CN101798671B - Novel ReB2/TaN high-hard nano-multilayer film, and preparation method and application thereof - Google Patents
Novel ReB2/TaN high-hard nano-multilayer film, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a novel ultra-hard ReB2/TaN nano-multilayer film, and a preparation method and the application thereof. The preparation method comprises the following steps: depositing TaN on a single-sided polished Si(100) substrate as a transition layer; and alternately depositing ReB2 and the TaN to form a multilayer film, wherein the modulation ratio of the ReB2 to TaN is 1:1-7:1; each cycle layer thickness is 10 to 40mm; the multilayer film comprises 20 to 40 layers of cycles; the total thickness is 400 to 700 mm; and determining the multilayer film related experiment parametersof a best result by comparing the experiment results obtained under different parameters. The novel high-hard ReB2/TaN nano-multilayer film has high comprehensive properties of high hardness, low residual stress and high film-substrate cohesion; and the multilayer film with the modulation cycle of 20 nm synthesized under the conditions of changing the modulation ratio and combining substrate heating has the hardness up to 34 GPa and the lower residual stress of 1.39 GPa. Therefore, the service life of a cutting tool is prolonged effectively and the tool has high comprehensive properties; and the machining efficiency is improved greatly. Thus, the novel ultra-hard ReB2/TaN nano-multilayer film has significance in improving cutting tool technology in China and prompting the development of manufacturing industry.
Description
Technical field
The present invention relates to the surface strengthening thin film technique field of all kinds of blade tools, mould.Say so more specifically and utilize magnetron sputtering technique to prepare by two boronation rheniums and tantalum nitride (ReB
2/ TaN) the novel high-hard nano multiple-level surface of composition is strengthened film and ReB thereof
2The preparation method of/TaN high-hard nano-multilayer film.
Background technology
The purposes of high hard material is very extensive, no matter is the drill bit of usefulness of drilling for oil and construct a road, or the anti-friction coating on precision instrument and wrist-watch surface, all needs to use superhard material.Two boronation rhenium (ReB
2) as a kind of novel high hard material, not only have high fusing point, high chemical stability, high hardness and excellent abrasive, and ReB
2Because it can be synthesized under normal pressure, be easy to processing, performance is excellent especially and be used as the boride ceramics that market potential is arranged very much.Develop ReB by the scientist of University of California in Los Angeles
2High hard material, on certain direction, " incompressibility " of two boronation rheniums is identical with diamond, and on another direction, " compressibility " of two boronation rheniums is only high slightly than diamond.Under low reactive force, the hardness of two boronation rheniums equates with the boron nitride of cubic structure, and boron nitride is the present second hard material.Under higher reactive force, the hardness of two boronation rheniums is only low slightly than boron nitride, and has extremely strong wear resistance and splitting resistance, but for two boronation rhenium ReB
2Research work as high hard coat just just begins; And the TaN pottery is a kind of non-oxidized substance engineering ceramics, and grey black is with the hexagonal of metalluster, 3000 ℃ of fusing points firmly.Water insoluble, hydrochloric acid, sulfuric acid are dissolved in the nitric acid of hydrofluoric acid slightly, and chemical property is more stable, constitutes a kind of thin film resistor on the sapphire substrate industrial it is deposited on, and its stability, precision are all more satisfactory.Machining is one of most widely used processing technology of modern manufacturing industry; this class superhard thin film then is applicable to materials such as cutting cast iron, superalloy and nickel-base alloy just; the tool surface enhanced protection coating that is particularly useful for roughing feed amount or interrupted cut; on the other hand; in conjunction with TaN is good film resistor material; can be widely used on the electronic component by strengthening its characteristic such as high temperature resistant, wear-resisting, corrosion-resistant.
At present, about ReB
2No matter the report of/TaN (two boronation rhenium/tantalum nitrides) nano-multilayer film is that patent or document there is no relevant report both at home and abroad.So, synthesize the ReB of performances such as having high rigidity, film-substrate cohesion is strong, wear-resistant
2/ TaN nano-multilayer film, this will effectively improve cutting tool work-ing life, make cutter obtain good comprehensive mechanical performance, thereby increase substantially mechanical workout efficient.Raising to the cutting tool technology of China promotes that manufacturing development is significant.
