CN109536908A - A kind of Pd/Zr-Co-Ce/Ti film getter and its preparation - Google Patents
A kind of Pd/Zr-Co-Ce/Ti film getter and its preparation Download PDFInfo
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Abstract
The invention discloses a kind of Pd/Zr-Co-Ce/Ti film getter for belonging to film getter preparation technical field and its preparations.Specifically include barrier layer, gettering layer and protective layer from bottom to top；The mass content of Ti is 99.95% or more in barrier layer, and Pd mass content is 99.95% or more in the protective layer；Gettering layer materials include 70~88wt.%Zr, 10~25wt.%Co, 2~5wt.%Ce；The present invention is sequentially depositing barrier layer, gettering layer and protective layer using magnetron sputtering on substrate; Pd/Zr-Co-Ce/Ti film getter obtained can realize activation in 300~450 DEG C, 10~30min; getter after activation has good pumping property at room temperature; and it shows wide in range inspiratory, can be used for eliminating the residual gas inside high vacuum microelectronic component.
Description
Technical field
The invention belongs to film getter preparation technical field, in particular to a kind of Pd/Zr-Co-Ce/Ti film getter
And its preparation.
Background technique
Influence vacuum device performance and the residual activity gas in service life are played to absorb by physics and chemical action and made
Specific function material is referred to as gettering material, referred to as getter or getter.Current main gettering material include with
Evaporable getter material based on barium, strontium, calcium, magnesium and its alloy and metals and its associated alloys such as including Ti, Zr, Hf, Y
Non evaporable getter material.The material, which is mainly used to realize, to be stored in electron tube or maintains and improved in device during one's term of military service
The vacuum quality in portion absorbs device inside residual activity gas, corresponding vacuum environment requirement is reached, to reach
To the performance for promoting device, the service life of device is improved, the purpose of application cost is controlled.
Evaporable air-absorbing agent has biggish activity under normal circumstances, therefore during absorbing to active gases
Absorption efficiency is very fast, has been widely used in the equipment such as kinescope, oscilloscope tube, receiving tube.At the same time, itself is inhaled
Also will will appear shortcoming during gas so that it in the microelectronics vacuum device of part using less.Its limitation
It is: (1) is not suitable for using in the environment of high temperature and pressure；(2) it can not be used in the excessively high electron tube of frequency；(3) exist
It fills in mercury or the electronic device of nitrogen charging, it is impaired to will lead to device performance.
Nonevaporable getter could play its air-breathing after generally requiring the processing of the activation by high temperature or high pressure well
Ability, and the form of material does not change in activation.It is material in high temperature or HIGH PRESSURE TREATMENT process that it, which activates principle,
Oxide on surface can be realized a degree of passivation and decompose, to obtain corresponding activity, make it in active gas
It can occur to react accordingly therewith in environment, to show good gettering ability.Non evaporable getter material is especially suitable
For devices such as travelling-wave tubes, magnetron, infrared detector, gyroscopes.Since its mechanism is not phase during being activated
With, therefore comparatively speaking the material of the material of the type and evaporable has certain advantage: (1) it using the material is inhaled
It can be realized larger amount of air-breathing engineering during gas, and the rate of its air-breathing is very fast；(2) size and shape of the material
Shape is that have certain flexibility, therefore it is suitable for the occupancy in space and little after the material is made
Microdevice；(3) use, active time length etc. can be activated repeatedly.
Common nonevaporable getter includes block getter and film getter again.In recent years, with MEMS device
Micromation and integrated technological trend, need volume smaller, the higher gettering material of unit area gettering ability improving and
Maintain the vacuum quality of device inside.For traditional air suction element since volume is big, activationary temperature is high, is difficult to be directly applied to MEMS true
In empty packaging, and novel thin membranous type gettering material has micromation, unit area gettering ability high, activation technology and device
Vacuum encapsulation process mutually significant advantages such as compatible, in micro-vacuum field using increasingly extensive, therefore in associated vacuum industry
It is also gradually more paid close attention in development.
