to the present invention.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the exemplary embodiments below are not intended to represent all implementations consistent with the present disclosure. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the present disclosure, as detailed in the appended claims.
Fig. 1 is a flow chart of a method for manufacturing a microchannel plate according to the present invention, as shown in fig. 1, the method includes the following steps:
s1: preparing an Nth first material layer on the inner wall of the microchannel plate body through atomic layer deposition;
wherein the initial value of N is 1.
S2: preparing an Nth second material layer on the Nth first material layer through atomic layer deposition to obtain an Nth thin film layer consisting of the Nth first material layer and the Nth second material layer;
in this embodiment, the first material is any one of a specific insulating material and a specific conductive material, and the second material is the other one of the specific insulating material and the specific conductive material.
Preferably, the atomic layer deposition in steps S1 and S2 is performed at any temperature between 100 ℃ and 400 ℃.
S3: and judging whether the total thickness of the current 1 st to N film layers reaches a preset thickness value range, if so, executing the step S6, otherwise, executing the step S4.
S4: and manufacturing an (N + 1) th first material layer on the Nth second material layer by atomic layer deposition.
S5: let N be N +1, and then return to execution of step S2.
S6: a microchannel plate including a high resistance film was obtained.
The high-resistance film has a laminated structure consisting of 1 st to N th film layers, and the thickness of the high-resistance film is within a preset thickness value range.
In this embodiment, an insulating material and a conductive material are laminated in a certain ratio to form a high-resistance film of a laminated structure, a first material layer and a second material layer with a certain thickness ratio are formed by deposition in each large cycle, and when the thickness of the high-resistance film after the deposition does not reach the standard, the next large cycle is continued by returning to step S1 until the thickness of the high-resistance film reaches the standard. The microchannel plate prepared by the preparation method has stable performance and long service life when used for a long time and at high temperature, and the problems in the prior art are solved because the preparation process does not relate to toxic and harmful substances.
In an alternative embodiment, in the method shown in fig. 1, the method for forming the first material layer by atomic layer deposition is: and n, circulating the first material through atomic layer deposition to obtain a first material layer. The method for manufacturing the second material layer by atomic layer deposition comprises the following steps: and circulating the second material through atomic layer deposition m to obtain a second material layer. Wherein n is a natural number, and m is a natural number. Namely: in this example, n cycles of the first material are deposited in each major cycle: and m-cycle second material, and according to the thickness requirement, obtaining the high-resistance film with the laminated structure and the thickness meeting the requirement through multiple rounds of large cycles.
Preferably, the first material is a specified insulating material, and the second material is the specified conductive material.
Preferably, the value of n is any integer between 5 and 15, and the value of m is any integer between 1 and 5.
Preferably, the specified conductive material includes, but is not limited to, Ir, IrO2、Ru、RuO2One kind of (1).
Preferably, the specified insulating material includes, but is not limited to, YSZ, HfO2、Ta2O5、Pr2O3One kind of (1).
Preferably, the preset thickness range is 100-200 nm.
Corresponding to the preparation method of the microchannel plate provided by the embodiment, the embodiment also provides a microchannel plate, which includes a microchannel plate body 1 and a high-resistance thin film 2 disposed on the inner wall of the microchannel plate body, as shown in fig. 2, the high-resistance thin film 2 has a laminated structure composed of 1 st to M thin film layers 21, and each thin film layer 21 includes a first material layer 211 made by atomic layer deposition and a second material layer 212 deposited on the first material layer by atomic layer deposition; the inner wall of the microchannel plate body 1 is provided with a first material layer 211 of a 1 st thin film layer 21, and the first material layer 211 of an ith thin film layer is deposited on a second material layer 212 of an ith-1 th thin film layer; the thickness of the high-resistance film 2 is within a preset thickness value range; wherein the first material is any one of a specified insulating material and a specified conducting material, and the second material is the other one of the specified insulating material and the specified conducting material; i 2, … M.
In one embodiment, the first material layer 211 is formed by cycling the first material by atomic layer deposition n, and the second material layer 212 is formed by cycling the second material by atomic layer deposition m; n is a natural number, and m is a natural number.
In one embodiment, the first material is a designated insulating material and the second material is the designated conductive material.
In one embodiment, n is any integer between 5 and 15, and m is any integer between 1 and 5.
In one embodiment, the deposition temperature for atomic layer deposition is any temperature between 100 ℃ and 400 ℃.
In one embodiment, the specified conductive material includes, but is not limited to, Ir, IrO2、Ru、RuO2One kind of (1).
In one embodiment, the specified insulating material includes, but is not limited to, YSZ, HfO2、Ta2O5、Pr2O3One kind of (1).
In one embodiment, the predetermined thickness range is 100-200 nm.
The following describes the technical scheme of the method embodiment of the present invention in detail by using 6 specific embodiments.
