CN103789730A - Preparation method of secondary-electron emission thin film - Google Patents
Preparation method of secondary-electron emission thin film Download PDFInfo
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- CN103789730A CN103789730A CN201410020285.5A CN201410020285A CN103789730A CN 103789730 A CN103789730 A CN 103789730A CN 201410020285 A CN201410020285 A CN 201410020285A CN 103789730 A CN103789730 A CN 103789730A
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Abstract
The invention discloses a preparation method of a secondary-electron emission thin film. The preparation method comprises the following steps: (1) depositing a buffer layer on a metal substrate; (2) depositing a magnesium oxide and metal mixed layer on the buffer layer by sputtering a magnesium target/magnesium oxide target and sputtering other metal targets; (3) depositing a surface on the magnesium oxide and metal mixed layer. In the step (2), the two targets are used for respectively depositing magnesium oxide and other metals, the sputtering power, the sputtering time, the flow rates of working gas and reactant gas and the temperature of the substrate are individually controlled so as to prepare the magnesium oxide and metal mixed layer with proper magnesium oxide and metal grain size, magnesium oxide crystallization orientation, metal content and distribution of metal grains in a membrane layer and thickness of the membrane layer. The secondary-electron emission thin film prepared by the method has high secondary electron emission yield and good electrical conductivity, and therefore, the secondary-electron emission thin film has high secondary-electron emission stability.
Description
Technical field
The invention belongs to photoelectron material and device technology field, relate to a kind of preparation method of the secondary electron emission film that can be used for electron-multiplier.
Background technology
Magnesium oxide (MgO) film, because have the advantages such as the good and preparation technology of high, the anti-charged particle bombardment performance of secondary electron yield is simple, is widely used in the devices such as image intensifier, photomultiplier, electron-multiplier, crossed field amplifier and plasma display at present.When for electron-multiplier, in order to make device obtain long work-ing life, secondary electron emission film must be able to tolerate higher-wattage stream of electrons and bombard for a long time, and therefore the MgO film thickness of preparation need to reach tens nanometers even more than 100 nanometers.But because magnesium oxide is insulating material, thicker MgO film can produce surface charge phenomenon under electron bombardment, this can make its secondary electron yield fast reducing also finally close to 1, thereby affects the stability of film secondary electron emission.This problem has limited the application of magnesia film in high-performance electronic multiplier.
Under electron bombardment, produce surface charge for fear of thicker MgO film, Henrich adopts and in MgO film, has mixed a certain proportion of gold to form MgO/ metallic cermet films, the electroconductibility of film is enhanced, and in order to make this film can there is the high secondary electron yield close to pure MgO film, form the very high thin layer (Appl.Phys.Lett. of one deck MgO content by art breading at film surface, 1973,23(7): 7-8).The concrete preparation method of this secondary electron emission film adopts radio frequency sputtering method sputter MgO/Au composition target in metal base, to prepare MgO/Au metallic cermet films, the Ar that is then 500ev with energy
+film surface is carried out to bombardment processing, utilize Ar
+thereby to golden sputter rate far above the sputter rate of MgO is formed to a thin layer with high MgO content on MgO/Au metallic cermet films surface.Due to mixing of Au, this MgO film conductivity is improved, make it in the time that rete is thicker, still can effectively avoid surface charge, thereby can be by increasing film thickness to improve the performance of film tolerance higher-wattage electron bombardment, and because have the thin layer that MgO content is very high to exist at film surface, this film also has higher secondary electron yield.When this secondary electron emission film is applied to electron-multiplier, can make electron-multiplier obtain higher gain and longer work-ing life.
Research shows, although this secondary electron emission film of reporting in above document has aforementioned advantages with respect to pure zirconia magnesium film, it also exists following obvious weak point:
(1) use a combined oxidation magnesium target that contains certain proportion gold composition to prepare secondary electron emission film, therefore, the magnesium oxide in film deposition process in target and gold are subject to the Ar of equal-wattage
+sputter.Due to Ar
+sputter rate to MgO and Au is widely different, causes the Au content being deposited in suprabasil film to change, inconsistent with the Au content in target; And, Ar
+the difference size of the sputter rate to MgO and Au also can change along with the change of the conditions such as sputtering power and working gas pressure; In addition the content of gold and the distribution of Jin Jing's grain in film and the Ar that bombards target in the growth of MgO and Au crystal grain, magnesium oxide crystalline orientation, film,
+energy and bi-material sedimentation rate separately relevant.Therefore, this film can not obtain suitable magnesium oxide and Jin Jing's particle size, magnesium oxide crystalline orientation, gold content and the distribution of Jin Jing's grain in film by regulating and controlling respectively the sputtering condition of MgO and Au, so be difficult to preparation technology to carry out meticulous optimization to obtain the secondary electron emission film of excellent performance.
