CN106637116B - A kind of simple preparation method of secondary film - Google Patents
A kind of simple preparation method of secondary film Download PDFInfo
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- CN106637116B CN106637116B CN201611166493.1A CN201611166493A CN106637116B CN 106637116 B CN106637116 B CN 106637116B CN 201611166493 A CN201611166493 A CN 201611166493A CN 106637116 B CN106637116 B CN 106637116B
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- sputtering
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- simple preparation
- film
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0089—Reactive sputtering in metallic mode
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
Abstract
The present invention discloses a kind of simple preparation method of secondary film, belongs to the preparation technical field of secondary cathode material.Using pure metallic silver/aluminium/titanium as matrix, pure metal magnesium serves as sputtering source substance, using straight argon as working gas, pure oxygen is reaction gas, under conditions of using resistance heating to matrix, by DC reactive magnetron sputtering technique, MgO film is prepared on silver/aluminium/Titanium base, secondary emission coefficient δ is up to 4.88.Preparing MgO film cathode using the method has many advantages, such as that preparation process is simple, film thickness is controllable, ingredient is uniform, good crystallinity, secondary emission coefficient are high, emitting performance is stable and resistance to electron bombardment.It is expected to be applied to the fields such as photomultiplier tube, cesium-beam atomic clock, magnetron.
Description
Technical field
The present invention relates to a kind of simple preparation methods of secondary film, and in particular to one kind is with silver/aluminium/titanium
Belong to the preparation method for being substrate using MgO film of the magnetron sputtering technique deposition with excellent secondary electron emissions performance, belongs to
The preparation technical field of secondary cathode material.
Background technique
With the development of electronic information technology, secondary electron emissions material plays more and more important in vacuum electron device
Effect, such as photomultiplier tube, cesium-beam atomic clock, magnetron are military, Domestic vacuum electronic device.Relative to other secondary emissions
Material, MgO film have excellent secondary emission performance, under the conditions of lower acceleration voltage (200-600eV), secondary emission
Coefficient can maintain 3 or more, meet the actual operation requirements of a variety of vacuum electron devices.Currently, preparing the side of magnesia film
There are many methods, such as traditional thermal activation treatment, sol-gel method, magnetron sputtering deposition, electron beam evaporation plating.Method for manufacturing thin film
And technique has a direct impact the pattern of MgO film, structure, surface roughness and film thickness, and then influences its secondary emission
Performance.For example, the secondary emission coefficient of amorphous state MgO film is lower, and the crystalline substance of acquisition is deposited under certain substrate temperature conditions
State MgO film then secondary emission coefficient with higher；Relatively thin MgO film is easy to be penetrated into substrate by electron beam, and compared with
Thick MgO film is unfavorable for the secondary electron evolution surface of film internal excitation again and is unfavorable for electronics in the benefit of cathode surface
It fills, thus secondary emission coefficient is poor, and only the moderate MgO film of thickness just has comparatively ideal secondary electron emissions system
Number.The traditional preparation methods of MgO film are thermal activation treatment Ag-Mg alloy, and the method can not achieve the accurate control of film thickness
System, the secondary emission stability of the cathode emitter of preparation is poor, and the service life is shorter.The MgO film ingredient of sol-gel method preparation
Structure is complicated, MgO layer it is second-rate, influence secondary emission coefficient.Using MgO target, magnetic control splashes on metal or glass substrate
Direct precipitation MgO film is penetrated, MgO is usually amorphous state, and secondary emission coefficient is undesirable；And in sputtering process heat substrate or
Subsequent heat treatment needs higher temperature to make MgO that crystalline state transformation occur, and temperature is excessively high is easy to make film separation and fail, at
Film uniformity is poor.