ReB
2As a kind of novel high hard material, owing to have near adamantine hardness, with excellent abrasive, and can synthesize at normal temperatures, be subjected to paying close attention to widely, just just begin as the research of hardness film; TaN is high temperature resistant, and the chemical stability height is an ideal industry resistance thin-film material comparatively, yet, do not see the report of pertinent literature as yet for the research of nano-multilayer film.
Summary of the invention
One object of the present invention is, a kind of novel ReB is provided
2/ TaN high-hard nano-multilayer film.
Another object of the present invention is to disclose novel ReB
2The preparation method of/TaN high-hard nano-multilayer film.It is with two boronation rhenium (ReB
2) and tantalum nitride (TaN) be the simple substance material, adopt ultrahigh vacuum(HHV) rf magnetron sputtering deposition technique synthetic by ReB
2/ TaN alternately forms novel ReB
2/ TaN nano-multilayer film.The hard ReB of novel height of the present invention
2/ TaN nanometer multimembrane has high rigidity, low unrelieved stress, the good overall characteristic of high film-substrate cohesion, change modulation ratio in conjunction with the substrate heating condition under synthetic modulation period be that 20nm multilayer film hardness is up to 34Gpa and low unrelieved stress 1.39GPa.The invention provides following technical scheme for achieving the above object:
A kind of ReB
2/ TaN nano-multilayer film is characterized in that the TaN of elder generation's deposition 50-80nm in Si (001) substrate at single-sided polishing (is TaN or ReB
2) as excessive layer, alternating deposit TaN and ReB again
2Do multilayer film, the phase bed thickness is 10-40nm weekly, and the cycle of multilayer film is the 20-40 layer, and total bed thickness is 400-700nm; ReB wherein
2: TaN modulation ratio 1: 1～7: 1.
ReB of the present invention
2/ TaN nano-multilayer film, wherein ReB
2: the modulation ratio of TaN is 3: 1, and be 20nm modulation period.
The present invention further discloses ReB
2The preparation method of/TaN nano-multilayer film comprises following step:
(1) at first Si (100) substrate of single-sided polishing is handled, 25-300 ℃ of control base reservoir temperature, preferred base reservoir temperature is 25-100 ℃.Use Ar
+Bombard ReB respectively
2With two targets of TaN, deposition TaN50-80nm adopts high vacuum rf magnetron sputtering alternating deposit TaN and ReB again as transition layer earlier in the Si (001) of single-sided polishing substrate
2Do multilayer film, control weekly phase bed thickness 10～40nm; The cycle of multilayer film is the 20-40 layer, and total bed thickness is 400-700nm; ReB wherein
2: the modulation ratio of TaN is 1: 1～7: 1;
(2) adopt mechanical pump and molecular pump, base vacuum 2.0 * 10
-4Pa～3.8 * 10
-4Pa, atmospheric pressure value is measured by ionization gauge, and sputter gas is selected pure Ar for use in the deposition process
2, control its flow with mass flow controller and remain on 40～45sccm; Operating air pressure total in the long-pending process keeps between 0.5Pa～0.6Pa.
Preparation method of the present invention, single-sided polishing Si (100) substrate is wherein handled and is referred to: use acetone, ethanol ultrasonic cleaning 15 minutes successively, send into immediately after drying up in the vacuum deposition chamber, then under operating air pressure 6Pa condition, with the Ar of bias voltage-400V
+Sample is cleaned 5min; During deposit film, with purity 99.9% ReB
2Alternately rotate to sputter position and the accurate sputtering time of controlling each target with the TaN target, use Ar equally
+Two target sources of alternating sputtering, processing parameter is penetrated in the radio-frequency sputtering source: frequency target ReB
2Sputtering power is 50W, and the TaN sputtering power is 110W, and target-substrate distance is 6-7cm, substrate bias-120V.