Example 1
Placing the microchannel plate in RCA standard cleaning solution SC-2 (HCl: H)2O2:H2O1: 1:5), ultrasonic cleaning at 85 ℃ for 15 minutes, and placing in an HF solution (HF: H) at room temperature2O1: 50), placing the cleaned microchannel plate into an atomic layer deposition chamber, and vacuumizing to 10-1Pa, and heating the deposition chamber and the microchannel plate to 250 deg.C to start YSZ deposition, wherein ZrO is present2:Y2O31, zirconium source is tetradimethylaminobenzyl (TDMAZr), yttrium source is tris (diisopropylacetamide) yttrium Y: (II)iPr-amd)3The TDMAZr source temperature is set to 75 ℃, Y: (iPr-amd)3The source temperature was set at 135 ℃. ZrO (ZrO)2The deposition process is TDMAZr/N2/H2O/N2＝(0.3s/15s/0.15s/15s)，Y2O3The deposition process is Y: (iPr-amd)3/N2/H2O/N2After 10 cycles, 1 Ir deposition was carried out with iridium triacetylacetone (Ir (acac))3),Ir(acac)3The source temperature is set to 150 ℃, and the Ir deposition process is Ir (acac)3/N2/O2/N2(0.2s/15s/0.5s/30 s). In this embodiment, 10 YSZ deposition cycles and 1 Ir deposition cycle are 1 major cycle, the deposition is stopped after 200 major cycles, the deposition chamber is cooled to room temperature, the deposition chamber is opened, the microchannel plate on which the Ir-doped YSZ film is deposited is taken out, and the high-resistance film has a thickness of 135nm as measured by an ellipsometer.
Example 2
Placing the microchannel plate in RCA standard cleaning solution SC-2 (HCl: H)2O2:H2O1: 1:5), ultrasonic cleaning at 85 ℃ for 15 minutes, and placing in an HF solution (HF: H) at room temperature2O1: 50), placing the cleaned microchannel plate into an atomic layer deposition chamber, and vacuumizing to 10-1Pa, and heating the deposition chamber and the microchannel plate to 200 deg.C to start YSZ deposition, wherein ZrO is present2:Y2O37:1, zirconium source is zirconium tetra-methylaminochloride (TDMAZr), yttrium source is tris (diisopropylacetamide) yttrium Y: (iii)iPr-amd)3The TDMAZr source temperature is set to 75 ℃, Y: (iPr-amd)3The source temperature was set at 135 ℃. ZrO (ZrO)2The deposition process is TDMAZr/N2/H2O/N2＝(0.03s/15s/1s/15s)，Y2O3The deposition process is Y: (iPr-amd)3/N2/H2O/N2After 10 cycles (0.03s/15s/1s/30s), IrO was performed 1 time2Depositing, wherein the iridium source is iridium triacetylacetonate (Ir (acac)3),Ir(acac)3The source temperature is set to 150 ℃, and the Ir deposition process is Ir (acac)3/N2/O3/N2(0.3s/15s/2s/30 s). In this example, 10 YSZ deposition cycles and 1 IrO2The deposition is 1 major cycle, the major cycle is carried out for 150 times, the deposition is stopped, after the deposition chamber is cooled to the room temperature, the deposition chamber is opened, the microchannel plate for depositing the Ir-doped YSZ film is taken out, and the thickness of the high-resistance film is measured to be 103nm by an ellipsometer.
Example 3
Placing the microchannel plate in RCA standard cleaning solution SC-2 (HCl: H)2O2:H2O1: 1:5), ultrasonic cleaning at 85 ℃ for 15 minutes, and placing in an HF solution (HF: H) at room temperature2O1: 50), placing the cleaned microchannel plate into an atomic layer deposition chamber, and vacuumizing to 10-1Pa, and the deposition chamber and microchannel plate were heated to 300 deg.C and HfO was started2Depositing, wherein the hafnium source is tetradimethylamino hafnium (TDMAHf), the TDMAHf source temperature is set to 80 ℃, and the deposition process is TDMAHf/N2/O2/N2After 8 cycles, 1 Ir deposition was carried out with an iridium source of triacetylacetone (Ir (acac))3),Ir(acac)3The source temperature is set to 150 ℃, and the Ir deposition process is Ir (acac)3/N2/O2/N2(0.2s/15s/0.5s/30 s). In this example, HfO was measured 8 times2After deposition cycle and 1 time of Ir deposition, namely 1 major cycle, the deposition is stopped after the major cycle is carried out for 250 times, after the deposition chamber is cooled to room temperature, the deposition chamber is opened, and deposited Ir-doped HfO is taken out2The thickness of the high-resistance film measured by an ellipsometer is 180 nm.
Example 4
Placing the microchannel plate in RCA standard cleaning solution SC-2 (HCl: H)2O2:H2O ═ 1:1:5), ultrasonically cleaned at 85 ℃ for 15 minutes, and then placed in an HF solution (HF: H) at room temperature2O1: 50), placing the microchannel plate into an atomic layer deposition chamber, and vacuumizing to 10-1Pa, and the deposition chamber and the microchannel plate were heated to 350 ℃ and Ta was started2O5Depositing, wherein the tantalum source is tetradimethylaminotantalum (TDMATa), the temperature of the TDMATa source is set to be 70 ℃, and the deposition process is TDMATa/N2/H2O/N2After 8 cycles (0.03/15/0.03/15), 1 Ru deposition was carried out, wherein the Ru source was ruthenium dicyclopentenyl (RuCp)2) The source temperature was set at 80 ℃ and the deposition process was RuCp2/N2/O2/N2(0.5s/10s/1s/10 s). In this example, Ta is 12 times2O5After deposition cycle and 3 times of Ru deposition, the cycle is 1 major cycle, and the major cycle is stopped after 130 times of the major cycleDepositing, opening the deposition chamber after the chamber is cooled to room temperature, taking out and depositing Ru doped Ta2O5The thickness of the high-resistance film measured by an ellipsometer is 155 nm.