(2) in order to improve the secondary electron yield of film, after thin film deposition completes, need to carry out sputter process to its surface with the argon ion of higher-energy (as 500ev), utilize Ar
+the differentiation sputter of MgO and Au is obtained to the thin layer of surperficial high MgO content.But the thickness of film surface MgO layer prepared by this method is difficult to accurate control, if surperficial MgO layer thickness is blocked up, can reduce film conductivity, thereby affects secondary electron emission stability, as crossed the thin secondary electron yield that can reduce film.And, Ar
+sputter process can cause the damage of top layer magnesium oxide crystal grain, reduces magnesian secondary electron yield.Particularly due to Ar
+difference size to various metals and magnesian sputter rate is also different, some metal due to sputter rate is lower or with MgO have the reason of stronger bonding force and the sputter rate difference of MgO little, cannot make to prepare in this way the thin layer of surperficial high magnesia content, the suitability of magnesia film that therefore the method is mixed different metal material to preparation is poor.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of secondary electron emission film, to overcome above-mentioned the deficiencies in the prior art.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for secondary electron emission film, comprises the following steps:
1), adopt the target of a kind of material in sputtered titanium, nickel, chromium, gold and silver, platinum or in metal base, deposit buffer layer by the composite target material that wherein different materials forms, its thickness is 3-100nm;
2), deposition of magnesium and metal mixed layer on buffer layer, magnesium oxide and metal mixed layer adopt the mode of sputter magnesium target/magnesium oxide target and other metallic targets of sputter to deposit and form, and other wherein said metallic targets are a kind of target in gold and silver, platinum material or by composite target material that wherein different materials forms; The total thickness of magnesium oxide and metal mixed layer is 30-300nm;
3), on magnesium oxide and metal mixed layer, deposit top layer, its thickness is 5-20nm.
The present invention further improves and is: top layer described in step 3) is the magnesium oxide layer of pure zirconia magnesium layer or other metal oxides that adulterate, and other metal oxides that adulterate in the magnesium oxide layer of described other metal oxides of doping are one or more in scandium oxide, calcium oxide, zinc oxide, zirconium white, yttrium oxide, titanium dioxide, aluminium sesquioxide; The mole percent level of other metal oxides except magnesium oxide in the magnesium oxide layer of other metal oxides of adulterating is 0.001%-9%.
The present invention further improves and is: the magnesium oxide layer of other metal oxides that adulterate in step 3) is prepared from by the form of sputter magnesium target/magnesium oxide target and other metal oxide targets.
The present invention further improves and is: step 2) in magnesium oxide and metal mixed layer by bottom to top, the content of metal successively decreases gradually, magnesian content increases progressively gradually.
The present invention further improves and is: in magnesium oxide and metal mixed layer, magnesian mole percent level is X, 70%≤X≤95%.
The present invention further improves and is: step 2) in magnesium oxide and metal mixed layer adopt the mode while formation of deposits of cosputtering magnesium target/magnesium oxide target and other metallic targets;
Or, step 2) in magnesium oxide and metal mixed layer adopt lasting sputter magnesium target/magnesium oxide target and the mode of other metallic targets of intermittent type sputter deposits and forms; Magnesium oxide and metal mixed layer comprise magnesium oxide layer and the magnesium oxide cermet coating that multi-turn is arranged; The thickness of every one deck magnesium oxide cermet coating is 15-40nm, and the thickness of every one deck magnesium oxide layer is 15-40nm;
Or, step 2) in magnesium oxide and metal mixed layer adopt the mode of alternating sputtering magnesium target/magnesium oxide target and other metallic targets to deposit to form; Magnesium oxide and metal mixed layer comprise magnesium oxide layer and the metal level that multi-turn is arranged; The thickness of every one deck magnesium oxide layer is 15-40nm, and the thickness of every one deck metal level is 10-20nm.
The present invention further improves and is: the magnesium oxide in magnesium oxide and metal mixed layer and metal exist with the form of 15-40nm and 10-20nm size crystal grain respectively, and the magnesium oxide in top layer exists with the form of 5-20nm size crystal grain.
The present invention further improves and is: while preparing magnesium oxide and metal mixed layer and top layer, metal base temperature is controlled between 300-550 ℃, and in control plated film cavity, the total gas pressure of argon gas and oxygen is 1.0 × 10
-2-5.0 × 10
-1pa, the throughput ratio of argon gas and oxygen is 10:1-1:1.
