CN107541713A - Carry method and its system that energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film - Google Patents
Carry method and its system that energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film Download PDFInfo
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Abstract
The invention discloses the method and its system that a kind of load energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film, substrate is used as using inorganic or organic substrate, before thin film deposition, sputter clean, activation and planarization process are carried out to substrate using energy ionized cluster beam beam is carried；DLC film is deposited in substrate surface using PECVD method, while the DLC film of deposition bombarded using energy ionized cluster beam beam is carried, obtains the DLC film of high compaction.Consistency, wearability, hardness and the film/base junction for substantially increasing DLC film in this way are made a concerted effort.Present invention process is easily controllable, can be applied to the surface plating diamond film in various instruments and part.
Description
Technical field
The present invention relates to a kind of preparation method of DLC film and its device, more particularly to a kind of chemical vapor deposition
Product prepares the method and its device of DLC film, applied to nanocomposite structural membrane preparing technical field.
Background technology
Carbon material plays an important role in the evolution of the mankind, and the extensive use of carbon material promotes industry
It is fast-developing.Into after 20th century, particularly the 1950s, under the background of world technology great development, occur in succession
Carbon fiber and its composite, diamond, carbon molecules and carbosphere, CNT, graphene etc..These new carbon materials
Characteristic can almost cover the even opposed two kinds of property of property of all substances on the earth, such as from most firmly to dead-soft,
From full extinction to full impregnated light, again to superconductor from insulator to semiconductor, from thermal insulation to good heat conduction, from paramagnetic to ferromagnetic, from super
Low-friction coefficient is to superelevation coefficient of friction, from surface super hydrophilic to super-hydrophobic etc..
In numerous carbon materials, DLC film causes worldwide widely studied heat with its excellent performance
Tide.DLC film is mainly the sp by diamond lattic structure3The sp of hydbridized carbon atoms and graphite-structure2Hydbridized carbon atoms are mutual
The three-dimensional network mixed is formed, usually amorphous state or amorphous-nano-crystalline composite construction.DLC carbon-base film has height
Hardness, excellent anti-wear and wear-resistant performance, high heat conductance, low-k, broad-band gap, good optical transmission and excellent
Chemical inertness and biocompatibility, in Aero-Space, machinery, electronics, optics, decorative appearance protection, the field such as biomedicine
Have broad application prospects.
Chemical vapor deposition processes include following three common key elements：1. one or several kinds of chemical reaction gas or liquid
The steam of body；2. the thermal source for promoting gas to chemically react；3. vacuum system, for keeping specific pressure, and arrange in time
Go out the accessory substance of chemical reaction.
And plasma enhanced chemical vapor deposition PECVD then introduces four elementses：Plasma.Plasma
Energy effect allow chemical vapour deposition reaction under relatively low substrate temperature with higher growth rate film.
PECVD is one kind in numerous chemical vapour deposition techniques, its integrated use glow plasma discharge and chemical vapor deposition
Technique is accumulated to grow solid film.During PECVD growing films, film can be easily controlled by adjusting technological parameter
Thickness and microstructure, compactness and stability good film uniform to obtain thickness and performance.PECVD is due to deposition
The advantages that temperature is low, diffractive good and one of as the most frequently used method of preparation DLC film.In gas discharge plasma
In, because low -velocity electron and gas atom collide, in addition to producing positive and negative ion, it can also produce substantial amounts of excited atom, molecule
Isoreactivity base, so as to greatly enhance the activity of reacting gas.Easily chemically reacted between these active components, and in life
Reaction heat is released while into reaction product.Therefore, in the low pressure nonequilibrium plasma of pecvd process process, high energy particle
Energy is provided for source material particle, it is not necessary to which extra heating can be to promote the generation of chemical reaction, so as to reduce macroscopic view
Chemical reaction temperature, make it possible the chemical reaction for being difficult to occur originally or reaction speed is very slow, this is namely
The basic reason of pyroreaction can be realized at low temperature.
The advantages of pecvd process, mainly there is at following 4 points：
1. substrate temperature can be greatly reduced.Particularly when material containing non-refractory in substrate, plasma increases
It is strong particularly necessary；
2. because plasma can greatly improve the ionization level of reacting gas, required gas gross can is reacted
Correspondingly reduce, so both reduced the consumption of high pure raw material, reduce cost, the discharge capacity of waste gas can be reduced again；
3. the sedimentation rate of film can be significantly improved；
4. the quality of film can be significantly improved, including uniformity of the uniformity of film thickness and performance etc..
According to the difference in plasma exciatiaon source, common PECVD technique has：Direct current glow discharge method, radio-frequency glow are put
Electrical method, electron cyclotron resonace (ECR) chemical vapor deposition etc..Occur pair that sedimentation rate is high and depositional area is big again in recent years
Radio frequency-direct current glow discharge (RF-DC) method, microwave-radio frequency (MW-RF) electric glow discharge method, electron cyclotron resonace-radio frequency (ECR-
RF) method etc..Here, the application of DLC film, Application No. CN201010246958.0 patent document are prepared as PECVD
Disclose and DLC film is deposited in PC resin using PECVD；Application No. CN201210398578.8 patent document discloses
The film of hydrocarbon polymer is deposited in flexible transistor using PECVD, to reach insulation effect；Application No.