Novel ReB of the present invention
2The preparation method that/TaN nano-multilayer film is more concrete is as follows:
Utilize FJL560CI2 type ultrahigh vacuum(HHV) rf magnetron sputtering system (MS), prepare ReB at first respectively
2/ TaN nano-multilayer film and ReB
2, the TaN monofilm.Purity is 99.9% ReB
2With the TaN compound target respectively by two radio frequency cathodic controls, adjust target base spacing and remain on 6cm, 7cm.ReB
2Be respectively 35W and 110W with the sputtering power of TaN.Monocrystalline (100) the Si sheet of single-sided polishing is adopted in substrate, uses acetone and dehydrated alcohol ultrasonic cleaning 15min respectively before the system film, and oven dry is placed on the rotating sample table.Before deposit film, the usefulness-400V of elder generation substrate bias, the Ar of 80sccm
+Under the operating air pressure of 6Pa, sample is cleaned 5min.Base vacuum is higher than 2 * 10 during plated film
-4Pa, sputter gas adopts Ar (99.999%), in the whole deposition process, total operating air pressure remains on 0.2-1.5Pa, substrate bias remains on-100 ± 20V, and before the deposit multilayer film, the TaN that the about 50-80nm of deposition is thick in the Si substrate is with the bonding force of enhanced film and substrate earlier.The modulating layer thickness of multilayer film passes through the computer system control substrate at ReB
2Control in the residence time of sputter position with the TaN target, be 10～40nm all modulation periods; Modulation ratio (ReB
2: TaN) 1: 1～7: 1.By the change sputtering power, bias voltage, base reservoir temperature, modulation period, parameters such as modulation ratio prepare a series of ReB
2/ TaN nano-multilayer film draws the ReB that influences the film principal element and obtain best effect thus
2/ TaN multilayer film.
Along with the appearance of nano-scale film, it is found that when the thickness of film is reduced to nanometer scale its these performances can obtain very big improvement.Therefore the present invention attempts selecting two boronation rhenium (ReB
2) and these two kinds of materials of tantalum nitride (TaN) form the nano-multilayer film system, they all belong to hexagonal system, because lattice parameter differs bigger, according to differ the superlattice theoretical model that causes superhard effect to produce under the bigger situation at lattice parameter, wish not only to obtain higher hardness, Young's modulus, and have nano-multilayer film than high-wearing feature and chemical stability, dystectic advantage separately.Two kinds of simple substance ultrathin films periodically exist according to a certain percentage, might make simple substance film forming core formation superlattice periodically again, so not only can stop moving and growing up of column crystal and dislocation in the simple substance film, stop the mutual diffusion of material phase, reduce high-temperature fusion each other, and low interfacial energy can alleviate unrelieved stress, increases between rete and bonding force whole and matrix, helps synthesizing the thicker surface peening coating system that is suitable for practical application.
The present invention is by analyzing the theoretical model that lattice dislocation causes producing superhard effect, select targetedly participating in experiment material, pass through ordering parameter, obtain superstructure preferably, hinder dislocation by alternating force-field type thus, promote multilayer film hardness, the superhard phenomenon of experimental result and theoretical prediction matches, the present invention has made full use of the good merit that MS technology many reference amounts can independently accurately be controlled, obtain reliable testing data, and obtained the parameter condition of optimal mechanical properties.
The present invention has selected a kind of high hard type material-two boronation rhenium (ReB in the synthesizing multilayer film
2), its bulk not only has ultrahigh hardness, and can synthesize under normal pressure, huge application potential is arranged, and be not applied to the report of the research of multilayer film.By with TaN synthesizing multilayer film, obtain to comprise two kinds of films novel multi-layer mould material of advantage separately.
The present invention experiment be respectively in control substrate Heating temperature by room temperature to 300 ℃; Modulation period 10-40nm; Modulation ratio (ReB
2: TaN) amount to four variables and prepare a series of ReB with substrate bias
2/ TaN nano-multilayer film has drawn the experimental result under each condition and has carried out the Mechanics Performance Testing analysis, thereby obtained optimum.
