CN108374151A - Metal and Zinc oxide doped magnesia secondary film and preparation method thereof - Google Patents
Metal and Zinc oxide doped magnesia secondary film and preparation method thereof Download PDFInfo
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- CN108374151A CN108374151A CN201810183512.4A CN201810183512A CN108374151A CN 108374151 A CN108374151 A CN 108374151A CN 201810183512 A CN201810183512 A CN 201810183512A CN 108374151 A CN108374151 A CN 108374151A
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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
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- 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
- C23C14/3464—Sputtering using more than one target
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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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
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- 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
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- C23C14/081—Oxides of aluminium, magnesium or beryllium
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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Abstract
A kind of metal and Zinc oxide doped magnesia secondary film and preparation method thereof, the Zinc oxide doped magnesia film layer and metal-doped magnesia film layer from top to bottom set gradually including substrate and in substrate, simple doping metals material or codope metal material and zinc oxide in metal-doped magnesia film layer, the atomicity percentage composition of metal is 6% 30% in the metal-doped magnesia film layer of simple doping metals material, the atomicity percentage composition of metal is 5% 25% in the metal-doped magnesia film layer of codope metal material and zinc oxide, the atomicity percentage composition of zinc is not higher than 5%；The size of Mg Zn O compound crystal grain formed in Zinc oxide doped magnesia film layer is 8nm 30nm, the atomicity percentage composition of zinc is 0.2% 8%, it is prepared using sputtering method, secondary electron yield can be effectively improved, enhance the stability of electron emission.
Description
Technical field
The invention belongs to photoelectron materials and device arts, and in particular to a kind of metal and Zinc oxide doped magnesia
Secondary film and preparation method thereof can be applied to the devices such as electron multiplier, photomultiplier.
Background technology
Secondary electron yield is high, resistance to charged particle bombardment performance is good and preparation process because having for magnesia film
The advantages that simple, has been widely used in image intensifier, electron multiplier, photoelectricity times currently as secondary electron emission material
Increase in the electronic devices such as pipe and crossed field amplifier.In order to make electronic device obtain longer service life, it to be used for therein two
Secondary electronic emission material must be resistant to the long-time bombardment of larger beam current density electron beam, therefore the magnesia film prepared is thick
Degree needs to reach tens nanometers even 100 nanometers or more.But since magnesia is insulating materials, thicker magnesia film
It will produce surface charging phenomenon under beam bombardment, this can make its secondary rapid decay, to influence film two
The stability of secondary electron emission.This problem limits application of the magnesia film in high-gain, long-life electron device.
It, can be in magnesia in order to avoid thicker magnesia film generates surface charging phenomenon under electron-beam sustainer bombardment
Certain proportion good conductivity is adulterated in film, the metal material that chemical property is stablized is answered with the magnesia for forming doping metals material
Close film.Due to the doping of metal material, there is the metallic particles of dispersion in laminated film, the electric conductivity of film is changed
It is kind, make it remain to effectively surface be avoided to charge when film layer is thicker, thus can be resistance to improve film by increasing film thickness
By the performance compared with the bombardment for a long time of large beam density electron beam.But experimental study shows metal-doped magnesia laminated film
There are still a degree of secondaries to decay under the beam bombardment of larger line, the reason is that in addition to having failed
It totally disappeared in addition to the charging phenomenon of surface, there is also magnesia caused by beam bombardment to decompose etching.It is mixed in magnesia film
The electric conductivity of film no doubt can be improved in metal material, but since the secondary electron yield of metal material is very low, and
Metallic particles is also easy to produce reunion in high temperature deposition thin-film process, increases the surface roughness of film, therefore excessively high metal is mixed
The secondary electron yield of film can be significantly reduced by entering amount, and the amount for mixing metal in magnesia film is caused to be restricted.It is few
Amount it is metal-doped so that the electric conductivity of magnesia film is obtained a degree of improvement, when metal-doped magnesia film by compared with
, can be to avoid surface charging phenomenon when the beam bombardment of low beam current density generates secondary, but work as it by higher
The constant bombardment of beam current density electron beam, when carrying out secondary, the electric conductivity of film still is apparent not enough, and causes film surface
The positive charge of Rapid Accumulation is difficult to eliminate in time.In addition, magnesia will produce point under the beam bombardment of higher beam current density
Solution etching, destroys the crystal structure of magnesia and changes the surface topography of film, secondary decaying occur.Therefore,
The metal-doped magnesia laminated film secondary performance (property especially under higher beam current density beam bombardment
Can) also need to be further improved.