CN201410671812.9 patent document, which discloses, is directly deposited on DLC film on aluminium base using PECVD；Application number
For CN201510456355.6 patent document disclose using PECVD technique large area prepare DLC film a kind of producer
Formula；Application No. CN201310157257.3 patent document discloses the DLC that 0.01-0.05um is prepared for using PECVD
One layer as fastness wear-resistant composite film of film.Simple PECVD technique growth DLC film, its coatings growth speed are several
Hundred nano-micrometres/hour.Because PECVD uses lower temperature growth process, its deposition velocity is too fast to cause membrane structure is loose to draw
Lower hardness is played, while the adhesion of film and substrate is weaker.
In field of vacuum coating, the load energy ion beam formed using the single atom after ionization under electric field acceleration comes auxiliary
Furtherance film directly participates in film to grow being a kind of routine techniques., can be in substrate material under load energy Assisted by Ion Beam effect
Expect that surface obtains the coating with compared with strong adhesive force and higher-density.But in this conventional bombardment process for carrying energy ion beam
In, the volume due to carrying energy ion is only equivalent to the volume size of single atom, and the movement velocity of ion is higher, then no
The injection phenomenon and sputtering phenomenon again of high-speed ion can occur with can avoiding.The former means that carrying energy ion is shot in in film
Portion depths, cause the impurity and microstructural defects for occurring higher density in film；The latter refers to carrying the table of energy ion and film
Face atom collides so that the atom of film surface leaves film, and this causes the speed of growth of film to slow down and significant loss.
In recent decades, on the basis of conventional ion beam, people proposed with load energy ionized cluster beam come generation exploratoryly
For single ion.The original research of ionized cluster beam, which starts from, is used for nanoprocessing the 1970s, from intert-gas atoms group,
Such as Arn, n=1000-3000, precious metal atom group arrive micel, such as B18H24, then the molecule C to discovery in 198560, ionization original
The unique texture and its unusual electricity, magnetics, optical property and chemical reaction characteristic of son group are found in succession, are caused a variety of
The common concern of subject, carrying the research of energy ionized cluster beam turns into multi-disciplinary joint, also turns into different interdisciplinary bridges
Beam and tie.At present, the research on carrying energy ionized cluster beam also focuses primarily upon formation mechenism and the effect of ionized cluster beam
Mechanism Study, and attempt the technology to be applied to semiconductor ultra-shallow junctions, material surface planarization, ultrathin nanometer material on this basis
Expect preparation field.Through inquiry, there is presently no see to prepare the reinforcing of the compactness of DLC film using energy ionized cluster beam beam is carried
The related report of technology, but perform etching technique and other related process using load energy ionized cluster beam beam.Application number
A kind of halogen-free gas cluster ion beam etching technics removal part is disclosed for CN201510131248.6 patent document
The copper metal layer of thickness；CN201480073422.X patent document discloses a kind of cluster gas for being used to perform various materials
The method and system of ion beam (GCIB) etching process；Application No. CN201410172010.3 patent document discloses one kind
Prepare the effect of cluster ions beam in FinFIET devices；Application No. CN201480023532.5 patent document discloses one
The method that kind is used to handle substrate surface uses neutral beam irradiation and resulting bag from gas cluster ion beam
Include the product of photoetching photomask-blank.
So-called ionized cluster beam is exactly to be initially formed the atomic group formed with hundreds and thousands of individual atoms, then ionizes the atom
Roll into a ball to obtain ionized cluster beam.On the basis of this thinking, people have made many trials, thus develop ionized cluster beam beam
Coating technique and process for modifying surface.The main points of ionized cluster beam beam technology are exactly to have increased considerably the quality for carrying energy ion,
Under conditions of the identical kinetic energy of load energy ion is assigned, because the mass of ion of atomic group is significantly larger than monatomic ion quality, institute
It is far smaller than the speed of the latter with the former movement velocity.Therefore, low speed and the ionized cluster beam of large volume will not be injected into thin
Inside film, and its surface region can only be had an effect, this reduces the impurity in film and defect.This causes ionization atom
Group, which can apply, is also mainly limited to the surface modification technologies such as material surface planarization, can ionization atom using load but without seeing
Group's beam is reported to prepare the related of the compactness reinforcement technique of DLC film.But actual conditions are, existing PECVD technique is overcome
Gone forward side by side in preparation DLC film technique between caused film/substrate the problem of adhesion weakness, density of film and lower hardness
One step influences DLC film in the service life in the machine applications such as cutter and mould field, significantly improves thin film surface planeness
Have become technical problem urgently to be resolved hurrily with thin film mechanical performance, it is great to the industry application value of DLC film.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Method and its system that energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film are carried, utilizes and carries energy ionized cluster beam
The intensive flotation of beam, significantly improve thin film surface planeness and thin film mechanical performance, prepared using conventional PECVD process
While DLC film, surface ion bombardment is carried out to the film grown to carry energy ionized cluster beam beam.Using this it is improved from
Beamlet assisted deposition processes can significantly improve the adhesion of film/substrate, film compactness and hardness, so as to increase substantially
Service life of the DLC film in the machine applications such as cutter and mould field.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of method that load energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film, can ionization original using carrying
The DLC film of sub- group's beam bombardment chemical vapour deposition technique growth, carry the bombardment DLC film and chemical gaseous phase of energy ionized cluster beam beam
Deposit DLC film to carry out simultaneously or alternately, while by adjusting the power of PECVD film forming, so as to which densification be prepared
DLC film.