The present invention further improves and is: the secondary electron emission film that step 3) is obtained is placed in 350-600 ℃ and 5.0 × 10
-1-1.0 × 10
3further oxidation and annealing in the high-temperature oxygen environment of Pa air pressure.
The secondary electron emission method for manufacturing thin film main difference point of the inventive method and existing bibliographical information is: secondary electron emission film has multilayered structure, i.e. buffer layer---magnesium oxide and metal mixed layer---magnesium oxide layer; Buffer layer is to have the metallic film compared with strong adhesive force with metal base material; Adopt independently magnesium target (or magnesium oxide target) and other metallic target deposition of magnesium metal mixed layers of sputter, by regulate the filming condition such as sputtering power and sputtering time, gas flow and base reservoir temperature of two targets in film process, to regulate and control magnesium oxide and metal grain size, magnesium oxide crystalline orientation, metal content and the distribution of metal grain in film; Adopt sputter magnesium target (or magnesium oxide target) deposition one deck magnesium oxide thin layer at film surface, or adopt the magnesium oxide thin layer of sputter magnesium target/magnesium oxide target and the doping of other metal oxide targets deposition one decks.The advantage of this method is that content and the film microstructure of various compositions in secondary electron emission film more easily accurately controlled, thereby is conducive to process parameter optimizing to prepare high performance secondary electron emission film.
Basic conception of the present invention is: the secondary electron emission film of preparation has multilayered structure, i.e. buffer layer---magnesium oxide and metal mixed layer---magnesium oxide layer.It is for strengthening magnesia film at suprabasil sticking power that buffer layer is set, and contributes to the growth of magnesium oxide crystal grain.Adopt radio frequency discharge mode sputter magnesium oxide target to carry out deposition of magnesium or adopt reactive sputtering to carry out deposition of magnesium with radio frequency discharge or direct-current discharge mode sputter magnesium target.For magnesium oxide and metal mixed layer, adopt respectively sputter independently magnesium target (or magnesium oxide target) and other metallic target deposition of magnesium and preparation of metals form, metal is wherein the metallic substance that good conductivity and physicochemical property are stable.The top layer of secondary electron emission film can be pure zirconia magnesium layer, makes film have the secondary electron coefficient close to pure zirconia magnesium; Other metal oxides can also suitably adulterate in the magnesium oxide of top layer, research shows, in magnesium oxide, mix a certain proportion of material that there is lower work function or can form impurity level in magnesium oxide forbidden band, can be conducive to the secondary electron emission of film, thereby obtain the secondary electron yield higher than pure zirconia magnesium.In the time of deposition of magnesium, in plated film cavity, pass into argon gas and oxygen, argon gas is the working gas of using as sputter, oxygen is as reactant gases.While adopting magnesium target to prepare magnesium oxide, the magnesium atom sputtering through with oxygen molecule generation chemical reaction after generate magnesium oxide; While adopting magnesium oxide target to prepare magnesium oxide, in plated film cavity, pass into the decomposition that appropriate oxygen contributes to inhibited oxidation magnesium, and can improve magnesian degree of crystallinity.When preparation secondary electron emission film, can be by regulating magnesium target (or magnesium oxide target) and other metallic targets sputtering power and sputtering time separately, working gas and reaction gas flow and base reservoir temperature are prepared has suitable magnesium oxide and metal grain size, magnesium oxide crystalline orientation, metal content, the distribution of metal grain in film and magnesium oxide metal mixed layer and the top layer magnesium oxide of thicknesses of layers, make the secondary electron emission film of preparing both there is high secondary electron yield, the electroconductibility simultaneously also having had produces surface charge phenomenon to prevent film in electron bombardment process, thereby improve the stability of film secondary electron emission.
Compared with prior art, the preparation method of secondary electron emission film of the present invention has following remarkable advantage:
(1) grain-size of magnesium oxide and metal, magnesium oxide crystalline orientation, metal content and metal grain distribution and the thicknesses of layers in film is easy to accurate control, make the existing good electroconductibility of film to avoid surface charge, guaranteed that again magnesium oxide has the microtexture of optimization, thereby film can obtain higher secondary electron yield and stability.
(2) film-forming process is flexible, relatively simple, without Ar
+differentiation sputter, film top layer magnesium oxide thickness is easily controlled, and is adapted to mix various metallic substance to form the secondary electron emission film with suitable top layer magnesium oxide thickness in magnesium oxide.
(3) in the magnesium oxide of film top layer, mix a certain proportion of material that there is lower work function or can form impurity level in magnesium oxide forbidden band, be conducive to the secondary electron emission of film, thereby obtain the secondary electron yield higher than pure zirconia magnesium.