Invention content
It is an object of the invention to the problems in for the above-mentioned prior art, provide a kind of metal and Zinc oxide doped oxidation
Magnesium secondary film and preparation method thereof, can effectively improve secondary electron yield, enhance the stabilization of electron emission
Property.
To achieve the goals above, metal of the invention is used with Zinc oxide doped magnesia secondary film
Technical solution is：The Zinc oxide doped magnesia film layer and metal from top to bottom set gradually including substrate and in substrate is mixed
Miscellaneous magnesia film layer, simple doping metals material or codope metal material and oxygen in the metal-doped magnesia film layer
Change zinc, wherein the atomicity percentage composition of metal is 6%- in the metal-doped magnesia film layer of simple doping metals material
30%, the atomicity percentage composition of metal is 5%- in the metal-doped magnesia film layer of codope metal material and zinc oxide
25%, the atomicity percentage composition of zinc is not higher than 5%；Mg-Zn-O formed in the Zinc oxide doped magnesia film layer
The size of compound crystal grain is 8nm-30nm, and the atomicity percentage composition of zinc is 0.2%-8%.
The metal material adulterated in the metal-doped magnesia film layer is gold, silver or platinum.
The thickness of metal-doped magnesia film layer is 40nm-300nm, and the thickness of Zinc oxide doped magnesia film layer is
10nm-40nm。
Metal buffer layer made of gold or silver is equipped between the substrate and metal-doped magnesia film layer.
The thickness of the metal buffer layer is 5nm-30nm.
The preparation method of metal of the present invention and Zinc oxide doped magnesia secondary film, includes the following steps：
1) splash-proofing sputtering metal target and magnesium target or magnesium oxide target are sputtered, the gold of simple doping metals material is deposited in substrate
Belong to doping magnesia film layer；Alternatively, splash-proofing sputtering metal target and magnesium target either magnesium oxide target and zinc target or zinc oxide target are sputtered,
The metal-doped magnesia film layer of codope metal material and zinc oxide is deposited in substrate；
2) in the metal-doped magnesia film layer of simple doping metals material or codope metal material and zinc oxide,
Magnesium target either magnesium oxide target and zinc target or zinc oxide target are sputtered, Zinc oxide doped magnesia film layer is deposited.
Step 1) and step 2) are in metal-doped magnesia film layer, the codope metal material for depositing simple doping metals material
When metal-doped magnesia film layer and the Zinc oxide doped magnesia film layer of material and zinc oxide, the temperature of substrate is maintained at 300
℃-550℃。
The method for manufacturing thin film sputters gold target or silver-colored target, metal buffer layer is deposited in substrate, then in gold first
Belong to and is sequentially depositing metal-doped magnesia film layer and Zinc oxide doped magnesia film layer on buffer layer.
For the metal buffer layer in deposition, the temperature of substrate is maintained at 10 DEG C -200 DEG C.
Step 1) and step 2) are plated in the deposition of magnesium by the way of sputtering magnesium target and zinc target and zinc oxide in membrane cavity
It is passed through argon gas and oxygen, the flow-rate ratio of argon gas and oxygen is (8:1)-(2:1)；Using the side of sputtering magnesium oxide target and zinc oxide target
It when formula deposition of magnesium and zinc oxide, plates and is passed through argon gas and oxygen in membrane cavity, the flow-rate ratio of argon gas and oxygen is (15:1)-(9:
1)。
The air pressure plated when deposition film in membrane cavity is maintained at 0.1Pa-0.8Pa.