Summary of the invention
Not easy to control, the secondary hair for traditional bianry alloy thermal activation treatment preparation MgO second emission cathode film thickness
The deficiencies of coefficient is unstable is penetrated, the present invention uses magnetron sputtering technique, and using magnesium metal as sputtering source substance, being passed through argon gas is work
Make gas, oxygen is reaction gas, is heated using resistance heating manner to metallic substrates, d.c. sputtering magnesium target, in gold
Belong to reactive deposition MgO film on substrate.By adjusting base reservoir temperature and oxygen argon gas stream flow ratio, successfully prepare film thickness it is controllable,
Ingredient uniformly, the good and stable MgO film of good crystallinity, secondary emission coefficient.The present invention provides a kind of preparation process letters
List, film thickness is controllable, secondary emission coefficient is high, emitting performance is stable and the preparation side of the cathode film material of resistance to electron bombardment
Method.
The preparation method of secondary MgO film provided by the present invention is accomplished by the following way:
A. clear with acetone and alcohol ultrasonic wave later through surface mill, polishing using pure metallic silver, aluminium, titanium as substrate material
It washes.The sputtering source substance of thin-film material is served as with pure metal magnesium；
B. it will be fixed on sample stage through the resulting substrate of step A, sample stage is put into magnetic control sputtering device Sample Room, substrate
In the once purged feeding rotatable metallic substrate of Sample Room.
C. confined reaction room is vacuumized, metallic substrates is heated；
D. it is evacuated to a certain degree to magnetic control sputtering device reaction chamber back end vacuum degree and metallic substrates in room temperature or is heated to one
Under the conditions of determining temperature, it is passed through the high pure oxygen and argon mixture gas of certain flow ratio, is gone up in reaction chamber vacuum degree to reaction pressure
When start pre-sputtering, pre-sputtering processing starts the sputtering of direct current magnesium target, the resulting magnesium of argon ion bombardment target and chamber after a certain period of time
Oxygen reaction in room, finally deposits in substrate surface and obtains MgO film.
In above method step A, the substrate material metallic silver, aluminium, titanium and magnesium metal target purity be
99.99%.
In above method step A, the surface mill, polishing process are as follows: respectively through 2000#, 3000#, 5000#SiC sand paper
Ag/Al/Ti substrate sample of polishing is conducive to the adventitious deposit of magnetron sputtering substance to obtain smooth planar surface.After through third
Ketone and alcohol distinguish ultrasonic cleaning 5min, after dried in vacuum oven, to remove sample surfaces adsorbing contaminant.
In above method step B, the cleaning is under an argon atmosphere by radio-frequency power supply in 50~100W power condition
The argon ion aura of lower generation cleans 300s.
In above method step C, the vacuum pumping method vacuumizes for molecular pump, and reaction chamber back end vacuum degree is 5 × 10-4
~8 × 10-4Pa, the heating method of metallic substrates are resistance-type heating, and the rate of heat addition is 20 DEG C/min.
In above method step D, the base reservoir temperature be room temperature sputtering the sample later period in vacuum tube furnace through 400~
600 DEG C, carry out 10~30min under the conditions of 10~20Pa high pure oxygen and be activated.
In above method step D, the base reservoir temperature is set between 200~500 DEG C, and sputtering source gas high purity oxygen gas is pure
Degree is 99.999%, and high-purity argon gas purity is 99.999%.
In above method step D, the gas flow ratio O2/ Ar is 1/90~10/90 (flux unit: sccm), reaction
Pressure control is between 0.8~1.0Pa.
In above method step D, the pre-sputtering is under conditions of flapper closure, using sputtering 5 under 50~200W power
~10min, to remove target material surface adsorbate and impurity.
In above method step D, the magnetically controlled DC sputtering power is 50~200W.
The present invention finally obtains high (the maximum emission ratio δ of secondary emission coefficientmax=4.88), resistance to electron bombardment is (primary
Electron energy be 400eV constant bombardment 72 hours after maximum secondary emission ratio δ be still greater than 3.0), secondary emission performance it is stable
MgO film cathode.Film surface microstructure is in flake shaped particle, and particle is uniformly distributed, size about 50nm~1.5 μm, section
For obvious column crystal.
