CN103849835A - Zr-Co-Re thin film getter provided with protection layer, and preparation method thereof - Google Patents
Zr-Co-Re thin film getter provided with protection layer, and preparation method thereof Download PDFInfo
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- CN103849835A CN103849835A CN201210500682.3A CN201210500682A CN103849835A CN 103849835 A CN103849835 A CN 103849835A CN 201210500682 A CN201210500682 A CN 201210500682A CN 103849835 A CN103849835 A CN 103849835A
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Abstract
The invention relates to a Zr-Co-Re thin film getter provided with a protection layer, and a preparation method thereof. The Zr-Co-Re thin film getter is composed of a getter layer and the protection layer; main components of the getter layer are Zr, Co, and one or more selected form rare earth elements La, Ce, Pr, and Nd; and main component of the protection layer is Ni. Pulsed laser deposition film plating is adopted, and deposition of the double-layer structured thin film getter containing the protection layer and the getter layer on texture monocrystalline silicon is carried out. The texture substrate is capable of increasing effective area of the getter thin film, and so that inspiratory flow rate and inspiratory capacity are increased. The surface of the getter layer is plated with a Ni protection layer; Ni is capable of realizing dissociation of hydrogen, and increasing absorption amount of hydrogen; and the Ni protection layer is capable of inhibiting absorption of oxygen and reducing activation temperature. Activation of the Zr-Co-Re thin film getter can be realized in roasting processes at a temperature of 180 to 350 DEG C; after roasting, the Zr-Co-Re thin film getter possesses excellent inspiration performance at room temperature, can be used for internal gas residue removing of high vacuum microelectronic devices.
Description
Technical field
The present invention relates to a kind of Zr-Co-Re film getter with matcoveredn and preparation method thereof, getter of the present invention is a kind of Zr-Co-Re high-performance low-temp activation non-evaporable film getter that contains Ni protective layer.
Background technology
Getter is by physics and chemistry effect some reactive gas molecule of sorption or the preparation of fixing atmosphere or the common name of device effectively, to claim again getter or getter.
Conventional getter material has alloy or the compound of barium, strontium, magnesium, calcium, titanium, zirconium, hafnium, vanadium, barium aluminium alloy or transition metal and aluminium or rare earth element, wherein binary alloy is as Ba-Al, Ti-V, Zr-Al etc., and ternary alloy is as Ba-Al-Ni, Zr-V-Fe, Ti-Zr-V etc.This class material generally has very high activity, low saturated vapor pressure and bigger serface, to the residual activity gas in electrovacuum as H
2, O
2, N
2, CO and C
mh
ndeng, the absorption that tool is very strong or receptivity.
Along with the microminiaturization more of modern precision electronic devices and components, the application of non-evaporable film getter material is more and more extensive.The film getter following advantage of comparing with block getter: the specific activity surface-area that (1) is higher, room temperature gettering rate is large; (2) 250 ℃ ~ 500 ℃ scopes can activate, activation process and microelectronic device package process compatible; (3) dimensional precision is high, and space occupancy is little, can be on different shapes substrate uniform deposition; (4) good at encapsulation cover plate or inner chamber sticking power, vibrated or impact time good mechanical stability; (5) without efflorescence or discrete particle phenomenon, Thermodynamically stable under packaging environment; (6) with most of wafer semiconductor process compatibles.
Film getter can use the preparation of pulsed laser deposition (PLD) method.Pulsed laser deposition technique is one of the most promising masking technique at present, and this technology is simple and have many good qualities.For film getter, use PLD method plated film, prepare surface particles strong, inside is the film of column short texture.This structure has great meaning to getter surface adsorption gas molecule and gas molecule in film internal divergence.
The film getter existing at present mainly contains Zr-V-Fe film getter, Ti-Zr-V film getter etc.And these existing film getters are mainly to use the method for magnetron sputtering to prepare.This class film getter has the following disadvantages: the oxide compound of (1) vanadium and vanadium is toxic, large to harm; (2) activationary temperature of getter is high, activation technology is complicated, has certain limitation for the use of high precision microelectronic device; (3) getter is very easily oxidized under the state that exposes atmosphere, and the life-span of getter is short.