Film gettering material be by vapor deposition means by non-evaporable getter alloys be deposited on substrate material (Si, Ge,
Metal, glass etc.) on and be made, substrate can be vacuum tube wall, the micro- shell of encapsulation, electronic chip etc..It meets current era
MEMS micro-vacuum device for the demand of gettering material property, can not only guarantee device best effort environment (vacuum,
Anhydrous or inert gas environment), and can be deposited directly on device inner wall before device encapsulation, compared to traditional block
Bulk getter has that space occupancy is small, dimensional accuracy is high, activationary temperature is low, inspiratory capacity is big, without dusting, without welding, technique
The advantages such as compatible.
Realize that the preparation to film gettering material is the method being most widely used at present by magnetron sputtering method, it is excellent
Gesture is that the pellicle film being prepared by this method is uniform, fine and close, internal flaw is few, adhesive force is strong, and can produce
The alloy film of stable components.
Summary of the invention
The purpose of the present invention is to provide a kind of Pd/Zr-Co-Ce/Ti film getter and its preparation, specific technical solutions
It is as follows:
A kind of Pd/Zr-Co-Ce/Ti film getter includes barrier layer, gettering layer and protective layer from bottom to top；
The mass content of Ti is 99.95% or more in the barrier layer, and Pd mass content is 99.95% in the protective layer
More than；
The gettering layer materials include 70~88wt.%Zr, 10~25wt.%Co, 2~5wt.%Ce.
The barrier layer is compact texture, without open gas diffusion paths, with a thickness of 50~300nm；
The gettering layer is porous columar structure, there are interface and gap between columnar structure, column diameter is wide by 20~
100nm, 1~2 μm of gettering layer thickness；
The protective layer is graininess packed structures, there are gap between particle, protective layer with a thickness of 10~50nm.
The activationary temperature of the Pd/Zr-Co-Ce/Ti film getter be 300~450 DEG C, activationary time be 10~
30min。
The Pd/Zr-Co-Ce/Ti film getter is using monocrystalline silicon as substrate.
The preparation method of the Pd/Zr-Co-Ce/Ti film getter the following steps are included:
(1) it is utilized respectively SPM solution, alcohol, deionized water cleaning monocrystalline silicon piece, the SPM solution is by H2SO4、H2O2With
4:1 volume ratio is mixed to get；
(2) obtained by the step (1) on monocrystalline silicon piece magnetron sputtering depositing Ti film as barrier layer；
(3) magnetron sputtering deposits Zr-Co-Ce film as gettering layer over the barrier layer；
(4) magnetron sputtering deposits Pd film as protective layer on gettering layer.
In the step (1), silicon wafer is impregnated to 10~20min in SPM solution first, then successively with alcohol, go from
Sub- water is respectively cleaned by ultrasonic 5~15min.
Before step (2) the depositing Ti film, first carry out pre-sputtering remove target material surface oxide layer: coating system it is true
Reciprocal of duty cycle reaches 1.0 × 10-6~1.0 × 10-4When Pa, it is passed through the high-purity argon gas of purity 99.99999% into chamber, gas will be sputtered
Voltage-controlled system is in 0.2~1Pa, 50~200W of sputtering power, 4~8cm of target-substrate distance, 10~20min of pre-sputtering.
The back end vacuum of coating chamber is evacuated to 1.0 × 10 in the step (2)-6~1.0 × 10-4Pa, then into chamber
It is passed through high-purity argon gas, sputtering pressure is 0.2~1Pa, and 50~200W of sputtering power, target-substrate distance is 4~8cm, sedimentation time 30
~120s.
Sputtering pressure is 2~8Pa in the step (3), and 50~200W of sputtering power, target-substrate distance is 4~8cm, when deposition
Between be 30~60min.
Sputtering pressure is 0.2~3Pa in the step (4), and 50~200W of sputtering power, target-substrate distance is 4~8cm, deposition
Time is 5~30s.
Ti metal targets, the purity of Pd metal targets are 99.95% or more in the step (2), (4).
Pd/Zr-Co-Ce/Ti film getter provided by the invention can be in lower temperature (300~450 DEG C) and shorter
Activation is realized in time (10~30min), the getter after activation has good pumping property, and table at room temperature
Reveal wide in range inspiratory, can be used for eliminating the residual gas inside high vacuum microelectronic component.