Detailed description of the invention
The present invention has 9 attached drawings, is now respectively described below:
Fig. 1 is the surface SEM pattern of the made MgO film of embodiment 1；
Fig. 2 is the section SEM pattern of the made MgO film of embodiment 1；
Fig. 3 is the surface SEM pattern of the made MgO film of embodiment 2；
Fig. 4 is the section SEM pattern of the made MgO film of embodiment 2；
Fig. 5 is primary electron energy-secondary emission coefficient relational graph of embodiment 1；
Fig. 6 is primary electron energy-secondary emission coefficient relational graph of embodiment 2；
Fig. 7 is primary electron energy-secondary emission coefficient relational graph of embodiment 3；
Fig. 8 is primary electron energy-secondary emission coefficient relational graph of embodiment 4；
Fig. 9 is secondary hair of the embodiment 3 at the primary electron constant bombardment MgO film surface that electron energy is 400eV
Penetrate life curve figure.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Metallic silver/aluminium/titanium sheet is after the pretreatment of 2000#, 3000#, 5000#SiC sand paper in following embodiment, through acetone and
Alcohol distinguishes ultrasonic cleaning 5min, and drying is stand-by.The size of following substrate material are as follows: 10mm × 10mm × 0.2mm.
Embodiment 1
By grinding and polishing light and the good metallic silver substrate of ultrasonic cleaning is put into magnetron sputtering Sample Room, is fixed on high temperature gummed tape
In metallic substrates.300s is cleaned by the argon ion aura that radio-frequency power supply generates under 50W power condition under an argon atmosphere.It
Sample is sent into reaction chamber and is vacuumized afterwards, is reduced to 5 × 10 to back end vacuum degree-4Pa starts to be passed through O2/ Ar mixed gas, O2/ Ar gas
Body flow-rate ratio is 1/90.It is 1Pa to reaction chamber vacuum degree, keeps flapper closure below magnesium target, start direct current pre-sputtering, sputters function
Rate is 150W, time 300s.Baffle, formal d.c. sputtering Mg, time 60min are opened later.Substrate does not heat, and is room temperature 25
℃.Atmosphere is filled to vacuum chamber after sputtering, takes out sample.By vacuum tube furnace under 400 DEG C, 20Pa high purity oxygen gas atmosphere
Further activation is dropped to furnace temperature but to 60 DEG C or less taking-up samples.Primary electron energy-secondary emission coefficient figure is shown in Fig. 5, and one
Secondary electron energy is that maximum secondary emission ratio δ is still greater than 3 after 400eV constant bombardment 72 hours.
Embodiment 2
By grinding and polishing light and the good metallic silver substrate of ultrasonic cleaning is put into magnetron sputtering Sample Room, is fixed on high temperature gummed tape
In metallic substrates.300s is cleaned by the argon ion aura that radio-frequency power supply generates under 50W power condition under an argon atmosphere.It
Sample is sent into reaction chamber and is vacuumized afterwards, and is heated to 400 DEG C to substrate.5 × 10 are reduced to back end vacuum degree-4Pa starts to be passed through
O2/ Ar mixed gas, O2/ Ar gas flow ratio is 1/90.It is 1Pa to reaction chamber vacuum degree, keeps flapper closure below magnesium target,
Start direct current pre-sputtering, sputtering power 150W, time 300s.Baffle, formal d.c. sputtering Mg are opened later, and the time is
60min.Atmosphere is filled to vacuum chamber after base reservoir temperature is cooled to 60 DEG C or less after sputtering, takes out sample.Primary electron energy
Amount-secondary emission coefficient figure is shown in Fig. 6, and primary electron energy is maximum secondary emission ratio δ after 400eV constant bombardment 72 hours
It is still greater than 3.