(4) buffer layer is set in metal base and can strengthens magnesia film at suprabasil sticking power, and contribute to the growth of magnesium oxide crystal grain.
Accompanying drawing explanation
Fig. 1 is the membrane structure schematic diagram that adopts the preparation method of the secondary electron emission film of the embodiment of the present invention 1 to prepare;
Fig. 2 is the membrane structure schematic diagram that adopts the preparation method of the secondary electron emission film of the embodiment of the present invention 2 to prepare;
Fig. 3 is the membrane structure schematic diagram that adopts the preparation method of the secondary electron emission film of the embodiment of the present invention 3 to prepare;
Fig. 4 is the membrane structure schematic diagram that adopts the preparation method of the secondary electron emission film of the embodiment of the present invention 4 to prepare;
Fig. 5 is the membrane structure schematic diagram that adopts the preparation method of the secondary electron emission film of the embodiment of the present invention 5 to prepare;
Fig. 6 is the membrane structure schematic diagram that adopts the preparation method of the secondary electron emission film of the embodiment of the present invention 6 to prepare;
Fig. 7 is that two kinds of different magnesium oxide grain-sizes of having that adopt prepared by the processing step of the embodiment of the present invention 2 mix the secondary electron yield δ of golden magnesium oxide secondary electron emission film with the change curve of incident electron energy Ep;
Fig. 8 is that two kinds of different metal content distribution of having that adopt that the processing step of the embodiment of the present invention 2 prepared in the metal refining mode of decreasing power and firm power sputter gold target respectively mix the curve of the secondary electron yield δ t decay in time of golden magnesium oxide secondary electron emission film.
Embodiment
Shown in Fig. 1, secondary electron emission film has multilayered structure, comprises buffer layer 1, magnesium oxide and the metal mixed layer 2 and the magnesium oxide layer 3 that are set in turn in metal base 4.
The preparation method of a kind of secondary electron emission film of the present invention, comprises the following steps:
First, adopt the target of a kind of material in sputtered titanium, nickel, chromium, gold and silver, platinum or in metal base 4, deposit buffer layer 1 by the composite target material that wherein different materials forms, its thickness is 3-100nm;
Then, deposition of magnesium and metal mixed layer 2 on buffer layer 1, this layer is to adopt mode while deposition of magnesium of cosputtering magnesium target (or magnesium oxide target) and other metallic targets and metal and the magnesium oxide cermet coating that forms, other metallic targets are wherein gold, silver, a kind of target of material or by composite target material that wherein different materials forms in platinum, by mixolimnion bottom to the deposition process at top, by regulating the sputtering power of magnesium target (or magnesium oxide target) and other metallic targets, make the sputtering power of other metallic targets reduce gradually or the sputtering power of magnesium target (or magnesium oxide target) is improved gradually, make the metal content distribution that tapers off to the position at top from mixolimnion bottom, the thickness of magnesium oxide and metal mixed layer 2 is 30-300nm,
Then, deposit pure zirconia magnesium layer 3 by sputter magnesium target (or magnesium oxide target) on magnesium oxide and metal mixed layer 2, its thickness is 5-20nm.
Shown in Fig. 2, secondary electron emission film has multilayered structure, comprises buffer layer 1, magnesium oxide and the metal mixed layer 2 and the magnesium oxide layer 3 that are set in turn in metal base 4.
The preparation method of a kind of secondary electron emission film of the present invention, comprises the following steps:
First, adopt the target of a kind of material in sputtered titanium, nickel, chromium, gold and silver, platinum or in metal base 4, deposit buffer layer 1 by the composite target material that wherein different materials forms, its thickness is between 3-100nm;
Then, deposition of magnesium and metal mixed layer 2 on buffer layer 1, magnesium oxide and metal mixed layer 2 are to adopt the magnesium oxide cermet coating 21 and magnesium oxide layer 22 that continue sputter magnesium target (or magnesium oxide target) and the mode of other metallic targets of intermittent type sputter and deposit multi-turn, other metallic targets are wherein gold, silver, a kind of target in platinum material or by composite target material that wherein different materials forms, by mixolimnion bottom to the deposition process at top, by regulating sputtering power and the sputtering time of magnesium target (or magnesium oxide target) and other metallic targets, sputtering power or the sputtering time of other metallic targets are reduced gradually, or sputtering power or the sputtering time of magnesium target (or magnesium oxide target) are increased gradually, make the metal content distribution that tapers off to the position at top from mixolimnion bottom, the thickness of every one deck magnesium oxide cermet coating 21 is 15-40nm, the thickness of every one deck magnesium oxide layer 22 is 15-40nm, the total thickness of magnesium oxide and metal mixed layer 2 is 30-300nm,
Then, deposit pure zirconia magnesium layer 3 by sputter magnesium target (or magnesium oxide target) on magnesium oxide and metal mixed layer 2, its thickness is 5-20nm.