As currently preferred technical scheme, before PECVD deposition DLC films are carried out, carrier substrate is carried out clear
Wash and dry, then with carry can ionized cluster beam beam bombardment carrier substrate surface, the surface of carrier substrate is carried out sputter clean,
Activation and planarization pretreatment.Before DLC film deposition is carried out, carrier substrate first passes around pretreatment and ionized cluster beam beam
Cleaning pretreatment comprehensive pretreatment, it is therefore an objective to remove surface adsorbate and oxide layer, it is often more important that formed on surface greatly
The dangling bonds of amount, these dangling bonds have very strong activity, so as to get deposition and atomic and ion up to surface are easy to and baseplate material
Strong bonded is formed, so as to improve adhesive strength of the plated film to matrix.
As the further preferred technical scheme of such scheme, the bombardment DLC film for carrying energy ionized cluster beam beam is utilized
When, the gas for forming ionized cluster beam beam is Ar, N2With any one gas in the gas containing carbons or any several mixed
Close gas；When carrying out PECVD deposition DLC films, the gas for participating in chemical gas phase reaction is appointing in the gases such as alkane, alkene and acetylenic
Anticipate a kind of gas or any several mixed gas.
As the further preferred technical scheme of such scheme, the bombardment DLC film for carrying energy ionized cluster beam beam is utilized
When, the gas containing carbons as the gas for forming ionized cluster beam beam includes CO2、CH4And C2H2；It is thin to carry out PECVD depositions DLC
During film, the gas for participating in chemical gas phase reaction is CH4And C2H2In any one gas or two kinds of mixed gas.
Above-mentioned carrier substrate preferably using monocrystalline silicon, glass, stainless steel, metallic aluminium, magnesium alloy, lucite, BT,
PPE or PET material are made.Substrate can use inorganic substrate or organic substrate, wherein inorganic substrate include monocrystalline silicon, sheet glass,
Stainless steel, metallic aluminium and magnesium alloy, organic substrate include lucite and BT, PPE and PET resin.
As currently preferred technical scheme, the accelerating potential applied to carrying energy ionized cluster beam beam is 500V-20kV；
When carrying out PECVD deposition DLC films and when utilizing the bombardment DLC film for carrying energy ionized cluster beam beam, setting substrate temperature is 25-
250 DEG C, it is 0.5-1.5Pa that pressure in vacuum tank scope is kept in coating process.When the present invention prepares DLC film, at 25 DEG C to 250
Under the conditions of DEG C, PECVD devices can each lead into gas with load in ionized cluster beam bundle device, can ionization original using PECVD and load
Son group's beam excitation apparatus deposits and carried energy ionized cluster beam to substrate alternately DLC film and bombards, or utilizes PECVD and load
Energy ionized cluster beam beam excitation apparatus carries out DLC film deposition to substrate and carries energy ionized cluster beam bombardment simultaneously, so as to realize
Carrying can ionized cluster beam beam auxiliary PECVD deposition DLC film.In order to improve the adhesion of film/substrate, film compactness with it is hard
The performance of the terms of mechanics such as degree, in the method that the present invention prepares DLC film, on energy ionized cluster beam beam excitation apparatus is carried,
The energy of ionized cluster beam beam can be changed by changing the voltage of accelerating field.
As the further preferred technical scheme of such scheme, the accelerating potential applied to carrying energy ionized cluster beam beam is
1500V-15kV；When carrying out PECVD deposition DLC films and when utilizing the bombardment DLC film for carrying energy ionized cluster beam beam, base is set
Plate temperature is 50-175 DEG C.
As the technical scheme still more preferably of such scheme, the accelerating potential applied to carrying energy ionized cluster beam beam
For 1500-9000V；When carrying out PECVD deposition DLC films and when utilizing the bombardment DLC film for carrying energy ionized cluster beam beam, set
Substrate temperature is 50-100 DEG C.
A kind of present invention that implements carries the enhancing that energy ionized cluster beam beam assistant chemical vapor deposition prepares the method for DLC film
Type PECVD system, including back cavity body device and ante-chamber body device, back cavity body device are load energy ionized cluster beam beam activating system,
Ante-chamber body device is PECVD system, carries the ionized cluster beam beam activating system chamber and PECVD of energy ionized cluster beam beam activating system
System inner chamber connects to form sysplex chamber, can ionized cluster beam beam activating system and PECVD system this two systems carrying
Between be provided with bonding in vacuum system, can carry out vacuum adjustment and control to sysplex chamber using bonding in vacuum system,
In sysplex chamber, the ionized cluster beam beam activating system chamber and PECVD system of energy ionized cluster beam beam activating system are being carried
Set baffle plate to separate between inner chamber, while opening is provided with baffle plate, the load for enabling load ionized cluster beam beam activating system to export
Can ionized cluster beam beam from the opening through rear, shine directly on the substrate surface being arranged in PECVD system inner chamber, utilize
Carry the beam bombardment of energy ionized cluster beam and the DLC film of chemical vapour deposition technique growth, control load energy are utilized in PECVD system inner chamber
The bombardment DLC film technique of ionized cluster beam beam is carried out or alternately simultaneously with chemical vapor deposition DLC film technique, simultaneously
By adjusting the power of PECVD film forming, so as to which the DLC film of densification be prepared on carrier substrate.