The invention has the benefit that
(1) present invention is using Zr, Co and rare earth element ce as air-breathing target material composition, and wherein Zr is main gettering material；
The effect of Co is to form solid solution with Zr, increases lattice parameter, increases the radius of interstitial void position, is conducive to hydrogen atom and is inhaling
Diffusion in gas agent；The activity ratio Zr high that rare earth element ce is shown, so ZrO2It can be restored by rare earth metal；
(2) for the present invention using Ti film as barrier layer, compact structure, there is no open gas diffusion paths, can be effective
Prevent substrate adsorbed gas to the diffusion of main film body gettering layer, and then playing prevents substrate deflation from film activity being caused to reduce
The effect that poisons that substrate is deflated to getter film is effectively reduced in effect, while being also beneficial to adjust the microstructure of getter film,
Obtain more preferably pumping property；
(3) the Zr-Co-Ce gettering layer of present invention deposit perfect porous columar structure in Ti film barrier layer, is increasing
While film specific surface area active, more diffusions are provided to the diffusion inside film and are led to for active gases molecule or ion
Road shows wide in range pumping property to various active gases, can also be adsorbed on the gas of substrate release during activated at
Body；
(4) the Pd protective layer that the present invention deposits on Zr-Co-Ce gettering layer is graininess packed structures, is conducive to gas
Molecule in the absorption of film surface and to the further diffusion inside film, while it is possible to prevente effectively from body layer it is open
Surface long term exposure atmosphere and caused by aoxidize, and since Pd penetrates characteristic to the selection of H, be conducive to H2In the suction of film surface
Echo dissociation diffusion；Simultaneously Pd metal active it is lower with respect to Zr, inoxidizability is strong, can be effectively reduced body layer because it is long when
Between contact reactive atmosphere and caused by activity surface and interface forfeiture a possibility that so that the adsorption rate and air-breathing of film
Amount maintains relatively high level in a long time, hence it is evident that improves the pumping property of film；
(5) Pd/Zr-Co- is made using barrier layer, gettering layer and protective layer is sequentially depositing on magnetron sputtering substrate in the present invention
Ce/Ti film getter, it is not in lining during being prepared that preferably with MEMS technology compatibility, deposition rate is fast
The excessively high situation of bottom temperature rise, and not will cause the damage of film layer, be conducive to the film that high quality is prepared, effectively improve
The microstructure of film is more advantageous to the absorption of gas molecule and the diffusion inside film.
(6) Pd/Zr-Co-Ce/Ti film getter provided by the invention can be applied in microelectromechanical systems
(MEMS), the vacuum level requirements such as flat-panel monitor, solar energy heat-insulating shield are high, require activation condition in harsh environment.
Detailed description of the invention
Attached drawing 1 is the structural schematic diagram of Pd/Zr-Co-Ce/Ti film getter of the invention；
Attached drawing 2 is the structural schematic diagram of film getter in comparative example 1；
Attached drawing 3 is the structural schematic diagram of film getter in comparative example 2；
Attached drawing 4 is the structural schematic diagram of film getter in comparative example 3；
Attached drawing 5 is the contrast curve chart of embodiment 1 and 1~3 dynamic method testing film pumping property of comparative example；
Label declaration: 1- substrate；The barrier layer 2-；3- gettering layer；4- protective layer.
Specific embodiment
The present invention provides a kind of Pd/Zr-Co-Ce/Ti film getter and its preparations, with reference to the accompanying drawings and examples
The present invention is described further.
The present invention has the three of barrier layer, gettering layer and protective layer in monocrystalline substrate surface deposition using magnetron sputtering method
The getter film of film structure；The structural schematic diagram of three-decker film getter in the present invention is as shown in Figure 1, in substrate 1
Upper plating barrier layer 2, plates gettering layer 3 on barrier layer 2, and the plating 4 on gettering layer 3 forms the Pd/Zr- of sandwich structure
Co-Ce/Ti film getter.