The novel super-hard ReB of the present patent application
2The positively effect that/TaN nano-multilayer film is compared with prior art had mainly is:
1, high hard ReB
2/ TaN nano-multilayer film and TiB
2/ Si
3N
4Nano-multilayer film technical matters difference, ReB
2/ Si
3N
4Adopt ion beam technology, ReB
2/ TaN nano-multilayer film is used magnetron sputtering technique, and two kinds of technology are compared, and magnetic control film coating efficient is higher, and the time spent is less, is more conducive to use, and has solved the ion beam deposition overlong time, and efficient is on the low side, is difficult to realize the problem of producing in enormous quantities.
2, the selected materials difference, particularly, ReB
2In a kind of novel superhard material that is synthesized recently, from block materials, ReB
2Hardness all be higher than ReB
2, Si
3N
4Be only second to diamond, and cubic boron nitride, simultaneously, the contrast diamond, more high temperature resistant, and than cubic boron nitride, ReB2 can synthesize under normal pressure, saves cost more, and its research in hardness film field just just begins; TaN has fusing point height (3000 ℃), and temperature coefficient of resistance is little, and the characteristics that stability is high are ideal resistance film materials.So, have the multilayer film of the ReB2/TaN of two kinds of material advantages, can not only satisfy the hardness requirement of modern cutting tool supercoat, simultaneously, its high-temperature stability also more helps promoting modern cutting technology.
The present invention further discloses ReB
2The application of/TaN nano-multilayer film aspect all kinds of blade tools of preparation, die surface strengthening film.
The present invention adopts the surface profiler (XP-2) of U.S. Ambios company that the thickness and the internal stress of film are measured to synthetic simple substance membrane and nano-multilayer film under the various processing condition.With the XP of American MTS company type nano-hardness tester film is carried out nano hardness and Young's modulus.
Experimental result shows: the hard ReB of novel height of the present invention
2/ TaN nanometer multimembrane has high rigidity, low unrelieved stress, the good overall characteristic of high film-substrate cohesion, change modulation ratio in conjunction with the substrate heating condition under synthetic modulation period be that 20nm multilayer film hardness is up to 34Gpa and low unrelieved stress 1.39GPa.
Description of drawings
Fig. 1: ReB in this series
2The structural representation of/TaN nano-multilayer film;
Fig. 2: ReB in this series
2The hardness of/TaN multilayer film contrast unitary film, the variation of Young's modulus;
Fig. 3: ReB in this series
2The unrelieved stress of/TaN multilayer film is with the variation of modulation ratio;
Fig. 4: FJL560CI2 type ultrahigh vacuum(HHV) radio frequency magnetron and ionic fluid associating sputtering system.1. gas inletes wherein; 2. sample plate washer; 3. substrate heating unit; 4. controlled sample rotary turnplate; 5. sample; 6.HTFB turbomolecular pump; 7. sample plate washer swivel arrangement; 8. magnetron cathode target.
Fig. 1 has represented ReB2The structure of/TaN multilayer film, Fig. 2 has represented ReB2The comparison diagram of the hardness of/TaN multilayer film, elastic modelling quantity and monofilm is 3: 1 in modulation ratio, and substrate is under the room temperature condition, and be the hard value of the multilayer film of 20nm and elastic modelling quantity maximum modulation period; Fig. 3 has represented ReB2/ TaN multilayer film residual stress is with the variation of modulation period, and the stress of multilayer film is all far below two monofilm stress mean values.
Above result proves: the present invention is " with the novel ReB of magnetron sputtering law technology preparation2/ TaN high-hard nano multimembrane " have high rigidity, low residual stress, a good overall characteristic such as high film-substrate cohesion. The hard ReB of novel height2/ TaN nano-multilayer film will have important application prospect in blade tool, die surface strengthening film.