Embodiment 3
By grinding and polishing light and the good metal aluminium base of ultrasonic cleaning is put into magnetron sputtering Sample Room, is fixed on high temperature gummed tape
In metallic substrates.300s is cleaned by the argon ion aura that radio-frequency power supply generates under 50W power condition under an argon atmosphere.It
Sample is sent into reaction chamber and is vacuumized afterwards, and is heated to 400 DEG C to substrate.5 × 10 are reduced to back end vacuum degree-4Pa starts to be passed through
O2/ Ar mixed gas, O2/ Ar gas flow ratio is 1/90.It is 1Pa to reaction chamber vacuum degree, keeps flapper closure below magnesium target,
Start direct current pre-sputtering, sputtering power 150W, time 300s.Baffle, formal d.c. sputtering Mg are opened later, and the time is
60min.Atmosphere is filled to vacuum chamber after base reservoir temperature is cooled to 60 DEG C or less after sputtering, takes out sample.Primary electron energy
Amount-secondary emission coefficient figure is shown in Fig. 7, and primary electron energy is maximum secondary emission ratio δ after 400eV constant bombardment 72 hours
It is still greater than 3.
Embodiment 4
By grinding and polishing light and the good Titanium substrate of ultrasonic cleaning is put into magnetron sputtering Sample Room, is fixed on high temperature gummed tape
In metallic substrates.300s is cleaned by the argon ion aura that radio-frequency power supply generates under 50W power condition under an argon atmosphere.It
Sample is sent into reaction chamber and is vacuumized afterwards, and is heated to 400 DEG C to substrate.5 × 10 are reduced to back end vacuum degree-4Pa starts to be passed through
O2/ Ar mixed gas, O2/ Ar gas flow ratio is 1/90.It is 1Pa to reaction chamber vacuum degree, keeps flapper closure below magnesium target,
Start direct current pre-sputtering, sputtering power 150W, time 300s.Baffle, formal d.c. sputtering Mg are opened later, and the time is
60min.Atmosphere is filled to vacuum chamber after base reservoir temperature is cooled to 60 DEG C or less after sputtering, takes out sample.Primary electron energy
Amount-secondary emission coefficient figure is shown in Fig. 8, and primary electron energy is maximum secondary emission ratio δ after 400eV constant bombardment 72 hours
It is still greater than 3.
The foregoing is merely main scheme for implementing said method of the invention, however the present invention is not limited to this, all not depart from this
Any modification, equivalent replacement or improvement for being made in the case where invention core etc., should be included within the scope of the present invention.
Claims (6)
1. a kind of simple preparation method of secondary film, which is characterized in that prepared essentially according to the following steps:
A. using pure metallic silver, aluminium, titanium as substrate material, through surface grinding, polishing, acetone and alcohol ultrasonic cleaning are used later；
The sputtering source substance of thin-film material is served as with pure metal magnesium；
B. will be fixed on sample stage through the resulting substrate of step A, sample stage is put into magnetic control sputtering device Sample Room, substrate into
Specimen chamber is sent into rotatable metallic substrate after pre-sputter cleaning；
C. confined reaction room is vacuumized, metallic substrates is heated；
D. it is evacuated to a certain degree and under the conditions of metallic substrates are heated to certain temperature to magnetic control sputtering device reaction chamber back end vacuum degree,
It is passed through the high purity oxygen gas of certain flow ratio and the mixed gas of argon gas, is started when reaction chamber vacuum degree is gone up to reaction pressure pre-
Sputtering, pre-sputtering processing start magnesium target d.c. sputtering, the oxygen in the resulting magnesium of argon ion bombardment target and chamber after a certain period of time
Solid/liquid/gas reactions finally deposit in substrate surface and obtain MgO film；
In step D, the base reservoir temperature is set in 200~500 DEG C；The gas flow ratio O2/ Ar is 1/90~10/90, reaction
Pressure control is between 0.8~1.0 Pa；Sputtering source gas high purity oxygen gas purity is 99.999%, and high-purity argon gas purity is
99.999%。
2. a kind of simple preparation method of secondary film according to claim 1, which is characterized in that in step A, institute
The purity for stating substrate material metallic silver, aluminium, titanium and magnesium metal target is 99.99%；Surface mill, polishing process are as follows: pass through respectively
2000#, 3000#, 5000# SiC sand paper polishing Ag/Al/Ti substrate sample are conducive to magnetic control and splash to obtain smooth planar surface
Penetrate the adventitious deposit of substance；After through acetone and alcohol distinguish 5 min of ultrasonic cleaning, after dried in vacuum oven, with
Remove sample surfaces adsorbing contaminant.