Example 5
Placing the microchannel plate in RCA standard cleaning solution SC-2 (HCl: H)2O2:H2O ═ 1:1:5), ultrasonically cleaned at 85 ℃ for 15 minutes, and then placed in an HF solution (HF: H) at room temperature2O1: 50), placing the microchannel plate into an atomic layer deposition chamber, and vacuumizing to 10-1Pa, and the deposition chamber and the microchannel plate were heated to 300 ℃ and Ta was started2O5Depositing, wherein the tantalum source is tetradimethylaminotantalum (TDMATa), the temperature of the TDMATa source is set to be 70 ℃, and the deposition process is TDMATa/N2/H2O/N2After 15 cycles (0.03/15/0.03/15), 5 RuO runs were performed2Deposition wherein the Ru source is ruthenium dicyclopentenyl (RuCp)2) The source temperature was set at 80 ℃ and the deposition process was RuCp2/N2/O3/N2(1s/10s/1s/10 s). In this example, Ta 15 times2O5After deposition cycle and 5 RuO runs2The deposition is 1 major cycle, the deposition is stopped after the major cycle is performed for 100 times, the deposition chamber is opened after the temperature of the deposition chamber is reduced to the room temperature, and the RuO deposited is taken out2Doped with Ta2O5The thickness of the high-resistance film is 160nm measured by an ellipsometer.
Example 6
Placing the microchannel plate in RCA standard cleaning solution SC-2 (HCl: H)2O2:H2O ═ 1:1:5), ultrasonically cleaned at 85 ℃ for 15 minutes, and then placed in an HF solution (HF: H) at room temperature2O1: 50), placing the microchannel plate into an atomic layer deposition chamber, and vacuumizing to 10-1Pa, and heating the deposition chamber and the microchannel plate to 300 ℃ to perform Pr2O3Deposition, wherein the Pr source is triethylcyclopentenyl (Pr (C)5H4Et)3)，Pr(C5H4 Et)3The source temperature is set to 130 ℃, and the deposition process is Pr (C)5H4Et)3/N2/H2O/N2After 12 cycles, 4 Ir depositions with iridium as the source of triacetylacetone (Ir (acac))3),Ir(acac)3The source temperature is set to 150 ℃, and the Ir deposition process is Ir (acac)3/N2/O2/N2(0.2s/15s/0.5s/30 s). In this example, Pr was 12 times2O3The deposition cycle and 4 times of Ir deposition are 1 major cycle, the deposition is stopped after the major cycle is carried out for 80 times, the deposition chamber is opened after the deposition chamber is cooled to the room temperature, the microchannel plate for depositing the Ir-doped YSZ film is taken out, and the thickness of the high-resistance film is 110nm measured by an ellipsometer.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
It will be understood that the present disclosure is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the present disclosure is limited only by the appended claims.
Claims (8)
1. A microchannel plate is characterized by comprising a microchannel plate body and a high-resistance film arranged on the inner wall of the microchannel plate body; the high-resistance film has a laminated structure composed of 1-M thin film layers, each thin film layer including a first material layer made by atomic layer deposition and a second material layer deposited on the first material layer by atomic layer deposition; the inner wall of the microchannel plate body is provided with a first material layer of a 1 st thin film layer, and the first material layer of the ith thin film layer is deposited on a second material layer of an i-1 th thin film layer; the thickness of the high-resistance film is within a preset thickness value range;
wherein the first material is any one of a specified insulating material and a specified conducting material, and the second material is the other one of the specified insulating material and the specified conducting material; i 2, … M.
2. The microchannel plate of claim 1, wherein the first material layer is obtained by atomic layer deposition n-cycling the first material and the second material layer is obtained by atomic layer deposition m-cycling the second material; n is a natural number, and m is a natural number.
3. The microchannel plate of claim 1 or 2, wherein the first material is a specified insulating material and the second material is the specified conductive material.
4. The microchannel plate of claim 2, wherein n is any integer between 5 and 15 and m is any integer between 1 and 5.
5. The microchannel plate of claim 1, wherein the atomic layer deposition temperature is any temperature between 100 ℃ and 400 ℃.
6. The microchannel plate of claim 1, wherein the specified conductive material includes, but is not limited to, Ir, IrO2、Ru、RuO2One kind of (1).
7. The microchannel plate of claim 1, wherein the specified insulating material includes, but is not limited to, YSZ, HfO2、Ta2O5、Pr2O3One kind of (1).
8. The microchannel plate of claim 1, wherein the predetermined thickness is in a range of 100 nm and 200 nm.
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