Shown in Fig. 3, secondary electron emission film has multilayered structure, comprises buffer layer 1, magnesium oxide and the metal mixed layer 2 and the magnesium oxide layer 3 that are set in turn in metal base 4.
The preparation method of a kind of secondary electron emission film of the present invention, comprises the following steps:
First, adopt the target of a kind of material in sputtered titanium, nickel, chromium, gold and silver, platinum or in metal base 4, deposit buffer layer 1 by the composite target material that wherein different materials forms, its thickness is 3-100nm;
Then, deposition of magnesium and metal mixed layer 2 on buffer layer 1, magnesium oxide and metal mixed layer 2 are to adopt the mode of alternating sputtering magnesium target (or magnesium oxide target) and other metallic targets to deposit the metal level 23 and magnesium oxide layer 24 of multi-turn, other metallic targets are wherein gold, silver, a kind of target in platinum material or by composite target material that wherein different materials forms, by mixolimnion bottom to the deposition process at top, by regulating sputtering power and the sputtering time of magnesium target (or magnesium oxide target) and other gold targets, sputtering power or the sputtering time of other metallic targets are reduced gradually, or sputtering power or the sputtering time of magnesium target (or magnesium oxide target) are increased gradually, make the metal content distribution that tapers off to the position at top from mixolimnion bottom, the thickness of every one deck metal level 23 is 10-20nm, the thickness of every one deck magnesium oxide layer 24 is 15-40nm, the total thickness of magnesium oxide and metal mixed layer 2 is 30-300nm,
Then, deposit pure zirconia magnesium layer 3 by sputter magnesium target (or magnesium oxide target) on magnesium oxide and metal mixed layer 2, its thickness is 5-20nm.
Embodiment 4
Shown in Fig. 4, secondary electron emission film has multilayered structure, comprises the buffer layer 1, magnesium oxide and the metal mixed layer 2 that are set in turn in metal base 4 and the magnesium oxide layer 5 of other metal oxides that adulterate.
The preparation method of a kind of secondary electron emission film of the present invention, comprises the following steps:
First, adopt the target of a kind of material in sputtered titanium, nickel, chromium, gold and silver, platinum or in metal base 4, deposit buffer layer 1 by the composite target material that wherein different materials forms, its thickness is 3-100nm;
Then, deposition of magnesium and metal mixed layer 2 on buffer layer 1, this layer adopts the mode while deposition of magnesium of cosputtering magnesium target (or magnesium oxide target) and other metallic targets and metal and the magnesium oxide cermet coating that forms, other metallic targets are wherein gold, silver, a kind of target in platinum material or by composite target material that wherein different materials forms, by mixolimnion bottom to the deposition process at top, by regulating the sputtering power of magnesium target (or magnesium oxide target) and other metallic targets, make the sputtering power of other metallic targets reduce gradually or the sputtering power of magnesium target (or magnesium oxide target) is increased gradually, make the metal content distribution that tapers off to the position at top from mixolimnion bottom, the thickness of magnesium oxide and metal mixed layer 2 is 30-300nm,
Then, by the magnesium oxide layer 5 of sputter magnesium target (or magnesium oxide target) and other metal oxide targets other metal oxides of dopant deposition on magnesium oxide and metal mixed layer 2 respectively, other metal oxide targets are wherein targets of a kind of material in scandium oxide, calcium oxide, zinc oxide, zirconium white, yttrium oxide, titanium dioxide, aluminium sesquioxide or by composite target material that wherein different materials forms; The mole percent level of other metal oxides except magnesium oxide in the magnesium oxide layer 5 of other metal oxides of adulterating is 0.001%-9%, and the thickness of the magnesium oxide layer 5 of other metal oxides that adulterate is 5-20nm.
Embodiment 5
Shown in Fig. 5, secondary electron emission film has multilayered structure, comprises the buffer layer 1, magnesium oxide and the metal mixed layer 2 that are set in turn in metal base 4 and the magnesium oxide layer 5 of other metal oxides that adulterate.