3. a kind of simple preparation method of secondary film according to claim 1, which is characterized in that in step B, institute
Stating cleaning is the argon ion aura cleaning generated under 50~100 W power conditions by radio-frequency power supply under an argon atmosphere
300s。
4. a kind of simple preparation method of secondary film according to claim 1, which is characterized in that in step C, institute
It states vacuum pumping method to vacuumize for molecular pump, reaction chamber back end vacuum degree is 5 × 10-4~8 × 10-4Pa, metallic substrates add
Hot mode is resistance-type heating, and the rate of heat addition is 20 DEG C/min.
5. a kind of simple preparation method of secondary film according to claim 1, which is characterized in that in step D, institute
Pre-sputtering is stated under conditions of flapper closure, using 5~10 min are sputtered under 50~200 W power, to remove target material surface suction
Addendum and impurity.
6. a kind of simple preparation method of secondary film according to claim 1, which is characterized in that in step D, institute
Stating magnetically controlled DC sputtering power is 50~200 W.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611166493.1A CN106637116B (en) | 2016-12-16 | 2016-12-16 | A kind of simple preparation method of secondary film |
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| CN201611166493.1A CN106637116B (en) | 2016-12-16 | 2016-12-16 | A kind of simple preparation method of secondary film |
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| CN108085651B (en) * | 2017-12-14 | 2020-09-25 | 北京工业大学 | Electron beam bombardment resistant secondary electron emission composite film and preparation method thereof |
| CN113471034B (en) * | 2021-05-29 | 2023-11-14 | 南京三乐集团有限公司 | Preparation method of magnesium oxide secondary emitter |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103243305A (en) * | 2013-04-22 | 2013-08-14 | 兰州空间技术物理研究所 | Secondary electron emission film preparation method |
| CN103726026A (en) * | 2014-01-10 | 2014-04-16 | 中国科学院长春光学精密机械与物理研究所 | Method of preparing thin film by magnetron sputtering of oxide ceramic target |
| CN103924205A (en) * | 2014-04-28 | 2014-07-16 | 中国人民解放军国防科学技术大学 | High temperature-resistant low-infrared emittance composite coating and preparation method thereof |
| CN104593742A (en) * | 2015-01-20 | 2015-05-06 | 清华大学深圳研究生院 | Equipment and method for preparing oxide film with biaxial texture |
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2016
- 2016-12-16 CN CN201611166493.1A patent/CN106637116B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103243305A (en) * | 2013-04-22 | 2013-08-14 | 兰州空间技术物理研究所 | Secondary electron emission film preparation method |
| CN103726026A (en) * | 2014-01-10 | 2014-04-16 | 中国科学院长春光学精密机械与物理研究所 | Method of preparing thin film by magnetron sputtering of oxide ceramic target |
| CN103924205A (en) * | 2014-04-28 | 2014-07-16 | 中国人民解放军国防科学技术大学 | High temperature-resistant low-infrared emittance composite coating and preparation method thereof |
| CN104593742A (en) * | 2015-01-20 | 2015-05-06 | 清华大学深圳研究生院 | Equipment and method for preparing oxide film with biaxial texture |
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