Summary of the invention
The object of this invention is to provide a kind of non-evaporable film getter, contain air suction layer and protective layer double-layer film structure, have and exempt from the feature activating and there is high pumping property.
In the present invention, adopt containing the alloys target of vanadium, and in alloy, add and there is highly active rare earth element.Can, effectively by the Zr existing with oxidation state or Co reduction, increase active surface at getter working process rare earth elements, improve pumping property.Prepare bilayer structure film, effectively reduce film surface oxidisability in the course of the work.And, use in the present invention textured mono-crystalline silicon substrate, can increase the useful area on film getter surface, improve gettering rate and the inspiratory capacity of getter.
The Zr-Co-Re(rare earth of band matcoveredn of the present invention) film getter; formed by air suction layer and protective layer; the main component of described air suction layer is one or more in Zr, Co and La, Ce, these four kinds of rare earth elements of Pr, Nd, and the main component of protective layer is Ni.
In the air suction layer of film getter, the mass content that the mass content of Zr is 68 ~ 88%, Co is that one or more the mass content in 10 ~ 24%, La, Ce, Pr, Nd is 2 ~ 10%.The mass percent sum of said components is 100%.
In the protective layer of film getter, the mass content of Ni is 99.5%.
The air suction layer of film getter is a kind of loose columnar structure, Presence of an interface and hole between columnar structure, and the diameter of columnar structure is at 20 ~ 50nm.The thickness of air suction layer is 300nm ~ 1 μ m.
The protective layer of film getter is a kind of loose grainy texture, has a large amount of gaps between particle, can further increase film specific surface area, and is conducive to absorption and the diffusion of gas molecule.The thickness of protective layer is 20 ~ 100nm.
The activationary temperature of film getter of the present invention is low, can directly realize afterwards surface activation 180 ~ 350 ℃ of bakings, has good pumping property, after activation to H
2, CO, O
2, N
2, isoreactivity gas has very high gettering rate and inspiratory capacity.
In the present invention, air suction layer is to the H except rare gas element
2, O
2, N
2, CO, CO
2and C
mh
nthere is good absorption ability Deng gas.And the protective layer above air suction layer is to the selective adsorption function of hydrogen atom, and can play a protective role to air suction layer, greatly reduce O
2to the oxidation of air suction layer.
The present invention provides a kind of preparation method of above-mentioned film getter simultaneously.The present invention uses pulsed laser deposition (PLD) in textured mono-crystalline silicon surface deposition one deck gas-absorbing layer, and at absorption layer surface deposition layer protective layer, prepares double-deck getter film.Bilayer structure film getter in the present invention as shown in Figure 1, plates air suction layer 2 on substrate 1, protective layer plating 3 on air suction layer 2.
PLD preparation method can make film surface graininess strengthens, film internal structure is loose and obtain thin film composition and target consistence of composition high (use in the component proportions of film and coating process the component proportions of target in full accord).
The present invention uses PLD coating technique, effectively improves the Surface and internal structure of film, is more conducive to the absorption of gas molecule and the diffusion at material internal.
The substrate that the present invention prepares film getter is textured mono-crystalline silicon.Common silicon single crystal corrodes through chemical solution, surface becomes pyramid matte, the substrate of this coarse structure forming core of particle at substrate surface that be conducive to evapotranspire in deposition process, and after deposition finishes, the surface of film also can thereby form rough surface topography due to the former of substrate, forms larger effective air-breathing area.In the present invention, adopt the textured mono-crystalline silicon substrate with bigger serface, at substrate surface deposition gases absorption layer, and at air suction layer surface deposition protective layer, textured mono-crystalline silicon substrate has improved the effective surface area of film getter.