Compared with prior art, the present invention has following advantageous effect：Existing metal-doped magnesia secondary electron
Transmitting film is mainly made of the thin pure zirconia magnesium film layer of metal-doped magnesia film layer and surface layer, metal-doped oxygen of the invention
Change simple doping metals material or codope metal material and zinc oxide, top layer in magnesium film layer and Zinc oxide doped magnesia is set
Film layer calculates the electronic structure of analysis magnesia and Zinc oxide doped magnesia using first principle pseudopotential method, the results showed that,
Compared with magnesia, the surface work function and energy gap of Zinc oxide doped magnesia are reduced, such as the atomicity hundred of zinc
The average surface work function and energy gap for the Zinc oxide doped magnesia that point content is 1% respectively reduced about 0.5eV and
0.39eV.In addition, experimental measurements are shown, suitable zinc oxide is mixed again in metal-doped magnesia film, moreover it is possible into
One step improves the electric conductivity of film.The surface layer of film of the present invention is Zinc oxide doped magnesia film layer, in this layer due to oxidation
The doping of zinc can form Mg-Zn-O compounds, and the compound has lower surface work function compared with magnesia, thus in film
There is secondary electron in more that can be escaped from film surface to form secondary, improves film secondary system
Number.The Mg-Zn-O compounds formed in film surface layer have lower energy gap compared with magnesia, and pass through control
The size of Mg-Zn-O compound crystal grain, can improve the electrons transport property of superficial film, be conducive in lasting secondary of film
So that the electronics from substrate is moved to film surface to neutralize the positive charge of accumulation in electron emission process, preferably inhibits film
Surface charge effects keep the stability of film secondary.For by metal with aoxidize zinc co-doped magnesium oxide films layer,
The metal of Zinc oxide doped magnesia film layer composition and the zinc co-doped magnesia film of oxidation, since the incorporation of zinc oxide can carry
The electric conductivity of high film, therefore under the premise of ensureing that film has certain electric conductivity, the appropriate incorporation for reducing metal can be kept away
Exempt from the metallic particles agglomeration occurred in membrane-film preparation process, makes film that there is lower surface roughness, it is thin to make
Film obtains high secondary electron yield.Metal has very high secondary with zinc co-doped magnesia film is aoxidized
Coefficient, therefore it is in electronic device in application, in the case where secondary electron yield is met the requirements, it is appropriate to reduce incidence
Electron energy can reduce electron beam and be etched to the decomposition of magnesia, and the secondary to slow down film decays, and extends electricity
The service life of sub- device.For these reasons, metal of the invention and the zinc co-doped magnesia secondary of oxidation are thin
Film has high secondary performance.
Description of the drawings
The membrane structure schematic diagram of metal buffer layer is not arranged by Fig. 1 present invention；
The membrane structure schematic diagram of metal buffer layer is arranged in Fig. 2 present invention；
The curve comparison figure that Fig. 3 film secondary electron yield δ change with incident electron energy Ep；
The curve comparison figure that Fig. 4 film secondary electron yield δ decay with beam bombardment time t.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment the present invention is described in further detail.
In order to further increase existing metal-doped magnesia film (usually by metal-doped magnesia film layer and surface layer
Thin pure zirconia magnesium film layer composition) electronic induction secondary performance, the method for use be mix again in the film it is suitable
The zinc oxide of amount is to form metal and aoxidize zinc co-doped magnesia film, and the film is mainly by metal-doped magnesia film layer
The thin Zinc oxide doped magnesia film layer in (or metal and the zinc co-doped magnesium oxide films layer of oxidation) and surface layer is constituted, using sputtering method
Successively by each film deposition in substrate.Since to form surface work function relatively low for the doping of zinc oxide in film superficial oxidation magnesium
Mg-Zn-O compounds, thus have secondary electrons in more that can be escaped from film surface to form secondary electron in film
Transmitting, to improve film secondary electron yield.The Mg-Zn-O compounds formed in film surface layer also have lower
Energy gap, and the size by controlling Mg-Zn-O compound crystal grain, can improve the electrons transport property of superficial film,
Be conducive to make the electronics from substrate move in and accumulate to film surface during film lasting secondary
Positive charge, preferably inhibit film surface charge effects, keep film secondary stability.For by metal with
It is thin to aoxidize zinc co-doped magnesium oxide films layer, the metal of Zinc oxide doped magnesia film layer composition and the zinc co-doped magnesia of oxidation
Film, since the incorporation of zinc oxide can improve the electric conductivity of film, under the premise of ensureing that film has certain electric conductivity
The incorporation that metal can suitably be reduced makes film to avoid the metallic particles agglomeration occurred in membrane-film preparation process
With lower surface roughness, to make film obtain higher secondary electron yield.Since metal and zinc oxide are total
Adulterating magnesia film has very high secondary electron yield, therefore in application, secondary in electronic device
Coefficient can suitably reduce incident electron energy in the case of meeting the requirements, and be carved to the decomposition of magnesia to reduce electron beam
Erosion, the secondary to slow down film decay, and extend the service life of electronic device.In conclusion the present invention is from principle
On can improve the emitting performance of secondary electron.