As the enhanced preferable technical scheme of PECVD system of the present invention, it is main to carry energy ionized cluster beam beam activating system
Unit, the ionization unit of atomic group are formed by atomic group and the atomic group of ionization is accelerated to carry energy ion cluster beam to be formed
It is all logical to form unit, the ionization unit of atomic group and accelerating field unit for accelerating field unit and baffle plate composition, wherein atomic group
Installation cooling device is crossed to cool, to maintain being stabilized for atomic group and ion cluster；In a pecvd system, pending growth
The carrier substrate of DLC film is fixedly installed on rotatable work rest, when carrying out PECVD deposition DLC films, work rest energy
Carrier substrate is driven to be rotated.
The principle of the present invention：
On the basis of traditional pecvd process, present invention introduces energy ionized cluster beam beam is carried, formed and carry energy ionization atom
Group's beam auxiliary pecvd process, on the basis of original higher film forming speed of pecvd process is kept, to carry energy ionized cluster beam beam
To improve the internal structure of film, consistency and hardness, and improve DLC film and the adhesion of substrate.
The present invention mainly pays attention to the real-time pre-control of following drip irrigation device：
First, carrying can ionized cluster beam beam energy：
Ionized cluster beam is by tens or hundreds of, or even thousands of individual atoms or molecular composition and the aggregation for carrying an electric charge
Body, such ionized cluster beam can form the load energy ion beam current of directed movement under accelerating field effect.Carrying can ionization original
The particle that son group is rolled into a ball from the energy that accelerating field is obtained by composed atom is divided equally, and is such as accelerated with 10kV voltage by 500 originals
Molecular ionized cluster beam, the kinetic energy that each atom obtains in atomic group is about 20eV, and the atom of this low kinetic energy can not
Intrinsic silicon depths can be injected into, and can only be dispersed in substrate surface or near-surface region.Further, since entrained by each atom
Kinetic energy and little, therefore density is relatively low the defects of it after film surface atomic collision to forming.
Ionized cluster beam quality is big, and its inertia is also big, and when it is collided with film surface, inelastic collision only can occur, because
This it most energy transmission has been given the atom or molecule of film surface, so as to drastically increase the consistency of film with
And the energy of top layer atom or molecule, so as to enhance the possibility that itself and reacting gas chemically react.
2nd, pre-process：
Present invention pretreatment refers to the strict ultrasonic wave cleaning carried out before substrate is put into vacuum chamber.Using " going
Five step standard law cleaning base plates of ion ethanol-water-acetone-alcohol-deionized water ", the scavenging period often walked are not less than 2 minutes.
Ultrasonic wave during the forward directed radiation of density interphase, produces ten hundreds of minute bubbles in cleaning fluid in liquid.These are stingy
Steep the negative pressuren zone formed in ultrasonic wave longitudinal propagation to be formed, grown, and be referred to as " cavitation in zone of positive pressure rapid closing, this phenomenon
Effect ", bubble can produce the instantaneous pressure of 1000 atmospheric pressure in closure, just as a series of small " blast " is constantly impacted
Workpiece surface, make the dirt rapid deterioration in workpiece surface and gap, so as to reach the purpose of cleaning workpiece.Ultrasonic wave cleans
Afterwards, substrate is placed in baking oven and toasted, and makes moisture evaporating completely.
In the method that the present invention prepares DLC film, the voltage of accelerating field especially accelerates between 500V-20kV
Voltage is arranged between 1.5kV-15kV, can improve the property of the terms of mechanics such as the adhesion, film compactness and hardness of film/substrate
Can, with the increase of accelerating potential, its hardness rises to 35GPa by 9GPa.The present invention prepares DLC film, mainly utilizes load
Energy ionized cluster beam beam auxiliary PECVD prepares good compactness, and film/base junction is strong with joint efforts, the big DLC film of hardness.Utilize vavuum pump
Vacuum chamber is vacuumized, and is separated using dividing plate and carries energy atomic group beam activating system and PECVD depositing systems.Vacuum cavity
Background vacuum close to 10-4Pa, deposition temperature range are 25 DEG C to 250 DEG C, and pressure in vacuum tank scope is kept in coating process
For 0.5-1.5Pa.During plated film, accelerating field, depositing temperature and the plated film time of energy atomic group beam activating system are carried by adjusting,
To meet different demands of the user to the hardness of DLC film, surface quality and thickness.The present invention is in order to improve film/substrate
The performance of the terms of mechanics such as adhesion, film compactness and hardness, in the method that the present invention prepares DLC film, sunk in PECVD
During product DLC film, on the premise of keeping carrying the energy and dosage of energy ionized cluster beam beam, the appropriate work(for reducing PECVD film forming
Rate, i.e., suitably reduce deposition velocity, uniformity, the more excellent film of compactness can be obtained.