The preparation method of the Zr-Co-Re film getter of band matcoveredn of the present invention, comprises the steps:
(1) use successively acetone, alcohol, deionized water ultrasonic cleaning monocrystalline silicon piece, after Wafer Cleaning, use High Purity Nitrogen to dry up;
(2) preparation silicon chip etchant solution, etchant solution is the aqueous solution of NaOH and Virahol, wherein NaOH content is 1 ~ 5wt.%, isopropanol content is 2 ~ 10wt.%, use thermostatic oven that solution is heated to 70 ~ 100 ℃ and keep constant temperature, the silicon chip cleaning up that step (1) is prepared is put into solution and is corroded 30 ~ 100min, and silicon chip extracting post-flush is clean, dries up with High Purity Nitrogen;
(3) substrate of being prepared by step (2) and the alloy target material identical with air suction layer composition are put into the sediment chamber of pulsed laser deposition together, vacuumize and pour high-purity argon gas in sediment chamber, use pulse laser ablation alloy target material, and deposition is prepared air suction layer;
(4) the deposition protective layer that uses the same method on the air suction layer of preparing in step (3), uses pulse laser ablation nickel target, and deposition is prepared protective layer.
In step (1), use successively acetone, alcohol, the each 10 ~ 20min of deionized water ultrasonic cleaning monocrystalline silicon piece.
In step (2), in described etchant solution, NaOH content is that 1 ~ 3wt.%, isopropanol content are 6 ~ 9wt.%, and solution is heated to 80 ~ 90 ℃ and keep constant temperature, the silicon chip cleaning up is put into solution and corrode 40 ~ 70min.
In step (3), while preparing air suction layer, the sediment chamber of PLD is vacuumized, when vacuum tightness reaches 1 × 10
-5~ 1 × 10
-3when Pa, be 99.99% high-purity argon gas to pouring purity in sediment chamber, ar pressure scope is 1 × 10
-4~ 15Pa, opens pulse laser after pressure is stable, and laser energy is 100 ~ 500mj, and laser frequency is 2 ~ 6Hz, and target-substrate distance is 4 ~ 8cm, target pre-sputtering 10 ~ 20min, and the thin film deposition time is 100 ~ 300min.
Preferably, the energy of pulse laser is 300 ~ 400mj, and frequency is 5 ~ 6Hz, and target-substrate distance is 5 ~ 6cm, and ar pressure is 0.2 ~ 10Pa, and depositing time is 100 ~ 200min.
In step (4), while preparing protective layer, ar pressure is 0.2 ~ 8Pa, and laser energy is 50 ~ 200mj, and laser frequency is 1 ~ 6Hz, and target-substrate distance is 4 ~ 8cm, preferably 5 ~ 6cm, and depositing time is 10 ~ 30min.The purity of described nickel target is 99.5wt.%.
Film getter of the present invention can be applied in microelectromechanical systems (MEMS), flat-panel monitor (OLED/FED/LCD), sun power heat-insulating shield equal vacuum degree require high, activation condition is required in strict environment.
Film getter advantage prepared by the present invention is: getter is bilayer structure film, and at air suction layer surface deposition protective layer, Ni has to hydrogen the function of dissociating, and can improve the adsorptive capacity of hydrogen, and protective layer can hinder the absorption of oxygen, reduction activationary temperature.Therefore, this getter can improve the uptake rate to hydrogen atom greatly.Air suction layer activity is very high, and very easily oxidation by air can reduce to a great extent the degree of oxidation of air suction layer under the effect of surperficial Ni protective layer, reduces the activationary temperature of film.The present invention can realize activation in 180 ~ 350 ℃ of bake process, can be good at coincideing with the working conditions of most of microelectronic device.The present invention adopts textured mono-crystalline silicon substrate, and post-depositional film effective surface area is very big, has greatly improved gettering rate and the inspiratory capacity of getter.
Below by the drawings and specific embodiments, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of film getter of the present invention.
Fig. 2 is the schematic diagram of comparative example 1.
Fig. 3 is the schematic diagram of comparative example 2.
Fig. 4 is the schematic diagram of comparative example 3.
Fig. 5 is dynamic method pumping property test curve.
Embodiment
The preparation method of film getter of the present invention adopts pulsed laser deposition (PLD) in textured mono-crystalline silicon surface deposition one deck gas-absorbing layer, and at absorption layer surface deposition layer protective layer, prepares double-deck getter film.