Embodiment
Below by embodiment, foregoing of the present invention is described in further detail, for further understanding content of the present invention, characteristics and effect, conjunction with figs. is described as follows:
(1) use equipment, step and method:
Use equipment: FJL560CI2 type ultrahigh vacuum(HHV) radio frequency magnetron and ionic fluid associating sputtering system are used for synthetic by ReB
2High hard ReB with the TaN composition
2/ TaN nanometer multilayer surface strengthening film is by Tianjin Normal University and Shenyang Scientific Instrument Factory, Chinese Academy of Sciences's joint research and development " FJL560CI2 type ultrahigh vacuum(HHV) radio frequency magnetron and ionic fluid associating sputtering system ", and its structure as shown in Figure 4.Purity is 99.9% ReB
2Be placed on respectively on the magnetron cathode target platform 8 in the vacuum chamber with the TaN target material, sample 5 is placed in the vacuum chamber on the controlled sample rotary turnplate sample table 4; Pumping system is finished by mechanical pump and HTFB turbomolecular pump 6, and atmospheric pressure value is measured by ionization gauge, and Ar enters vacuum chamber through gas inlet mouth 1, Ar and N
2Charge flow rate control by mass flowmeter.Computer program is accurately controlled the sputtering time of each target.Can obtain their the single thin film deposition and the nano-multilayer film of different modulating cycle and modulation ratio by the depositing time that changes each target.
(2) concrete synthesis technologic parameter:
Ar flow: 40～45sccm; Base vacuum degree: 2.0 * 10
-4Pa～3.8 * 10
-4Pa; Operating air pressure: 0.5Pa; Radio-frequency sputtering source processing parameter: radio frequency target ReB
2Sputtering power is 50W, and the TaN sputtering power is 110W.Its processing parameter: target-substrate distance is respectively 6cm, 7cm, substrate bias-120V.Substrate Heating temperature: room temperature.3: 1 (TiB of modulation ratio
2: BN), modulation period 20nm.Need to prove: the magnetic control sputtering system of other models (MS) equipment can use.
The preparation method
(1) uses acetone and raw spirit to Si sheet ultrasonic cleaning 15min successively before the experiment, put the magnetron sputtering plating chamber after the oven dry into.
(2) chamber is vacuumized, make the interior base vacuum degree of chamber 2.0 * 10
-4Pa～3.8 * 10
-4Pa.
(3) regulate push-pull valve, making operating air pressure is 6Pa, with mass rate under meter control Ar charge flow rate, make it to remain on 80sccm, open grid bias power supply, regulate substrate bias-400V, it is normal that electric current is played table, bombards at least with Ar ion pair sample and clean 5min, closes grid bias power supply, regulate push-pull valve, making operating air pressure is 3Pa.
(4) open the 500W radio-frequency power supply,, make it to remain on 40～45sccm, regulate radio-frequency power supply, regulate operating air pressure to 0.5Pa, radio frequency target ReB to normal build-up of luminance with mass flowmeter control Ar charge flow rate
2Sputtering power is 50W, and the TaN sputtering power is 110W.Open grid bias power supply and regulate substrate bias to-120V.
(5) experiment condition room temperature confirms that heating power supply is in closing condition.
(6) keep operating air pressure at 0.5Pa this moment.Accurately control the sputtering time of each target with computer program.Can obtain their single thin film and the multilayer film of different modulating cycle and modulation ratio by the depositing time that changes each target.The thickness of film is about 600nm.
(7) film behind the band inside and outside air pressure balance, is opened chamber and is taken out in high vacuum chamber.
Change modulation ratio in conjunction with the down synthetic ReB of substrate heating condition
2/ TaN nano-multilayer film:
Deposition parameter: substrate temperature bottom compartment temperature; 1: 1 (ReB of modulation ratio
2: TaN), modulation period 30nm; 40 layers of multilayer film preparations, Ar flow: 40～45sccm; Base vacuum degree: 2.0 * 10
-4Pa～3.8 * 10
-4Pa; Operating air pressure: 0.5Pa; Radio-frequency sputtering source processing parameter: radio frequency target ReB
2Sputtering power is 50W, and the TaN sputtering power is 110W; Target-substrate distance is 6cm, 7cm, substrate bias-120V.The TaN transition region thickness is at 50nm, and depositing time is controlled at about 450s.
For top condition, as above (1)-(5) are described for the preparation work before the experiment, by modulating layer thickness and modulation ratio, calculate individual layer ReB
2Thickness is 15nm, and TaN thickness is 15nm, then according to ReB
2With the deposition of TaN, calculate the time of their sputters.Be set in 30 cycles that come and go between two targets.Base reservoir temperature keeps room temperature.So just can obtain the ReB of needs
2/ TaN nano-multilayer film.