Present invention process includes the formation and ionization of atomic group, and the kinetic energy lifting of ionized cluster beam, carrying can ionization atom
The effect of group to film surface etc..Specifically, first in a vacuum chamber, gas atom forms atom by adiabatic expansion
Group.These atomic groups form the ionized cluster beam of one positive charge of band after the ionization of ionization intracavitary.Ionized cluster beam is accelerating
Accelerate to form ionized cluster beam beam towards substrate orientation under electric field action.If in synchronization, otherwise to substrate
Surface coating, then carry energy ionized cluster beam beam and strike the film surface, because ionized cluster beam inertia is big, atom can be achieved
Group's ion transmits most of energy to film surface.Meanwhile by this effect of impact, the microcosmic knot of film can be significantly improved
Structure, hence it is evident that the adhesive force between lifting film and substrate, while the loose structure of film surface is effectively removed, and then improve film
Bulk density.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the present invention prepares film using load energy ionized cluster beam beam and plasma enhanced chemical vapor deposition (PECVD)
Method, comprehensive mechanical property and film/substrate adhesion, the film compactness and hardness of film can be effectively improved, so as to big
Amplitude improves service life of the DLC film in the machine applications such as cutter and mould field；
2. this invention ensures that PECVD low-temperature epitaxy characteristic, in the case where not significantly reducing the PECVD speeds of growth,
Using ionized cluster beam beam complex technique, film/base junction that DLC film greatly improved is made a concerted effort and film hardness, is significantly reduced
Roughness of film and skin-friction coefficient；
3. the present invention using carry can the DLC film for preparing of ionized cluster beam Shu Fuhe pecvd processes, its hardness is considerably beyond list
Solely use DLC film made from pecvd process；Meanwhile the present invention uses load energy ionized cluster beam Shu Fuhe pecvd process preparations
Film/base junction of DLC film is made a concerted effort also above DLC film made from exclusive use pecvd process；
4. present invention process parameter is easily controllable, can large area prepare DLC film, before having wide industrialization
Scape.
Brief description of the drawings
Fig. 1 is the principle schematic of one enhanced PECVD system of the embodiment of the present invention.
Fig. 2 is that the load energy ionized cluster beam beam of different-energy bombards material surface Contrast on effect schematic diagram, wherein Fig. 2 (a)
Material surface effect is bombarded for low energy ionized cluster beam beam；Wherein Fig. 2 (b) is that high-energy ionized cluster beam beam bombards material table
Face effect；
Fig. 3 is that the embodiment of the present invention one carries the DLC film of energy ionized cluster beam Shu Fuhe PECVD acquisitions (in Fig. 3
Left side) imitated with comparative example using the anti-wear performance test comparison of the DLC film (being located at the right side in Fig. 3) of PECVD acquisition merely
Fruit is schemed.
Fig. 4 is the micro Raman spectra figure of the DLC film of the preparation of the embodiment of the present invention one~tri-.
Embodiment
Such scheme is described further below in conjunction with specific examples of the implementation.It should be understood that these examples are to be used to say
It is bright the present invention and be not limited to limit the scope of the present invention.The experiment condition used in example is further adjusted as the case may be
It is whole.For ease of comparing, the present invention it is following be embodiment using coated basal plate use (100) be orientated monocrystalline silicon buffing base
Plate.Before plated film, substrate is cleaned according to the flow of " deionization ethanol-water-acetone-alcohol-deionized water-drying ", often
Scavenging period is walked to be not less than 2 minutes.Substrate after cleaning dries 1 hour to remove moisture removal in 130 DEG C of baking oven.
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, referring to Fig. 1, a kind of enhanced PECVD system, including back cavity body device and ante-chamber body device,
For back cavity body device to carry energy ionized cluster beam beam activating system, ante-chamber body device is PECVD system, and carrying can ionized cluster beam Shu Ji
The ionized cluster beam beam activating system chamber of hair system connects to form sysplex chamber with PECVD system inner chamber, can ionization carrying
Bonding in vacuum system is provided between atomic group beam activating system and PECVD system this two systems, utilizes bonding in vacuum system energy
Vacuum adjustment and control are carried out to sysplex chamber, can ionized cluster beam Shu Jifa systems carrying in sysplex chamber
Set baffle plate to separate between the ionized cluster beam beam activating system chamber of system and PECVD system inner chamber, while be provided with and open on baffle plate
Mouthful, the load energy ionized cluster beam beam that load ionized cluster beam beam activating system exports is shone directly into from the opening through rear
It is arranged on the substrate surface in PECVD system inner chamber, can ionized cluster beam beam bombardment profit in PECVD system inner chamber using carrying
The DLC film grown with chemical vapour deposition technique, control carry the bombardment DLC film technique and chemical gaseous phase of energy ionized cluster beam beam
Deposit DLC film technique to carry out simultaneously or alternately, while by adjusting the power of PECVD film forming, so as in carrier substrate
On be prepared densification DLC film.
In the present embodiment, referring to Fig. 1, carry can ionized cluster beam beam activating system unit, right is mainly formed by atomic group
The atomic group of ionization is accelerated to form to form the accelerating field unit for carrying energy ion cluster beam and baffle plate, and wherein atomic group is formed
Unit and accelerating field unit are all cooled by installing cooling device, to maintain being stabilized for atomic group and ion cluster；
In PECVD system, the carrier substrate of pending growth DLC film is fixedly installed on rotatable work rest, is carrying out PECVD
When depositing DLC film, work rest can drive carrier substrate to be rotated.