Embodiment 1
Referring to Fig. 1, when metal buffer layer 4 is not arranged by the present invention, by positioned at 1 surface of substrate gold doping magnesia film layer and
Zinc oxide doped magnesia film layer 3 composition in top layer, each film layer are all made of sputtering method preparation, specifically include following steps：
1) deposition gold adulterates magnesia film layer on the base 1 by the way of radio-frequency sputtering magnesium target and d.c. sputtering gold target,
In deposition process, the temperature of substrate 1 is made to be maintained at 300 DEG C, argon gas and oxygen, argon gas and oxygen are passed through simultaneously in plating membrane cavity
Flow-rate ratio be 5:1, total gas pressure is 0.2Pa in plated film cavity, and the thickness of the gold doping magnesia film layer of deposition is 100nm, gold
It is 30% to adulterate atomicity percentage composition golden in magnesia film layer.
2) by the way of radio-frequency sputtering magnesium target and zinc target, the deposited oxide zinc doping oxidation in gold doping magnesia film layer
Magnesium film layer 3, in deposition process, base reservoir temperature is maintained at 500 DEG C, plates in membrane cavity and is passed through argon gas and oxygen, argon gas and oxygen simultaneously
The flow-rate ratio of gas is 4:1, total gas pressure is 0.4Pa in plated film cavity, and the thickness of the Zinc oxide doped magnesia film layer 3 of deposition is
40nm, the atomicity percentage composition of zinc are that the average-size of 8%, Mg-Zn-O compound crystal grain is about 25nm.
Embodiment 2
Referring to Fig. 1, when metal buffer layer 4 is not arranged by the present invention, by the gold and the zinc co-doped oxygen of oxidation positioned at 1 surface of substrate
Change magnesium film layer and Zinc oxide doped magnesia film layer 3 composition in top layer, each film layer is all made of sputtering method preparation；
Specifically include following steps：
1) by the way of radio-frequency sputtering magnesium oxide target and zinc oxide target and d.c. sputtering gold target on the base 1 deposition gold with
Zinc co-doped magnesium oxide films layer is aoxidized, in deposition process, base reservoir temperature is maintained at 400 DEG C, plates in membrane cavity and is passed through argon gas simultaneously
And oxygen, the flow-rate ratio of argon gas and oxygen is 10:1, total gas pressure is 0.25Pa in plated film cavity, and the gold of deposition is co-doped with zinc oxide
The thickness of miscellaneous magnesia film layer is 50nm, and golden atomicity percentage composition is 15%, and the atomicity percentage composition of zinc is 6%.
2) it by the way of radio-frequency sputtering magnesium oxide target and zinc oxide target, in gold and aoxidizes on zinc co-doped magnesium oxide films layer
Deposited oxide zinc doping magnesium oxide films layer 3, in deposition process, base reservoir temperature is maintained at 520 DEG C, plates in membrane cavity and is passed through argon simultaneously
The flow-rate ratio of gas and oxygen, argon gas and oxygen is 12:1, total gas pressure is 0.3Pa, the Zinc oxide doped oxygen of deposition in plated film cavity
The thickness for changing magnesium film layer 3 is 20nm, and the atomicity percentage composition of zinc is about for the average-size of 4%, Mg-Zn-O compound crystal grain
15nm。
Embodiment 3
Referring to Fig. 2, the present invention increases the membrane structure of metal buffer layer 4, by golden buffer layer, the gold positioned at 1 surface of substrate
Magnesia film layer and Zinc oxide doped magnesia film layer 3 composition in top layer are adulterated, each film layer is all made of sputtering method preparation.