The preparation method of a kind of secondary electron emission film of the present invention, comprises the following steps:
First, adopt the target of a kind of material in sputtered titanium, nickel, chromium, gold and silver, platinum or in metal base 4, deposit buffer layer 1 by the composite target material that wherein different materials forms, its thickness is 3-100nm;
Then, deposition of magnesium and metal mixed layer 2 on buffer layer 1, magnesium oxide and metal mixed layer 2 are to adopt the magnesium oxide cermet coating 21 and magnesium oxide layer 22 that continue sputter magnesium target (or magnesium oxide target) and the mode of other metallic targets of intermittent type sputter and deposit multi-turn, other metallic targets are wherein gold, silver, a kind of target in platinum material or by composite target material that wherein different materials forms, by mixolimnion bottom to the deposition process at top, by regulating sputtering power and the sputtering time of magnesium target (or magnesium oxide target) and other metallic targets, sputtering power or the sputtering time of other metallic targets are reduced gradually, or sputtering power or the sputtering time of magnesium target (or magnesium oxide target) are increased gradually, make the metal content distribution that tapers off to the position at top from mixolimnion bottom, the thickness of every one deck magnesium oxide cermet coating 21 is 15-40nm, the thickness of every one deck magnesium oxide layer 22 is 15-40nm, the total thickness of magnesium oxide and metal mixed layer 2 is 30-300nm,
Then, by the magnesium oxide layer 5 of sputter magnesium target (or magnesium oxide target) and other metal oxide targets other metal oxides of dopant deposition on magnesium oxide and metal mixed layer 2 respectively, other metal oxide targets are wherein targets of a kind of material in scandium oxide, calcium oxide, zinc oxide, zirconium white, yttrium oxide, titanium dioxide, aluminium sesquioxide or by composite target material that wherein different materials forms; The mole percent level of other metal oxides except magnesium oxide in the magnesium oxide layer 5 of other metal oxides of adulterating is 0.001%-9%, and the thickness of the magnesium oxide layer 5 of other metal oxides that adulterate is 5-20nm.
Embodiment 6
Shown in Fig. 6, secondary electron emission film has multilayered structure, comprises the buffer layer 1, magnesium oxide and the metal mixed layer 2 that are set in turn in metal base 4 and the magnesium oxide layer 5 of other metal oxides that adulterate.
The preparation method of a kind of secondary electron emission film of the present invention, comprises the following steps:
First, adopt the target of a kind of material in sputtered titanium, nickel, chromium, gold and silver, platinum or in metal base 4, deposit buffer layer 1 by the composite target material that wherein different materials forms, its thickness is 3-100nm;
Then, deposition of magnesium and metal mixed layer 2 on buffer layer 1, magnesium oxide and metal mixed layer 2 are to adopt the mode of alternating sputtering magnesium target (or magnesium oxide target) and other metallic targets to deposit the metal level 23 and magnesium oxide layer 24 of multi-turn, other metallic targets are wherein gold, silver, a kind of target in platinum material or by composite target material that wherein different materials forms, by mixolimnion bottom to the deposition process at top, by regulating sputtering power and the sputtering time of magnesium target (or magnesium oxide target) and other metallic targets, sputtering power or the sputtering time of other metallic targets are reduced gradually, or sputtering power or the sputtering time of magnesium target (or magnesium oxide target) are increased gradually, make the metal content distribution that tapers off to the position at top from mixolimnion bottom, the thickness of every one deck metal level 23 is 10-20nm, the thickness of every one deck magnesium oxide layer 24 is 15-40nm, the total thickness of magnesium oxide and metal mixed layer 2 is 30-300nm,
Then, by the magnesium oxide layer 5 of sputter magnesium target (or magnesium oxide target) and other metal oxide targets other metal oxides of dopant deposition on magnesium oxide and metal mixed layer 2 respectively, other metal oxide targets are wherein targets of a kind of material in scandium oxide, calcium oxide, zinc oxide, zirconium white, yttrium oxide, titanium dioxide, aluminium sesquioxide or by composite target material that wherein different materials forms; The mole percent level of other metal oxides except magnesium oxide in the magnesium oxide layer 5 of other metal oxides of adulterating is 0.001%-9%, and the thickness of the magnesium oxide layer 5 of other metal oxides that adulterate is 5-20nm.
In the above-described embodiments, in magnesium oxide and metal mixed layer 2, magnesian mole percent level is X, 70%≤X≤95%, and the metal content distribution that tapers off to the position at top from the bottom of magnesium oxide and metal mixed layer 2, such secondary electron emission film is because the electroconductibility that rete bottom has higher metal content that film has been had has high secondary electron yield at the higher film that makes of the magnesian content in the position the closer to film surface simultaneously.