Change modulation ratio in conjunction with the down synthetic ReB of substrate heating condition
2/ TaN nano-multilayer film:
Deposition parameter: substrate temperature bottom compartment temperature; 3: 1 (ReB of modulation ratio
2: TaN), modulation period 20nm; 25 layers of multilayer film preparations, Ar flow: 45sccm; Base vacuum degree: 2.0 * 10
-4Pa～3.8 * 10
-4Pa; Operating air pressure: 0.5Pa; Radio-frequency sputtering source processing parameter: radio frequency target ReB
2Sputtering power is 50W, and the TaN sputtering power is 110W; Target-substrate distance is 6cm, 7cm, substrate bias-120V.The TaN transition region thickness is at 50nm, and depositing time is controlled at about 450s.
For top condition, as above (1)-(5) are described for the preparation work before the experiment, by modulating layer thickness and modulation ratio, calculate individual layer ReB
2Thickness is 15nm, and TaN thickness is 5nm, then according to ReB
2With the deposition of TaN, calculate the time of their sputters.Be set in 30 cycles that come and go between two targets.Base reservoir temperature keeps room temperature.So just can obtain the ReB of needs
2/ TaN nano-multilayer film.
Embodiment 4
Change modulation ratio in conjunction with the down synthetic ReB of substrate heating condition
2/ TaN nano-multilayer film:
Deposition parameter: substrate temperature bottom compartment temperature; Modulation ratio 6; 1 (ReB
2: TaN), modulation period 30nm; 25 layers of multilayer film preparations, Ar flow: 45sccm; Base vacuum degree: 2.0 * 10
-4Pa～3.8 * 10
-4Pa; Operating air pressure: 0.5Pa; Radio-frequency sputtering source processing parameter: radio frequency target ReB
2Sputtering power is 50W, and the TaN sputtering power is 110W; Target-substrate distance is 6cm, 7cm, substrate bias-120V.The TaN transition region thickness is at 50nm, and depositing time is controlled at about 450s.
For top condition, as above (1)-(5) are described for the preparation work before the experiment, by modulating layer thickness and modulation ratio, calculate individual layer ReB
2Thickness is 24nm, and TaN thickness is 4nm, then according to ReB
2With the deposition of TaN, calculate the time of their sputters.Be set in 30 cycles that come and go between two targets.Base reservoir temperature keeps room temperature.So just can obtain the ReB of needs
2/ TaN nano-multilayer film.
The excessive layer of deposition 50nm TaN conduct earlier, alternating deposit TaN and ReB again in the Si (100) of single-sided polishing substrate
2Do multilayer film, the phase bed thickness is 10nm weekly, and the cycle of multilayer film is 20 layers, and total bed thickness is 400nm; (ReB wherein
2: TaN) 3: 1.As above (1)-(5) are described for preparation work before the experiment, by modulating layer thickness and modulation ratio, calculate individual layer ReB
2Thickness is 15nm, and TaN thickness is 5nm, then according to ReB
2With the deposition of TaN, calculate the time of their sputters.Be set in 30 cycles that come and go between two targets.Base reservoir temperature keeps room temperature.So just can obtain the ReB of needs
2/ TaN nano-multilayer film.
The excessive layer of deposition 50nm TaN conduct earlier, alternating deposit TaN and ReB again in the Si (001) of single-sided polishing substrate
2Do multilayer film, phase bed thickness 40nm weekly, the cycle of multilayer film is 40 layers, total bed thickness 700nm; Modulation ratio (ReB wherein
2: TaN) 3: 1.
As above (1)-(5) are described for preparation work before the experiment, by modulating layer thickness and modulation ratio, calculate individual layer ReB
2Thickness is 30nm, and TaN thickness is 10nm, then according to ReB
2With the deposition of TaN, calculate the time of their sputters.Be set in 20 cycles that come and go between two targets.Base reservoir temperature keeps room temperature.So just can obtain the ReB of needs
2/ TaN nano-multilayer film.