Preparation method specifically includes following steps：
1) by the way of d.c. sputtering gold target, golden buffer layer, in deposition process, base reservoir temperature are deposited on the base 1
100 DEG C are maintained at, plates and is passed through argon gas in membrane cavity, total gas pressure is 0.5Pa in plated film cavity, and the thickness of the golden buffer layer of deposition is
10nm。
2) gold doping magnesium oxide films are deposited on golden buffer layer by the way of radio-frequency sputtering magnesium target and d.c. sputtering gold target
Layer, in deposition process, base reservoir temperature is maintained at 450 DEG C, plates in membrane cavity and is passed through argon gas and oxygen, the stream of argon gas and oxygen simultaneously
Amount is than being 4:1, total gas pressure is 0.15Pa in plated film cavity, and the thickness of the gold doping magnesia film layer of deposition is 200nm, gold doping
Golden atomicity percentage composition is 20% in magnesia film layer.
3) by the way of radio-frequency sputtering magnesium target and zinc target, the deposited oxide zinc doping oxidation in gold doping magnesia film layer
Magnesium film layer 3, in deposition process, base reservoir temperature is maintained at 450 DEG C, plates in membrane cavity and is passed through argon gas and oxygen, argon gas and oxygen simultaneously
The flow-rate ratio of gas is 6:1, total gas pressure is 0.6Pa in plated film cavity, and the thickness of the Zinc oxide doped magnesia film layer 3 of deposition is
16nm, the atomicity percentage composition of zinc are that the average-size of 2%, Mg-Zn-O compound crystal grain is about 8nm.
Embodiment 4
Referring to Fig. 2, the present invention increases the membrane structure of metal buffer layer 4, by silver-colored buffer layer, the silver positioned at 1 surface of substrate
It is formed with the Zinc oxide doped magnesia film layer 3 in top layer with zinc co-doped magnesium oxide films layer is aoxidized, each film layer, which is all made of, splashes
Method preparation is penetrated, preparation method specifically includes following steps：
1) by the way of d.c. sputtering silver target, deposition of silver buffer layer on the base 1, in deposition process, base reservoir temperature
20 DEG C are maintained at, plates and is passed through argon gas in membrane cavity, total gas pressure is 0.7Pa in plated film cavity, and the thickness of the silver-colored buffer layer of deposition is
8nm。
2) deposition of silver is co-doped with zinc oxide on silver-colored buffer layer by the way of radio-frequency sputtering magnesium target and d.c. sputtering silver target
Miscellaneous magnesia film layer, in deposition process, base reservoir temperature is maintained at 400 DEG C, plates in membrane cavity and is passed through argon gas and oxygen, argon gas simultaneously
Flow-rate ratio with oxygen is 7:1, total gas pressure is 0.5Pa in plated film cavity, the silver of deposition with aoxidize zinc co-doped magnesium oxide films layer
Thickness be 150nm, silver-colored atomicity percentage composition is 16%, and the atomicity percentage composition of zinc is 3%.
3) by the way of radio-frequency sputtering magnesium target and zinc target, in silver and deposited oxide on the zinc co-doped magnesium oxide films layer of oxidation
Zinc doping magnesia film layer 3, in deposition process, base reservoir temperature is maintained at 550 DEG C, plates in membrane cavity and is passed through argon gas and oxygen simultaneously
The flow-rate ratio of gas, argon gas and oxygen is 5:1, total gas pressure is 0.4Pa, the Zinc oxide doped magnesia film layer of deposition in plated film cavity
3 thickness is 18nm, and the atomicity percentage composition of zinc is that the average-size of 3%, Mg-Zn-O compound crystal grain is about 10nm.
Embodiment 5
Referring to Fig. 2, the present invention increases the membrane structure of metal buffer layer 4, by golden buffer layer, the platinum positioned at 1 surface of substrate
It is formed with the Zinc oxide doped magnesia film layer 3 in top layer with zinc co-doped magnesium oxide films layer is aoxidized, each film layer, which is all made of, splashes
Method preparation is penetrated, preparation method specifically includes following steps：
1) by the way of d.c. sputtering gold target, golden buffer layer, in deposition process, base reservoir temperature are deposited on the base 1
30 DEG C are maintained at, plates and is passed through argon gas in membrane cavity, total gas pressure is 0.7Pa in plated film cavity, and the thickness of the golden buffer layer of deposition is
8nm。
2) platinum and oxidation are deposited on golden buffer layer by the way of radio-frequency sputtering magnesium target and zinc target and d.c. sputtering platinum target
Zinc co-doped magnesia film layer, in deposition process, base reservoir temperature is maintained at 420 DEG C, plates in membrane cavity and is passed through argon gas and oxygen simultaneously
The flow-rate ratio of gas, argon gas and oxygen is 7:1, total gas pressure is 0.5Pa in plated film cavity, the platinum of deposition with aoxidize zinc co-doped oxidation
The thickness of magnesium film layer is 150nm, and the atomicity percentage composition of platinum is 10%, and the atomicity percentage composition of zinc is 7%.