For above-described embodiment, magnesium oxide in magnesium oxide and metal mixed layer 2 and metal exist with the form of 15-40nm and 10-20nm size crystal grain respectively, and in top layer (magnesium oxide layers 5 of pure zirconia magnesium layer 3 or other metal oxides that adulterate), magnesium oxide exists with the form of 5-10nm size crystal grain.While preparing magnesium oxide and metal mixed layer and top layer magnesium oxide, base reservoir temperature is controlled between 300-550 ℃ and makes magnesium oxide and metal have suitable grain-size to guarantee that film has the positive charge accumulating on the simultaneous oxidation magnesium crystal grain of high secondary electron yield and can be neutralized to avoid film surface charged from the electronics of substrate by the conduction of metal grain, and, to the deposition process at magnesium oxide top, film top layer, keep base reservoir temperature constant in the bottom from magnesium oxide and metal mixed layer, or make base reservoir temperature reduce gradually to reduce the diffusion of atoms metal to film surface, while preparing magnesium oxide and metal mixed layer and top layer magnesium oxide, by changing the flow of argon gas and oxygen, control total gas pressure 1.0 × 10
-2-5.0 × 10
-1between Pa, the throughput ratio of argon gas and oxygen is 10:1-1:1, make the magnesium oxide of deposition there is suitable crystalline orientation, and, to the magnesian deposition process in top layer, keep the throughput ratio of argon gas and oxygen constant in the bottom from magnesium oxide and metal mixed layer, or by regulating the flow of argon gas and oxygen to make their throughput ratio prepare to improve the magnesian degree of crystallinity near film top layer in the mode of successively decreasing, after secondary electron emission thin film deposition completes, film is placed in to 350-600 ℃ and 5.0 × 10
-1-1.0 × 10
3in the high-temperature oxygen environment of Pa air pressure, carry out further oxidation and the annealing of 30-120 minute, object is to make the magnesium atom in film fully be oxidized and eliminate membrane stress, and improves magnesia film compactness.
Figure 7 shows that the magnesium oxide grain-size that adopts the processing step of the embodiment of the present invention 2 to prepare is respectively 5-20nm and (distinguishes corresponding curve a and curve b) with two kinds that the are less than 2nm secondary electron yield δ that mix golden magnesium oxide secondary electron emission film with the curve of incident electron energy Ep variation.Can find out, compared with the secondary electron yield of the film of larger magnesium oxide crystal grain and the film of less magnesium oxide crystal grain, the former is apparently higher than the latter.If but magnesium oxide grain-size is excessive, film easily produces surface charge under the bombardment of stream of electrons.Therefore, for the secondary electron emission performance obtaining, must deposit have suitable magnesium oxide grain-size film.
Figure 8 shows that two kinds of different metal content distribution of having that adopt that the processing step of the embodiment of the present invention 2 prepared in the metal refining mode of 35W to 22W decreasing power and 30W firm power sputter gold target respectively mix the curves of secondary electron yield δ t decay in time of golden magnesium oxide secondary electron emission film (corresponding curve a and curve are b) respectively in rete.Can find out, along with the growth of incident electron stream bombardment time, the taper off secondary electron emission film of distribution of the position metal content at bottom to the top by magnesium oxide and metal mixed layer that adopts decreasing power sputter gold target to prepare has higher secondary electron yield all the time.
As can be seen from the above embodiments, compared with existing secondary electron emission method for manufacturing thin film, magnesium oxide in film and the grain-size of metal, magnesium oxide crystalline orientation, metal content and the distribution of metal grain in film are easy to accurate control, thereby can make film obtain higher secondary electron yield and stability; Film-forming process is flexible, relatively simple, is adapted to mix various metallic substance to improve its electroconductibility in magnesium oxide, without adopting Ar
+differentiation sputter, film skin depth is easily controlled; In the magnesium oxide of film top layer, mix a certain proportion of material that there is lower work function or can form impurity level in magnesium oxide forbidden band, be conducive to film secondary electron emission, thereby obtain the secondary electron yield higher than pure zirconia magnesium.
Although the present invention has made detailed description with above-mentioned preferred embodiment to the present invention, not limit the present invention with above-described embodiment.The preparation method of secondary electron emission film of the present invention is not limited to above-mentioned several scheme, as long as according to basic conception of the present invention, adopt independently magnesium target (or magnesium oxide target) and metallic target of sputter, by accurately controlling respectively the sputtering power of magnesium target (or magnesium oxide target) and metallic target, sputtering time, working gas and reaction gas flow and base reservoir temperature preparation have suitable magnesium oxide and metal grain size, magnesium oxide crystalline orientation, metal content, the distribution of metal grain in film and magnesium oxide metal mixed layer and the top layer magnesium oxide of thicknesses of layers, make secondary electron emission film obtain higher secondary electron yield and the object of stability to reach, all belong to protection scope of the present invention.