First, prepare textured mono-crystalline silicon as deposition substrate.Use successively acetone, alcohol, the each 10 ~ 20min of deionized water ultrasonic cleaning monocrystalline silicon piece, after Wafer Cleaning, use High Purity Nitrogen to dry up; Preparation silicon chip etchant solution, etchant solution is the aqueous solution of NaOH and Virahol, wherein NaOH content is 1 ~ 5wt.%, isopropanol content is 2 ~ 10wt.%, use thermostatic oven that solution is heated to 70 ~ 100 ℃ and keep constant temperature, the ready silicon chip cleaning up is put into solution and corrode 30 ~ 100min, silicon chip extracting post-flush is clean, dries up with High Purity Nitrogen.
Adopt pulsed laser deposition (PLD) film coating method to prepare film, textured mono-crystalline silicon sheet after cleaning and alloys target (Zr68 ~ 88-Co10 ~ 24-Re2 ~ 10wt.%, Re is one or more in La, Ce, Pr, Nd) are put into the sediment chamber of pulsed laser deposition.Use molecular pump that coating system is evacuated to 1 × 10
-5~ 1 × 10
-3pa, passes into high-purity argon gas (99.99%) to sediment chamber, pressure is stabilized in 1 × 10
-415Pa.Open laser transmitter, accurately to the defocused pulse laser of opening, use pulse laser ablation alloy target material, pre-sputtering 10 ~ 20min, to remove target material surface zone of oxidation, starts thin film deposition after pre-sputtering.The energy of pulse laser is that 100 ~ 500mj, frequency are 2 ~ 6Hz, and target-substrate distance is 4 ~ 8cm, and sputtering time is 100 ~ 300min, formation of deposits film under this condition.
Use pulse laser ablation nickel target, deposit again layer of Ni protective layer at the film surface of deposition.The processing parameter of protective layer: pulsed laser energy is that 50 ~ 200mj, frequency are 1 ~ 5Hz, and target-substrate distance is 4 ~ 8cm, and sputtering time is 10 ~ 30min, and ar pressure is 0.2 ~ 5Pa, and the purity of described nickel target is 99.5wt.%.
Working method of the present invention is with comparative example 2 is identical below, and unique different place is that deposition substrate is used the textured mono-crystalline silicon in comparative example 3.Under this condition, the thickness of film air suction layer is 300nm ~ 1 μ m, and columnar organization diameter is 20 ~ 50nm, and the thickness of protective layer is 20 ~ 100nm, becomes grainy texture.Bilayer structure film getter of the present invention as shown in Figure 1, plates air suction layer 2 on substrate 1, protective layer plating 3 on air suction layer 2.
Adopt pulsed laser deposition (PLD) to prepare double-deck getter film.
First, prepare textured mono-crystalline silicon as deposition substrate.Use successively acetone, alcohol, the each 15min of deionized water ultrasonic cleaning monocrystalline silicon piece, after Wafer Cleaning, use High Purity Nitrogen to dry up; Preparation silicon chip etchant solution, etchant solution is the aqueous solution of NaOH and Virahol, wherein NaOH content is 3wt.%, isopropanol content is 5wt.%, use thermostatic oven that solution is heated to 80 ℃ and keep constant temperature, the ready silicon chip cleaning up is put into solution and corrode 50min, silicon chip extracting post-flush is clean, dries up with High Purity Nitrogen.
Adopt pulsed laser deposition (PLD) film coating method to prepare film, the textured mono-crystalline silicon sheet after cleaning and alloys target (Zr80.8-Co14.2-Re5wt.%, Re is one or more in La, Ce, Pr, Nd) are put into the sediment chamber of pulsed laser deposition.Use molecular pump that coating system is evacuated to 1 × 10
-4pa, passes into high-purity argon gas (99.99wt.%) to sediment chamber, pressure is stabilized in 5Pa.Open laser transmitter, accurately to the defocused pulse laser of opening, use pulse laser ablation alloy target material, pre-sputtering 10min, to remove target material surface zone of oxidation, starts thin film deposition after pre-sputtering.The energy of pulse laser is that 500mj, frequency are 5Hz, and target-substrate distance is 5cm, and sputtering time is 300min, formation of deposits film under this condition.