3) by the way of radio-frequency sputtering magnesium target and zinc target, in platinum and deposited oxide on the zinc co-doped magnesium oxide films layer of oxidation
Zinc doping magnesia film layer 3, in deposition process, base reservoir temperature is maintained at 510 DEG C, plates in membrane cavity and is passed through argon gas and oxygen simultaneously
The flow-rate ratio of gas, argon gas and oxygen is 5:1, total gas pressure is 0.35Pa, the Zinc oxide doped magnesium oxide films of deposition in plated film cavity
The thickness of layer 3 is 25nm, and the atomicity percentage composition of zinc is that the average-size of 4%, Mg-Zn-O compound crystal grain is about 15nm.
Referring to Fig. 3, comparison is made using disclosed by the invention and document report secondary method for manufacturing thin film
Standby gold is aoxidized with the zinc co-doped magnesia film of oxidation (the atomicity percentage composition of zinc is 1% in film surface layer), gold doping
The curve that the secondary electron yield δ of magnesium film changes with incident electron energy Ep, it can be seen that gold and oxidation are zinc co-doped
Magnesia film has higher secondary electron yield, especially under the bombardment of the incident electron of higher-energy.
Referring to Fig. 4, comparison is made using disclosed by the invention and document report secondary method for manufacturing thin film
Standby gold is aoxidized with the zinc co-doped magnesia film of oxidation (the atomicity percentage composition of zinc is 1% in film surface layer), gold doping
The magnesium film curve that secondary electron yield δ decays with beam bombardment time t under the bombardment of identical energy electron beam, energy
Enough find out, with the growth of incident electron bombardment time, gold has higher two always with zinc co-doped magnesia film is aoxidized
Secondary electron emission coefficiency.Compared with gold adulterates magnesia film, due to gold with the zinc co-doped magnesia film of oxidation with higher
Secondary electron yield works, and positive charge, but the secondary electron hair of the film can be generated with faster speed on its surface
Decaying is penetrated therefore not accelerate.This result shows that, gold has better secondary electricity with zinc co-doped magnesia film is aoxidized
Son transmitting fade performance.
By embodiments above and related description, it can be seen that compared with existing secondary electron emission material, this hair
Bright metal is with the zinc co-doped magnesia film of oxidation due to having lower surface work function and preferable electrons transport property etc. former
Cause makes it that there is higher secondary electron yield and better secondary electron to send out under compared with large beam density beam bombardment
Penetrate fade performance.
Although the present invention is described in detail in above-mentioned specific implementation mode, not use it to limit the present invention.
The present invention is not limited to said program, as long as basic conception according to the invention, using metal and the zinc co-doped oxidation of oxidation
Magnesium complex thin film structure and corresponding method for manufacturing thin film, for improving the electronic induction secondary of magnesia film
Performance, achieve the purpose that film is made to obtain higher secondary electron yield and launch stability, belong to the present invention
Protection domain.
Claims (9)
1. a kind of metal and Zinc oxide doped magnesia secondary film, it is characterised in that：Including substrate (1) and
The Zinc oxide doped magnesia film layer (3) from top to bottom set gradually in substrate (1) and metal-doped magnesia film layer (2)；
Simple doping metals material or codope metal material and zinc oxide in the metal-doped magnesia film layer (2),
Wherein, the atomicity percentage composition of metal is 6%-30% in the metal-doped magnesia film layer (2) of simple doping metals material,
The atomicity percentage composition of metal is 5%- in the metal-doped magnesia film layer (2) of codope metal material and zinc oxide
25%, the atomicity percentage composition of zinc is not higher than 5%；Mg- formed in the Zinc oxide doped magnesia film layer (3)
The size of Zn-O compound crystal grain is 8nm-30nm, and the atomicity percentage composition of zinc is 0.2%-8%.
2. metal according to claim 1 and Zinc oxide doped magnesia secondary film, it is characterised in that：Institute
It is gold, silver or platinum to state the metal material adulterated in metal-doped magnesia film layer (2).