Embodiment 1
The film getter of magnetron sputtering method preparation three-decker is utilized using following step:
(1) by monocrystalline silicon piece in SPM solution (H2SO4:H2O2=4:1) in impregnate 10~20min, then successively with alcohol,
Deionized water is respectively cleaned by ultrasonic 5~15min, is finally dried up with high pure nitrogen；
(2) film is prepared using magnetron sputtering method, the monocrystalline silicon piece after cleaning is put into coating chamber, and by Ti metal
Target, Zr84.95Co12.39Ce2.66Alloy target material (by quality proportioning), Pd metal targets are mounted on corresponding target position；Unlatching machine
The back end vacuum of coating system is evacuated to 1.0 × 10 by tool pump and molecular pump-6~1.0 × 10-4Pa is passed through into chamber
99.99999% high-purity argon gas adjusts sputtering pressure and stablizes in 3Pa, opens shielding power supply and start pre-sputtering, pre-sputtering 15min
To ensure that the oxide layer of target material surface is thoroughly removed；Then start to deposit barrier film, rotation sample carrier makes substrate face
The position of Ti target, adjusting sputtering pressure are 0.2Pa, sputtering power 100W, target-substrate distance 6cm, sedimentation time 60s, are formed fine and close
Ti film barrier layer；
(3) on the barrier layer Ti, rotation sample carrier makes the position of substrate face Zr-Co-Ce alloy target material, adjusts sputtering gas
It is pressed onto 3Pa, sputtering power 100W, target-substrate distance 6cm, sedimentation time 60min, forms the Zr-Co-Ce air-breathing of porous columar structure
Layer；
(4) rotation sample carrier makes the position of substrate face Pd target, adjusts sputtering pressure to 0.5Pa, sputtering power 50W,
Target-substrate distance 6cm, sedimentation time 5s form the Pd protective layer of graininess packed structures on the surface of gettering layer；The Pd target
Purity is 99.95%.
Ti film barrier layer made from embodiment 1 with a thickness of 100nm, be compact texture；The thickness of Zr-Co-Ce gettering layer
Degree is 1.8 μm, the wide 20~100nm of column crystal；Pd protective layer with a thickness of 10nm, be in particle packing structure.
Embodiment 2
The film getter of magnetron sputtering method preparation three-decker is utilized using following step:
(1) by monocrystalline silicon piece in SPM solution (H2SO4:H2O2=4:1) in impregnate 10~20min, then successively with alcohol,
Deionized water is respectively cleaned by ultrasonic 5~15min, is finally dried up with high pure nitrogen；
(2) film is prepared using magnetron sputtering method, the monocrystalline silicon piece after cleaning is put into coating chamber, and by Ti metal
Target, Zr-Co-Ce alloy target material, Pd metal targets are mounted on corresponding target position；Membrane system will be plated by opening mechanical pump and molecular pump
The back end vacuum of system is evacuated to 1.0 × 10-6~1.0 × 10-4Pa is passed through high-purity argon gas (99.99999%) into chamber, and adjusting is splashed
Stable gas pressure is penetrated in 3Pa, shielding power supply is opened and starts pre-sputtering, pre-sputtering 15min is thorough with the oxide layer for ensuring target material surface
It removes at bottom；Then start to deposit barrier film, rotation sample carrier makes the position of substrate face Ti target, adjusts sputtering pressure and is
0.5Pa, sputtering power 100W, target-substrate distance 6cm, sedimentation time 60s form fine and close Ti film barrier layer；
(3) on the barrier layer Ti, rotation sample carrier makes the position of substrate face Zr-Co-Ce alloy target material, adjusts sputtering gas
It is pressed onto 5Pa, sputtering power 100W, target-substrate distance 6cm, sedimentation time 60min, forms the Zr-Co-Ce air-breathing of porous columar structure
Layer；
(4) rotation sample carrier makes the position of substrate face Pd target, adjustment sputtering pressure to 1.5Pa, sputtering power 50W,
Target-substrate distance 6cm, sedimentation time 10s form the Pd protective layer of graininess packed structures on the surface of gettering layer；The Pd target
Purity is 99.95%；
The Ti film barrier layer that embodiment 2 obtains with a thickness of 120nm, be compact texture；The thickness of Zr-Co-Ce gettering layer
Degree is 1.9 μm, the wide 20~100nm of column crystal；Pd protective layer with a thickness of 22nm, be in particle packing structure.