Use pulse laser ablation nickel target, deposit again layer of Ni protective layer at the film surface of deposition.The processing parameter of protective layer: pulsed laser energy is that 100mj, frequency are 5Hz, and target-substrate distance is 5cm, and sputtering time is 30min, and ar pressure is 5Pa, and the purity of described nickel target is 99.5wt.%.
The thickness that the present embodiment obtains film air suction layer is 1 μ m, and columnar organization diameter is 30-50nm, and the thickness of protective layer is 60nm, becomes grainy texture.
Adopt pulsed laser deposition (PLD) to prepare double-deck getter film.
First, prepare textured mono-crystalline silicon as deposition substrate.Use successively acetone, alcohol, the each 15min of deionized water ultrasonic cleaning monocrystalline silicon piece, after Wafer Cleaning, use High Purity Nitrogen to dry up; Preparation silicon chip etchant solution, etchant solution is the aqueous solution of NaOH and Virahol, wherein NaOH content is 2wt.%, isopropanol content is 3wt.%, use thermostatic oven that solution is heated to 90 ℃ and keep constant temperature, the ready silicon chip cleaning up is put into solution and corrode 60min, silicon chip extracting post-flush is clean, dries up with High Purity Nitrogen.
Adopt pulsed laser deposition (PLD) film coating method to prepare film, the textured mono-crystalline silicon sheet after cleaning and alloys target (Zr68-Co24-Re8wt.%, Re is one or more in La, Ce, Pr, Nd) are put into the sediment chamber of pulsed laser deposition.Use molecular pump that coating system is evacuated to 1 × 10
-4pa, passes into high-purity argon gas (99.99%) to sediment chamber, pressure is stabilized in 8Pa.Open laser transmitter, accurately to the defocused pulse laser of opening, use pulse laser ablation alloy target material, pre-sputtering 10min, to remove target material surface zone of oxidation, starts thin film deposition after pre-sputtering.The energy of pulse laser is that 300mj, frequency are 5Hz, and target-substrate distance is 5cm, and sputtering time is 300min, formation of deposits film under this condition.
Use pulse laser ablation nickel target, deposit again layer of Ni protective layer at the film surface of deposition.The processing parameter of protective layer: pulsed laser energy is that 150mj, frequency are 5Hz, and target-substrate distance is 5cm, and sputtering time is 15min, and ar pressure is 8Pa, and the purity of described nickel target is 99.5wt.%.
The thickness that the present embodiment obtains film air suction layer is 600nm, and columnar organization diameter is 30-50nm, and the thickness of protective layer is 40nm, becomes grainy texture.
Adopt pulsed laser deposition (PLD) to prepare double-deck getter film.
First, prepare textured mono-crystalline silicon as deposition substrate.Use successively acetone, alcohol, the each 15min of deionized water ultrasonic cleaning monocrystalline silicon piece, after Wafer Cleaning, use High Purity Nitrogen to dry up; Preparation silicon chip etchant solution, etchant solution is the aqueous solution of NaOH and Virahol, wherein NaOH content is 4wt.%, isopropanol content is 7wt.%, use thermostatic oven that solution is heated to 80 ℃ and keep constant temperature, the ready silicon chip cleaning up is put into solution and corrode 40min, silicon chip extracting post-flush is clean, dries up with High Purity Nitrogen.
Adopt pulsed laser deposition (PLD) film coating method to prepare film, the textured mono-crystalline silicon sheet after cleaning and alloys target (Zr75-Co18-Re7wt.%, Re is one or more in La, Ce, Pr, Nd) are put into the sediment chamber of pulsed laser deposition.Use molecular pump that coating system is evacuated to 1 × 10
-4pa, passes into high-purity argon gas (99.99%) to sediment chamber, pressure is stabilized in 3Pa.Open laser transmitter, accurately to the defocused pulse laser of opening, use pulse laser ablation alloy target material, pre-sputtering 10min, to remove target material surface zone of oxidation, starts thin film deposition after pre-sputtering.The energy of pulse laser is that 200mj, frequency are 6Hz, and target-substrate distance is 5cm, and sputtering time is 300min, formation of deposits film under this condition.