In the present embodiment, conventional PECVD system, load energy ionized cluster beam are included using equipment referring to Fig. 1, the present embodiment
Bonding in vacuum system between beam activating system and this two systems.The flat-plate type PECVD device that the present embodiment uses, substrate
It is placed in the electrode side of earth point position.The one side relative with substrate on high-frequency electrode, provided with a large amount of openings, argon gas or acetylene by
This opening sprays.Protected, kept between radome and high-frequency electrode several millimeters with the radome of earth point position around high-frequency electrode
Following gap.The present embodiment carries energy ionized cluster beam beam activating system and is mainly made up of 3 parts：Atomic group forms unit, right
The atomic group of ionization is accelerated to form the accelerating field unit and baffle plate of load energy ion cluster beam.Wherein, the first two unit is all
Need cooling device is installed and cool, to ensure being stabilized for atomic group and ion cluster.The rear end of sysplex chamber is by carrying
Can ionized cluster beam beam activating system composition, the front end of sysplex chamber is made up of PECVD system, between the two by baffle plate every
Open, there is opening to may insure that ion beam is irradiated to substrate surface after from the opening on baffle plate.Round piece on the right side of baffle plate
Frame can rotate.Substrate is fixed on round piece frame, and work rest rotates in coating process.The present embodiment can ionization using load
Atomic group beam auxiliary PECVD carries out DLC film growth, and ionized cluster beam is utilized while DLC film is prepared using PECVD
Shu Jinhang bombards.After ionized cluster beam beam bombardment substrate surface, the gas after atomic group is broken is discharged by exhaust apparatus.
In the present embodiment, referring to Fig. 1, it is 50 DEG C to set substrate temperature, and the accelerating potential of ionized cluster beam beam is
1500V, compound PECVD prepare DLC film.
Silicon chip after drying is placed on round piece frame by the present embodiment, and round piece frame rotates in deposition process.
Filming equipment is vacuumized, and its base vacuum is nearly 10-4pa.It is 50 DEG C to set substrate temperature.Carrying energy ionization atom first
Argon gas is passed through in group's beam exciter, the Bombardment and cleaning of ionized cluster beam beam is carried out to silicon chip, accelerating potential now is arranged to
2000V.After continuous bombardment 10-20 minutes, regulation accelerating potential continues to bombard to 1500V, while leads in PECVD system side
Enter acetylene gas, plated film 2 hours, DLC film thickness is 1 μm.
Experimental test and analysis：
After taking out DLC samples prepared by embodiment one, it is put into in-situ nano impression instrument and tests hardness.In-situ nano impression
The loading force of instrument is 5000 μ N, loads 5s, protects and carries 5s, unloads 5s.
Test result shows that the hardness of DLC film prepared by embodiment one is 9GPa, modulus of elasticity 90GPa.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, 100 DEG C of substrate temperature, the accelerating potential 3000V, compound PECVD of ionized cluster beam beam are set
Prepare DLC film.
The present embodiment use with the identical method of embodiment one is placed on work rest substrate and with load energy ionized cluster beam
Beam Bombardment and cleaning substrate.It is 100 DEG C to set substrate temperature.Set carry can the accelerating potential of ionized cluster beam beam activating system be
3000V, is then turned on PECVD precipitation equipments, plated film 2 hours, and DLC film thickness is 1 μm.
Experimental test and analysis：
Embodiment two is using the nano-indentation hardness with the identical method of embodiment one and parameter testing DLC film.Test knot
Fruit shows that the hardness of DLC film prepared by embodiment two is 15GPa, modulus of elasticity 110GPa.
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, 100 DEG C of substrate temperature, the accelerating potential 9000V, compound PECVD of ionized cluster beam beam are set
Prepare DLC film.
The present embodiment uses and the identical processing step pretreated substrate surface of embodiment one and preparation DLC film, setting
Substrate temperature is 100 DEG C, but 9000V is arrived in accelerating potential regulation, and DLC film thickness is 1 μm.
Experimental test and analysis：
Embodiment three is using the nano-indentation hardness with the identical method of embodiment one and parameter testing DLC film.Test knot
Fruit shows that the hardness of DLC film prepared by embodiment three is 35GPa, modulus of elasticity 140GPa.
Comparative example：
In this comparative example, pecvd process is used alone and prepares DLC film.
Substrate is placed on work rest using with the identical method of embodiment one, round piece frame revolves in deposition process
Turn.Filming equipment is vacuumized, and its base vacuum is nearly 10-4pa.Acetylene gas is passed through in PECVD devices side, plated film 2 is small
When, it is 100 DEG C to set substrate temperature, 1.2 μm of DLC film thickness.
Experimental test and analysis：
Comparative example is using the nano-indentation hardness with the identical method of embodiment one and parameter testing DLC film.Test result
Show, the hardness for contrasting the DLC film of preparation is 7GPa, modulus of elasticity 70GPa.