Claims (9)
1. a preparation method for secondary electron emission film, is characterized in that, comprises the following steps:
1), adopt the target of a kind of material in sputtered titanium, nickel, chromium, gold and silver, platinum or by composite target material that wherein different materials form at the upper buffer layer (1) that deposits of metal base (4), its thickness is 3-100nm;
2), at the upper deposition of magnesium of buffer layer (1) and metal mixed layer (2), magnesium oxide and metal mixed layer (2) adopt the mode of sputter magnesium target/magnesium oxide target and other metallic targets of sputter to deposit and form, and other wherein said metallic targets are a kind of target in gold and silver, platinum material or by composite target material that wherein different materials forms; The total thickness of magnesium oxide and metal mixed layer (2) is 30-300nm;
3), on the upper deposition of magnesium oxide and metal mixed layer (2) top layer, its thickness is 5-20nm.
2. the preparation method of a kind of secondary electron emission film according to claim 1, it is characterized in that, top layer described in step 3) is the magnesium oxide layer of pure zirconia magnesium layer or other metal oxides that adulterate, and other metal oxides that adulterate in the magnesium oxide layer of described other metal oxides of doping are one or more in scandium oxide, calcium oxide, zinc oxide, zirconium white, yttrium oxide, titanium dioxide, aluminium sesquioxide; The mole percent level of other metal oxides except magnesium oxide in the magnesium oxide layer of other metal oxides of adulterating is 0.001%-9%.
3. the preparation method of a kind of secondary electron emission film according to claim 1, is characterized in that, the magnesium oxide layer of other metal oxides that adulterate in step 3) is prepared from by the form of sputter magnesium target/magnesium oxide target and other metal oxide targets.
4. the preparation method of a kind of secondary electron emission film according to claim 1, is characterized in that step 2) in magnesium oxide and metal mixed layer (2) by bottom to top, the content of metal successively decreases gradually, magnesian content increases progressively gradually.
5. the preparation method of a kind of secondary electron emission film according to claim 1, is characterized in that, in magnesium oxide and metal mixed layer (2), magnesian mole percent level is X, 70%≤X≤95%.
6. the preparation method of a kind of secondary electron emission film according to claim 1, is characterized in that step 2) in magnesium oxide and metal mixed layer (2) adopt the mode while formation of deposits of cosputtering magnesium target/magnesium oxide target and other metallic targets;
Or, step 2) in magnesium oxide and metal mixed layer (2) adopt lasting sputter magnesium target/magnesium oxide target and the mode of other metallic targets of intermittent type sputter deposits and forms; Magnesium oxide and metal mixed layer (2) comprise the magnesium oxide cermet coating (21) and magnesium oxide layer (22) that multi-turn is arranged; The thickness of every one deck magnesium oxide cermet coating (21) is 15-40nm, and the thickness of every one deck magnesium oxide layer (22) is 15-40nm;
Or, step 2) in magnesium oxide and metal mixed layer (2) adopt the mode of alternating sputtering magnesium target/magnesium oxide target and other metallic targets to deposit to form; Magnesium oxide and metal mixed layer (2) comprise the metal level (23) and magnesium oxide layer (24) that multi-turn is arranged; The thickness of every one deck metal level (23) is 10-20nm, and the thickness of every one deck magnesium oxide layer (24) is 15-40nm.
7. the preparation method of a kind of secondary electron emission film according to claim 1, it is characterized in that, magnesium oxide in magnesium oxide and metal mixed layer (2) and metal exist with the form of 15-40nm and 10-20nm size crystal grain respectively, and the magnesium oxide in top layer exists with the form of 5-20nm size crystal grain.
8. the preparation method of a kind of secondary electron emission film according to claim 1, it is characterized in that, while preparing magnesium oxide and metal mixed layer (2) and top layer, metal base (4) temperature is controlled between 300-550 ℃, and in control plated film cavity, the total gas pressure of argon gas and oxygen is 1.0 × 10
-2-5.0 × 10
-1pa, the throughput ratio of argon gas and oxygen is 10:1-1:1.
9. the preparation method of a kind of secondary electron emission film according to claim 1, is characterized in that, the secondary electron emission film that step 3) is obtained is placed in 350-600 ℃ and 5.0 × 10
-1-1.0 × 10
3further oxidation and annealing in the high-temperature oxygen environment of Pa air pressure.
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| 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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