Use pulse laser ablation nickel target, deposit again layer of Ni protective layer at the film surface of deposition.The processing parameter of protective layer: pulsed laser energy is that 200mj, frequency are 3Hz, and target-substrate distance is 5cm, and sputtering time is 30min, and ar pressure is 3Pa, and the purity of described nickel target is 99.5wt.%.
The thickness that the present embodiment obtains film air suction layer is 700nm, and columnar organization diameter is 20-30nm, and the thickness of protective layer is 100nm, becomes grainy texture.
Embodiment 4
Adopt pulsed laser deposition (PLD) to prepare double-deck getter film.
First, prepare textured mono-crystalline silicon as deposition substrate.Use successively acetone, alcohol, the each 15min of deionized water ultrasonic cleaning monocrystalline silicon piece, after Wafer Cleaning, use High Purity Nitrogen to dry up; Preparation silicon chip etchant solution, etchant solution is the aqueous solution of NaOH and Virahol, wherein NaOH content is 5wt.%, isopropanol content is 9wt.%, use thermostatic oven that solution is heated to 70 ℃ and keep constant temperature, the ready silicon chip cleaning up is put into solution and corrode 50min, silicon chip extracting post-flush is clean, dries up with High Purity Nitrogen.
Adopt pulsed laser deposition (PLD) film coating method to prepare film, the textured mono-crystalline silicon sheet after cleaning and alloys target (Zr88-Co10-Re2wt.%, Re is one or more in La, Ce, Pr, Nd) are put into the sediment chamber of pulsed laser deposition.Use molecular pump that coating system is evacuated to 1 × 10
-4pa, passes into high-purity argon gas (99.99%) to sediment chamber, pressure is stabilized in 2Pa.Open laser transmitter, accurately to the defocused pulse laser of opening, use pulse laser ablation alloy target material, pre-sputtering 10min, to remove target material surface zone of oxidation, starts thin film deposition after pre-sputtering.The energy of pulse laser is that 100mj, frequency are 6Hz, and target-substrate distance is 5cm, and sputtering time is 300min, formation of deposits film under this condition.
Use pulse laser ablation nickel target, deposit again layer of Ni protective layer at the film surface of deposition.The processing parameter of protective layer: pulsed laser energy is that 50mj, frequency are 6Hz, and target-substrate distance is 5cm, and sputtering time is 30min, and ar pressure is 2Pa, and the purity of described nickel target is 99.5wt.%.
The thickness that the present embodiment obtains film air suction layer is 400nm, and columnar organization diameter is 20-30nm, and the thickness of protective layer is 60nm, becomes grainy texture.
Comparative example 1
Prepare a coarse monocrystalline silicon piece, clean 15min at acetone, alcohol, deionized water for ultrasonic ripple successively, after cleaning, dry up with high pure nitrogen.Adopt pulsed laser deposition (PLD) film coating method to prepare film, silicon chip and alloys target (Zr68 ~ 88-Co10 ~ 24-Re2 ~ 10wt.%, Re is one or more in La, Ce, Pr, Nd) after cleaning are put into sediment chamber.Use molecular pump that coating system is evacuated to 1 × 10
-5~ 1 × 10
-3pa
,pass into high-purity argon gas to sediment chamber, pressure is stabilized in 1 × 10
-4~ 12Pa.Open laser transmitter, accurately to the defocused pulse laser of opening, pre-sputtering 10 ~ 20min, to remove target material surface zone of oxidation, starts thin film deposition after pre-sputtering.The energy of pulse laser, frequency are respectively 100 ~ 500mj, 2 ~ 6Hz, and target-substrate distance is 4 ~ 8cm, and sputtering time is 100 ~ 300min.
The film thickness depositing under this condition is 300nm ~ 1 μ m, and the diameter of columnar organization is about 20 ~ 50nm.Fig. 2 is the schematic diagram of comparative example 1 gained film, and 1 ' is monocrystalline substrate, and 2 ' is air suction layer.