By contrasting above-described embodiment and comparative example：
DLC film prepared by pecvd process is used alone in comparative example can ionized cluster beam Shu Fuhe pecvd process systems with carrying
The performance comparision of standby DLC film is as shown in figure 4, three curves are respectively embodiment one, the and of embodiment two from top to bottom in Fig. 4
The micro Raman spectra curve of DLC film prepared by embodiment three.As a result show, can ionized cluster beam Shu Fuhe using carrying
DLC film prepared by pecvd process, DLC film made from its hardness considerably beyond exclusive use pecvd process.Meanwhile above-mentioned implementation
Example makes a concerted effort individually to make also above comparative example using the film/base junction for carrying DLC film prepared by energy ionized cluster beam Shu Fuhe pecvd processes
The DLC film made from pecvd process.Fig. 3 is that the embodiment of the present invention one carries energy ionized cluster beam Shu Fuhe PECVD acquisitions
DLC film (being located at the left side in Fig. 3) uses merely the resistance to of the DLC film (being located at the right side in Fig. 3) of PECVD acquisition with comparative example
Grind performance test contrast effect figure.As can be known from Fig. 3, the embodiment of the present invention one carries energy ionized cluster beam Shu Fuhe PECVDs and obtained
The hardness of the DLC film obtained is higher, and film/base junction of DLC film is stronger with joint efforts.The above embodiment of the present invention technological parameter is easily controllable,
Can large area prepare DLC film, have wide industrialization prospect.
Fig. 2 is that the load energy ionized cluster beam beam of different-energy bombards material surface effect diagram:(a) it is low energy ionization
Atomic group beam bombards；(b) bombarded for high-energy ionized cluster beam beam.During plated film, energy atomic group Shu Jifa systems can be carried by adjusting
Accelerating field, depositing temperature and the plated film time of system, to meet difference of the user to the hardness of DLC film, surface quality and thickness
Demand.
Above-described embodiment prepares DLC film, mainly prepares consistency using load energy ionized cluster beam beam auxiliary PECVD
Good, film/base junction is strong with joint efforts, the big DLC film of hardness.Vacuum chamber is vacuumized using vavuum pump, and separated using dividing plate
Carrying can atomic group beam activating system and PECVD depositing system.The background vacuum of vacuum cavity is close to 10-4Pa, depositing temperature model
Enclose for 50 DEG C to 100 DEG C, it is 0.5-1.5Pa that pressure in vacuum tank scope is kept in coating process.Above-described embodiment prepares DLC film
Method by carry can ionized cluster beam beam aid in PECVD to deposit DLC film, with carry can ionized cluster beam beam it is thin to what is grown
Film carries out surface ion bombardment, significantly improves the adhesion, film compactness and hardness of film/substrate.
Example IV：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, 25 DEG C of substrate temperature, the accelerating potential 500V of ionized cluster beam beam, compound PECVD systems are set
Standby DLC film.
The present embodiment uses and the identical processing step pretreated substrate surface of embodiment one and preparation DLC film, setting
Substrate temperature is 25 DEG C, but 500V is arrived in accelerating potential regulation, and DLC film thickness is 1 μm.
Experimental test and analysis：
Example IV is using the nano-indentation hardness with the identical method of embodiment one and parameter testing DLC film.Test knot
Fruit shows that the hardness of DLC film prepared by example IV is 9GPa, modulus of elasticity 85GPa.
Embodiment five：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, 175 DEG C of substrate temperature, the accelerating potential 15kV of ionized cluster beam beam, compound PECVD systems are set
Standby DLC film.
The present embodiment uses and the identical processing step pretreated substrate surface of embodiment one and preparation DLC film, setting
Substrate temperature is 175 DEG C, but 15kV is arrived in accelerating potential regulation, and DLC film thickness is 1 μm.
Experimental test and analysis：
Embodiment five is using the nano-indentation hardness with the identical method of embodiment one and parameter testing DLC film.Test knot
Fruit shows that the hardness of DLC film prepared by embodiment five is 38GPa, modulus of elasticity 146GPa.
Embodiment six：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, 250 DEG C of substrate temperature, the accelerating potential 20kV of ionized cluster beam beam, compound PECVD systems are set
Standby DLC film.
The present embodiment uses and the identical processing step pretreated substrate surface of embodiment one and preparation DLC film, setting
Substrate temperature is 250 DEG C, but 20kV is arrived in accelerating potential regulation, and DLC film thickness is 1 μm.
Experimental test and analysis：
Embodiment six is using the nano-indentation hardness with the identical method of embodiment one and parameter testing DLC film.Test knot
Fruit shows that the hardness of DLC film prepared by embodiment six is 14GPa, modulus of elasticity 103GPa.Compared with comparative example, implement
The result of example four, five and six shows, all super using the DLC film for carrying energy ionized cluster beam Shu Fuhe pecvd process preparations, its hardness
DLC film made from exclusive use pecvd process is crossed.This shows, DLC can be effectively improved using energy ionized cluster beam beam is carried
The comprehensive mechanical property of film.
The above embodiment of the present invention to substrate sputter clearly before thin film deposition using energy ionized cluster beam beam is carried
Wash, activate and planarization process；DLC film is deposited in substrate surface using PECVD method, while can ionization atom using carrying
Group's beam is bombarded the DLC film of deposition, obtains the DLC film of high compaction.It is thin that DLC is substantially increased in this way
Consistency, wearability, hardness and the film-substrate cohesion of film.Present invention process is easily controllable, can be applied in various instruments and portion
The surface plating diamond film of part.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with
A variety of changes are made according to the purpose of the innovation and creation of the present invention, under all Spirit Essence and principle according to technical solution of the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Being carried without departing from the present invention can the method for ionized cluster beam beam assistant chemical vapor deposition preparation DLC film and its skill of system
Art principle and inventive concept, belong to protection scope of the present invention.