Embodiment 3
The film getter of magnetron sputtering method preparation three-decker is utilized using following step:
(1) by monocrystalline silicon piece in SPM solution (H2SO4:H2O2=4:1) in impregnate 10~20min, then successively with alcohol,
Deionized water is respectively cleaned by ultrasonic 5~15min, is finally dried up with high pure nitrogen；
(2) film is prepared using magnetron sputtering method, the monocrystalline silicon piece after cleaning is put into coating chamber, and by Ti metal
Target, Zr-Co-Ce alloy target material, Pd metal targets are mounted on corresponding target position；Membrane system will be plated by opening mechanical pump and molecular pump
The back end vacuum of system is evacuated to 1.0 × 10-6~1.0 × 10-4Pa is passed through high-purity argon gas (99.99999%) into chamber, and adjusting is splashed
Stable gas pressure is penetrated in 3Pa, shielding power supply is opened and starts pre-sputtering, pre-sputtering 15min is thorough with the oxide layer for ensuring target material surface
It removes at bottom；Then start to deposit barrier film, rotation sample carrier makes the position of substrate face Ti target, adjusts sputtering pressure and is
0.2Pa, sputtering power 100W, target-substrate distance 6cm, sedimentation time 60s form the fine and close barrier layer Ti；
(3) on the barrier layer Ti, rotation sample carrier makes the position of substrate face Zr-Co-Ce alloy target material, adjusts sputtering gas
It is pressed onto 8Pa, sputtering power 100W, target-substrate distance 6cm, sedimentation time 60min, forms the Zr-Co-Ce air-breathing of porous columar structure
Layer；
(4) rotation sample carrier makes the position of substrate face Pd target, adjustment sputtering pressure to 3Pa, sputtering power 50W, target
Cardinal distance 6cm, sedimentation time 10s form the Pd protective layer of graininess packed structures on the surface of gettering layer；The Pd target it is pure
Degree is 99.95%.
The Ti film barrier layer that embodiment 3 obtains with a thickness of 100nm, be compact texture；The thickness of Zr-Co-Ce gettering layer
Degree is 2 μm, the wide 20~100nm of column crystal；Pd protective layer with a thickness of 25nm, be in particle packing structure.
Comparative example 1
In monocrystalline silicon piece Direct precipitation Zr-Co-Ce film gettering layer:
By monocrystalline silicon piece in SPM solution (H2SO4:H2O2=4:1) in impregnate 10~20min, then successively with alcohol, go
Ionized water is respectively cleaned by ultrasonic 5~15min, is finally dried up with high pure nitrogen；Film is prepared using magnetron sputtering method, after cleaning
Silicon wafer is fitted into coating chamber, and installs Zr-Co-Ce alloy target material, and the back end vacuum of vacuum system is evacuated to 1.0 × 10-6~
1.0×10-4Then Pa is passed through high-purity argon gas (99.99999%) into chamber, sputtering pressure is controlled in 3Pa, pre-sputtering 10
Then~20min starts to deposit air-breathing layer film, sputtering pressure is 2~8Pa, sputtering power to remove target material surface oxide layer
50~200W, target-substrate distance are 4~8cm, and sedimentation time is 30~60min；
The Zr-Co-Ce film gettering layer that comparative example 1 deposits is porous with a thickness of 1~2 μm, the wide 20~100nm of column diameter
Column structure；Fig. 2 is the resulting film schematic diagram of comparative example 1, is only coated with gettering layer 3 on substrate 1.
Comparative example 2
On monocrystalline silicon piece depositing Ti barrier layer, Zr-Co-Ce film gettering layer:
Operating method is identical as comparative example 1, increases by one layer of barrier layer Ti between Zr-Co-Ce gettering layer and substrate, specifically
Technological parameter: 0.2~1Pa of sputtering pressure, 50~200W of sputtering power, 4~8cm of target-substrate distance, 30~120s of sedimentation time.
Ti film barrier layer prepared by comparative example 2 is compact texture with a thickness of 50~300nm；Fig. 3 is 2 gained of comparative example
The schematic diagram of film plates barrier layer 2 on substrate 1, and gettering layer 3 is plated on barrier layer 2.
Comparative example 3
Zr-Co-Ce film gettering layer, Pd protective layer are deposited in monocrystalline silicon piece:
Operating method is identical as comparative example 1, deposits one layer of Pd protective layer, the purity of Pd target in Zr-Co-Ce air-breathing layer surface
It is 99.95%, specific technological parameter: 0.2~3Pa of sputtering pressure, 50~200W of sputtering power, 4~8cm of target-substrate distance, deposition
5~30s of time.