Comparative example 2
Working method is identical with comparative example 1, and unique different place is the film surface deposition layer of Ni protective layer of deposition in comparative example 1.The processing parameter of protective layer: pulsed laser energy, frequency are respectively 50 ~ 200mj, 1 ~ 5Hz, target-substrate distance is 4 ~ 8cm, and sputtering time is 10 ~ 30min, and ar pressure is 0.2 ~ 5Pa, and the purity of described nickel target is 99.5wt.%.
The protective layer thickness obtaining under this processing parameter is 20 ~ 100nm, becomes grainy texture.Fig. 3 is the schematic diagram of comparative example 2 gained films, 1 " and be monocrystalline substrate, 2 " be air suction layer, 3 " be protective layer.
Comparative example 3
Working method is identical with comparative example 1, and the substrate that unique different place is deposit film is selected textured mono-crystalline silicon.The making step of textured mono-crystalline silicon is as follows: (1) is used acetone, alcohol, deionized water ultrasonic cleaning monocrystalline silicon piece 15min successively.(2) preparation silicon chip etchant solution, concrete composition is: NaOH massfraction 1 ~ 5%, Virahol massfraction 2 ~ 10%, use thermostatic oven that solution is heated to 70 ~ 100 ℃ and keep constant temperature, the Si sheet that the 1st step is cleaned up is put into solution and is corroded 30 ~ 100min.After the corrosion of Si sheet, use high pure nitrogen to dry up.
The film thickness that uses textured mono-crystalline silicon to prepare is 300nm ~ 1 μ m, and the diameter of columnar organization is about 20 ~ 50nm, and the effective surface area of film surface increases greatly.Fig. 4 is the schematic diagram of comparative example 3,1 " ' be textured mono-crystalline silicon substrate, 2 " ' be air suction layer.
Contrast test and result
In this experiment, the sample of above-mentioned comparative example 3 and embodiment 1 is carried out to the test of dynamic method pumping property at ambient temperature.The test of film getter room temperature pumping property is to carry out according to standard A STMF798-82 (2002).
Film getter sample is fixed on the middle part of quartz glass samples chamber, first test macro is evacuated to 1 × 10
-51 × 10
-3pa then toasts the metallic conduit (350 ℃, 3h) of testing apparatus in vacuumizing, sample real time temperature is measured by K-type thermocouple, and wherein the temperature in sample chamber remains on 140 ~ 160 ℃, after baking finishes, treat that sample temperature drops to room temperature, and in sample chamber, vacuum tightness maintains 10
-6pa.Pass into test gas (H
2), pressure Pg to 2.7 × 10 of adjusting sample chamber
-4pa, constant Pg, records known capillary conductance the other end Pm over time, calculate gettering rate and accumulation inspiratory capacity, if Fig. 5 is dynamic method pumping property test curve, curve 1,2 represent respectively embodiment 1 and comparative example 3, and wherein the unit of gettering rate is ml/ (scm
-2), the unit of inspiratory capacity is Paml/cm
2.Can see, the gettering rate of embodiment 1 and inspiratory capacity are all apparently higher than comparative example 3.
The sample of embodiment 2-4 is carried out respectively to above-mentioned test, obtain the result similar to embodiment 1, can show that equally the gettering rate of embodiment 2-4 and inspiratory capacity are all apparently higher than the conclusion of comparative example 3.
The air suction layer main raw of getter of the present invention is one or more in Zr, Co and La, Ce, these four kinds of rare earth elements of Pr, Nd, and the main raw of protective layer is Ni.The present invention adopts the preparation of pulsed laser deposition film coating method, and on textured mono-crystalline silicon, deposition is containing the bilayer structure film getter of matcoveredn and air suction layer.Matte substrate can increase getter film useful area, thereby improves gettering rate and inspiratory capacity.Air suction layer surface is coated with Ni protective layer, and Ni has to hydrogen the function of dissociating, and can improve the adsorptive capacity of hydrogen, and protective layer can hinder the absorption of oxygen, reduction activationary temperature.The present invention can realize activation in the process of 180 ~ 350 ℃ of bakings, and after baking, getter has good pumping property at ambient temperature, can be used for, in high vacuum microelectronic device, eliminating inner residual gas.