3. metal according to claim 1 and Zinc oxide doped magnesia secondary film, it is characterised in that：Gold
The thickness for belonging to doping magnesia film layer (2) is 40nm-300nm, and the thickness of Zinc oxide doped magnesia film layer (3) is 10nm-
40nm。
4. metal according to claim 1 and Zinc oxide doped magnesia secondary film, it is characterised in that：Institute
Metal buffer layer (4) made of gold or silver is equipped between the substrate (1) and metal-doped magnesia film layer (2) stated.
5. metal according to claim 4 and Zinc oxide doped magnesia secondary film, it is characterised in that：Institute
The thickness for stating metal buffer layer (4) is 5nm-30nm.
6. one kind metal as described in any one claim in claim 1-3 is sent out with Zinc oxide doped magnesia secondary electron
Penetrate the preparation method of film, which is characterized in that include the following steps：
1) splash-proofing sputtering metal target and magnesium target or magnesium oxide target are sputtered, the gold of simple doping metals material is deposited in substrate (1)
Belong to doping magnesia film layer (2)；Alternatively, splash-proofing sputtering metal target and sputtering magnesium target either magnesium oxide target and zinc target or zinc oxide
Target deposits the metal-doped magnesia film layer (2) of codope metal material and zinc oxide in substrate (1)；
2) on the metal-doped magnesia film layer (2) of simple doping metals material or codope metal material and zinc oxide,
Magnesium target either magnesium oxide target and zinc target or zinc oxide target are sputtered, Zinc oxide doped magnesia film layer (3) is deposited.
7. preparation method according to claim 6, it is characterised in that：Step 1) and step 2) are depositing simple doping metals
The metal-doped magnesia film layer (2) of material, the metal-doped magnesia film layer (2) of codope metal material and zinc oxide and
When Zinc oxide doped magnesia film layer (3), the temperature of the substrate (1) is maintained at 300 DEG C -550 DEG C.
8. preparation method according to claim 7, it is characterised in that：Gold target or silver-colored target are sputtered first, are sunk in substrate (1)
Product goes out metal buffer layer (4), then metal-doped magnesia film layer (2) and doped zinc oxide are sequentially depositing on metal buffer layer (4)
Miscellaneous magnesia film layer (3), for the metal buffer layer (4) in deposition, the temperature of substrate (1) is maintained at 10 DEG C -200 DEG C.
9. according to the preparation method described in any one claim in claim 6-8, it is characterised in that：Using sputtering magnesium target
It when with the mode deposition of magnesium and zinc oxide of zinc target, plates and is passed through argon gas and oxygen in membrane cavity, the flow-rate ratio of argon gas and oxygen is
(8:1)-(2:1)；The deposition of magnesium and when zinc oxide by the way of sputtering magnesium oxide target and zinc oxide target, plates and is passed through in membrane cavity
The flow-rate ratio of argon gas and oxygen, argon gas and oxygen is (15:1)-(9:1)；The air pressure plated when deposition film in membrane cavity is maintained at
0.1Pa-0.8Pa。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789730A (en) * | 2014-01-16 | 2014-05-14 | 西安交通大学 | Preparation method of secondary-electron emission thin film |
| CN104599923A (en) * | 2015-01-12 | 2015-05-06 | 西安交通大学 | MgO/ ZnO composite medium protecting film and preparation method thereof |
| CN106637079A (en) * | 2016-12-02 | 2017-05-10 | 西安交通大学 | Buffer layer of secondary electron emission film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789730A (en) * | 2014-01-16 | 2014-05-14 | 西安交通大学 | Preparation method of secondary-electron emission thin film |
| CN104599923A (en) * | 2015-01-12 | 2015-05-06 | 西安交通大学 | MgO/ ZnO composite medium protecting film and preparation method thereof |
| CN106637079A (en) * | 2016-12-02 | 2017-05-10 | 西安交通大学 | Buffer layer of secondary electron emission film and preparation method thereof |
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| ANDRÉ BIKOWSKI等: "Influence of the deposition temperature on electronic transport and structural properties of radio frequency magnetron-sputtered Zn1-xMgxO:Al and ZnO:Al films", 《JOURNAL OF MATERIALS RESEARCH》 * |
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