Thinfilm protective coating prepared by comparative example 3 is in particle packing state with a thickness of 10~50nm；Fig. 4 is that 3 gained of comparative example is thin
The schematic diagram of film plates gettering layer 3, the plating 4 on gettering layer 3 on substrate 1.
Dynamic method pumping property survey is carried out at room temperature to getter made from Examples 1 to 3 and comparative example 1~3
Examination, testing standard is carried out according to standard ASTMF798-97, and specific testing procedure is as follows:
(1) film sample is fixed in sample room, then extracts the foreign gas in test macro using vacuum pump group,
Internal system vacuum degree is set to be higher than 3.0 × 10-3Pa；
(2) baking oven power supply is opened, is handled by high-temperature baking and thoroughly goes the residual gas for being adsorbed on metal pipe internal wall
It removes, the temperature setting of baking is 250 DEG C, baking time 3h；
(3) heat activation processing is carried out to sample after bakeout degassing is completed, is needed when being activated using K-type
Thermocouple is monitored the temperature of sample；
(4) it when the temperature of sample drops to room temperature, needs high-purity to be passed through into test macro by corresponding regulating valve
Argon gas controls sample chamber pressure Pg 1.0 × 10-4Pa, record Pm change with time, and calculate gettering rate and air-breathing
Amount.
Fig. 5 is Examples 1 to 3, the dynamic method pumping property of getter made from comparative example 1~3 at room temperature is surveyed
Try curve, it can be seen that the gettering rate and inspiratory capacity of Examples 1 to 3 are obviously higher than comparative example 1~3.
Claims (8)
1. a kind of Pd/Zr-Co-Ce/Ti film getter, which is characterized in that including barrier layer, gettering layer and guarantor from bottom to top
Sheath；
The mass content of Ti is 99.95% or more in the barrier layer, in the protective layer Pd mass content be 99.95% with
On；
The gettering layer materials include 70~88wt.%Zr, 10~25wt.%Co, 2~5wt.%Ce.
2. Pd/Zr-Co-Ce/Ti film getter according to claim 1, which is characterized in that the barrier layer is densification
Structure, without open gas diffusion paths, with a thickness of 50~300nm；
The gettering layer is porous columar structure, and there are interface and gap between columnar structure, the wide 20~100nm of column diameter inhales
1~2 μm of gas pay thickness；
The protective layer is graininess packed structures, there are gap between particle, protective layer with a thickness of 10~50nm.
3. Pd/Zr-Co-Ce/Ti film getter according to claim 1, which is characterized in that the Pd/Zr-Co-Ce/
The activationary temperature of Ti film getter is 300~450 DEG C, and activationary time is 10~30min.
4. Pd/Zr-Co-Ce/Ti film getter according to claim 1, which is characterized in that the Pd/Zr-Co-Ce/
Ti film getter is using monocrystalline silicon as substrate.
5. the preparation method of any one of Claims 1 to 4 Pd/Zr-Co-Ce/Ti film getter, which is characterized in that packet
Include following steps:
(1) it is utilized respectively SPM solution, alcohol, deionized water cleaning monocrystalline silicon piece, the SPM solution is by H2SO4、H2O2With 4:1 body
Product ratio is mixed to get；
(2) obtained by the step (1) on monocrystalline silicon piece magnetron sputtering depositing Ti film as barrier layer；
(3) magnetron sputtering deposits Zr-Co-Ce film as gettering layer over the barrier layer；
(4) magnetron sputtering deposits Pd film as protective layer on gettering layer.
6. preparation method according to claim 1, which is characterized in that the back end vacuum of coating chamber in the step (2)
It is evacuated to 1.0 × 10-6~1.0 × 10-4Then Pa is passed through high-purity argon gas into chamber, sputtering pressure is 0.2~1Pa, sputters function
50~200W of rate, target-substrate distance are 4~8cm, and sedimentation time is 30~120s.
7. preparation method according to claim 1, which is characterized in that sputtering pressure is 2~8Pa in the step (3), is splashed
50~200W of power is penetrated, target-substrate distance is 4~8cm, and sedimentation time is 30~60min.
8. preparation method according to claim 1, which is characterized in that sputtering pressure is 0.2~3Pa in the step (4),
50~200W of sputtering power, target-substrate distance are 4~8cm, and sedimentation time is 5~30s.
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