Claims (10)
1. a kind of method that load energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film, it is characterised in that：Utilize load
The DLC film of energy ionized cluster beam beam bombardment chemical vapour deposition technique growth, the bombardment DLC of the load energy ionized cluster beam beam are thin
Film and chemical vapor deposition DLC film are carried out or alternately simultaneously, while by adjusting the power of PECVD film forming, so as to make
It is standby to obtain the DLC film of densification.
2. carrying the method that energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film according to claim 1, it is special
Sign is：Before PECVD deposition DLC films are carried out, carrier substrate is cleaned and dried, then can ionization atom with load
Group's beam bombardment carrier substrate surface, sputter clean, activation and planarization pretreatment are carried out to the surface of carrier substrate.
3. the method that load energy ionized cluster beam beam assistant chemical vapor deposition according to claim 1 or claim 2 prepares DLC film,
It is characterized in that：During using the bombardment DLC film for carrying energy ionized cluster beam beam, the gas of the formation ionized cluster beam beam is
Ar、N2With any one gas in the gas containing carbons or any several mixed gas；Carry out PECVD deposition DLC films
When, the gas for participating in chemical gas phase reaction is any one gas in the gas of alkane, alkene and acetylenic or any several
Mixed gas.
4. carrying the method that energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film according to claim 4, it is special
Sign is：During using the bombardment DLC film for carrying energy ionized cluster beam beam, the institute as the gas of the formation ionized cluster beam beam
Stating gas containing carbons includes CO2、CH4And C2H2；When carrying out PECVD deposition DLC films, the gas for participating in chemical gas phase reaction
Body is CH4And C2H2In any one gas or two kinds of mixed gas.
5. the method that load energy ionized cluster beam beam assistant chemical vapor deposition according to claim 1 or claim 2 prepares DLC film,
It is characterized in that：The carrier substrate is using monocrystalline silicon, glass, stainless steel, metallic aluminium, magnesium alloy, lucite, BT, PPE
Or PET material is made.
6. the method that load energy ionized cluster beam beam assistant chemical vapor deposition according to claim 1 or claim 2 prepares DLC film,
It is characterized in that：The accelerating potential applied to the load energy ionized cluster beam beam is 500V-20kV；It is thin to carry out PECVD depositions DLC
When during film and using the bombardment DLC film for carrying energy ionized cluster beam beam, it is 25-250 DEG C to set substrate temperature, is protected in coating process
It is 0.5-1.5Pa to hold pressure in vacuum tank scope.
7. carrying the method that energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film according to claim 6, it is special
Sign is：The accelerating potential applied to the load energy ionized cluster beam beam is 1500V-15kV；Carry out PECVD deposition DLC films
When and using carry can ionized cluster beam beam bombardment DLC film when, set substrate temperature be 50-175 DEG C.
8. carrying the method that energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film according to claim 7, it is special
Sign is：The accelerating potential applied to the load energy ionized cluster beam beam is 1500-9000V；Carry out PECVD deposition DLC films
When and using carry can ionized cluster beam beam bombardment DLC film when, set substrate temperature be 50-100 DEG C.
9. a kind of implement to carry the method that energy ionized cluster beam beam assistant chemical vapor deposition prepares DLC film described in claim 1
Enhanced PECVD system, it is characterised in that：Including back cavity body device and ante-chamber body device, the back cavity body device is load energy
Ionized cluster beam beam activating system, the ante-chamber body device are PECVD system, the load energy ionized cluster beam beam activating system
Ionized cluster beam beam activating system chamber connects to form sysplex chamber with PECVD system inner chamber, can ionized cluster beam beam carrying
Bonding in vacuum system is provided between activating system and PECVD system this two systems, can be comprehensive to system using bonding in vacuum system
Fit chamber carries out vacuum adjustment and control, in sysplex chamber, in the load energy ionized cluster beam beam activating system
Set baffle plate to separate between ionized cluster beam beam activating system chamber and PECVD system inner chamber, while opening is provided with baffle plate, make
The load energy ionized cluster beam beam of load energy ionized cluster beam beam activating system output shines directly into and set from the opening through rear
It is placed on the substrate surface in PECVD system inner chamber, is utilized using the beam bombardment of energy ionized cluster beam is carried in PECVD system inner chamber
The DLC film of chemical vapour deposition technique growth, control the bombardment DLC film technique of the load energy ionized cluster beam beam and chemical gas
Mutually deposition DLC film technique is carried out or alternately simultaneously, while by adjusting the power of PECVD film forming, so as in carrier base
The DLC film of densification is prepared on plate.
10. enhanced PECVD system according to claim 8, it is characterised in that：The load energy ionized cluster beam Shu Jifa systems
System mainly forms unit, the ionization unit of atomic group by atomic group and the atomic group of ionization is accelerated to carry energy ion to be formed
The accelerating field unit and baffle plate composition of group's beam, wherein atomic group form unit, the ionization unit of atomic group and acceleration electricity
Unit is all cooled by installing cooling device, to maintain being stabilized for atomic group and ion cluster；In the PECVD system
In, the carrier substrate of pending growth DLC film is fixedly installed on rotatable work rest, and carrying out, PECVD depositions DLC is thin
During film, work rest can drive carrier substrate to be rotated.
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| CN111850470A (en) * | 2020-08-04 | 2020-10-30 | 中国科学院兰州化学物理研究所 | Ultra-lubricity metal/hydrogen-carbon composite film and preparation method thereof |
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