Claims (10)
1. the Zr-Co-Re film getter with matcoveredn, is made up of air suction layer and protective layer, it is characterized in that: described air suction layer is one or more in Zr, Co and rare earth element La and Ce, Pr, Nd, and protective layer is Ni.
2. the Zr-Co-Re film getter with matcoveredn according to claim 1, it is characterized in that: in described air suction layer, the mass content of Zr is that the mass content of 68 ~ 88%, Co is that one or more mass content in 10 ~ 24%, La, Ce, Pr, Nd is 2 ~ 10%; In described protective layer, the mass content of Ni is 99.5%.
3. the Zr-Co-Re film getter with matcoveredn according to claim 1; it is characterized in that: described air suction layer is a kind of loose columnar structure; Presence of an interface and hole between columnar structure, the diameter of columnar structure is 20 ~ 50nm, the thickness of air suction layer is 300nm ~ 1 μ m.
4. the Zr-Co-Re film getter with matcoveredn according to claim 1, is characterized in that: described protective layer is a kind of loose grainy texture, has gap between particle, and the thickness of protective layer is 20 ~ 100nm.
5. the Zr-Co-Re film getter with matcoveredn according to claim 1, is characterized in that: the activationary temperature of described film getter is 180 ~ 350 ℃.
6. the preparation method of the Zr-Co-Re film getter with matcoveredn described in any one in claim 1-5, comprises the steps:
(1) use successively acetone, alcohol, deionized water ultrasonic cleaning monocrystalline silicon piece, after Wafer Cleaning, use High Purity Nitrogen to dry up;
(2) preparation silicon chip etchant solution, wherein NaOH content is 1 ~ 5wt.%, isopropanol content is 2 ~ 10wt.%, use thermostatic oven that solution is heated to 70 ~ 100 ℃ and keep constant temperature, the silicon chip cleaning up is put into solution and corrode 30 ~ 100min, silicon chip extracting post-flush is clean, dries up with High Purity Nitrogen;
(3) silicon chip substrate of being prepared by step (2) and the alloy target material identical with air suction layer composition are put into the sediment chamber of pulsed laser deposition together, vacuumize and pour high-purity argon gas in sediment chamber, use pulse laser ablation alloy target material, deposition is prepared air suction layer;
(4) the deposition protective layer that uses the same method on the air suction layer of preparing in step (3), uses pulse laser ablation nickel target, and deposition is prepared protective layer.
7. the preparation method of the Zr-Co-Re film getter with matcoveredn according to claim 6, is characterized in that: while preparing air suction layer, the sediment chamber of PLD is vacuumized, when vacuum tightness reaches 1 × 10
-51 × 10
-3when Pa, be 99.99% high-purity argon gas to pouring purity in sediment chamber, ar pressure is 1 × 10
-4~ 15Pa, opens pulse laser after pressure is stable, and laser energy is 100 ~ 500mj, and laser frequency is 2 ~ 6Hz, and target-substrate distance is 4 ~ 8cm, target pre-sputtering 10 ~ 20min, and the thin film deposition time is 100 ~ 300min.
8. the preparation method of the Zr-Co-Re film getter with matcoveredn according to claim 7; it is characterized in that: the laser energy of described pulse laser is 300 ~ 400mj, laser frequency is 5 ~ 6Hz, and target-substrate distance is 5 ~ 6cm; ar pressure is 0.2 ~ 10Pa, and depositing time is 100 ~ 200min.
9. the preparation method of the Zr-Co-Re film getter with matcoveredn according to claim 6; it is characterized in that: while preparing protective layer; ar pressure is 0.2 ~ 8Pa; laser energy is 50 ~ 200mj; laser frequency is 1 ~ 6Hz; target-substrate distance is 4 ~ 8cm, and depositing time is 10 ~ 30min, and the purity of described nickel target is 99.5wt.%.
10. the application of the Zr-Co-Re film getter with matcoveredn described in any one in microelectromechanical systems, flat-panel monitor, sun power heat-insulating shield in claim 1-5.
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