The present invention has utilized the XP-2 surface topographic apparatus fo of the nanometer mechanics test macro of American MTS and the U.S. to carry out comprising that performances such as nano hardness, bonding force, unrelieved stress test respectively to synthetic simple substance membrane and nano-multilayer film under the various processing condition.The data results of test sees the following form, and main result is as follows:
1, with regard to simple substance membrane: ReB
2Not high with the hardness of TaN two simple substance films, be respectively 11.9GPa and 11.1GPa, ReB
2The stress of simple substance film is higher, surpasses 1.79GPa, just begins to scale off the unrelieved stress of TaN simple substance film then relatively low (0.617GPa) when finding thin film deposition to certain thickness in the experiment.
2, with regard to multilayer film: suitably modulation ratio and modulation period in conjunction with and certain thickness TaN transition layer under a series of multilayer film hardness of synthetic generally be higher than two simple substance films, unrelieved stress is also than ReB
2Simple substance film much lower, this mainly is because the TaN that unrelieved stress is lower periodically is inserted into ReB
2In the layer, make that its unrelieved stress is necessarily alleviated.Be the multilayer film hardness the highest (34GPa) of 20nm modulation period, simultaneously unrelieved stress also lower (1.39GPa).
Generally speaking: the nano hardness of synthetic multilayer film, film-substrate cohesion stress are all than synthetic simple substance ReB under the similarity condition under each condition
2All obviously improve with the corresponding performance mean value of TaN film; Comparatively speaking, it is the most obvious that synthetic is that the mechanical property of the multilayer film of 20nm is improved modulation period, and nano hardness can reach 34GPa, unrelieved stress is 1.39GPa, and unrelieved stress has obtained obvious release, for the application of reality provides the foundation.Further can prepare ReB with good mechanical characteristics by control process parameters
2/ TaN nano-multilayer film.
This year, the requirement that heat treated part, high hardness material, difficult-to-machine material adopt cutting (even DRY CUTTING) mode to process is constantly surging, in addition, adopt the requirement of a kind of coated material cutter energy machining from the soft to the high hardness material also very strong.And ReB
2/ TaN nano-multilayer film can satisfy these and require cutter coat of new generation, one, ReB
2/ TaN fusing point is higher, makes it can adapt to the requirement of high temperature process workpiece; Two, because its multilayer film, compared with single coating, for example TiCN, TiAlN owing to have the high rigidity effect that superlattice cause, can significantly improve the hardness of surface film, both can prolong cutter life, can improve the hardness of cutter cutting material again; Three, ReB
2, TaN chemical property stable, oxidation-resistance is good, effectively reducing cutter oxidation in use influences it.So, ReB
2/ TaN nano-multilayer film has application prospect first-class, and market potential is huge.
The present invention's magnetron sputtering (MS) method open and that propose prepares superhard ReB
2/ TaN nano-multilayer film, those skilled in the art can be by using for reference this paper content, and links such as appropriate change raw material, processing parameter realize.Method of the present invention and product are described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to method as herein described with product is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (5)
1. ReB
2/ TaN nano-multilayer film is characterized in that depositing earlier in Si (100) substrate at single-sided polishing 50-80nm TaN as transition layer, again alternating deposit TaN and ReB
2Do multilayer film, the phase bed thickness is 10-40nm weekly, and the cycle of multilayer film is the 20-40 layer, and total bed thickness is 400-700nm; ReB wherein
2: the modulation ratio of TaN is 1: 1～7: 1.
2. the described ReB of claim 1
2/ TaN nano-multilayer film, wherein ReB
2: the TaN modulation ratio is 3: 1, and the cycle of multilayer film is that the multilayer film hardness of 20nm reaches the highest.
3. the described ReB of claim 1
2The preparation method of/TaN nano-multilayer film is characterized in that carrying out according to following step:
(1) at first Si (100) substrate of single-sided polishing is handled, the control base reservoir temperature is at 25-300 ℃;
(2) use Ar
+Bombard ReB respectively
2With two targets of TaN, adopt mechanical pump and molecular pump to make base vacuum 2.0 * 10
-4Pa～3.8 * 10
-4Pa, atmospheric pressure value is measured by ionization gauge, and sputter gas is selected pure Ar for use in the deposition process
2, control its flow with mass flow controller and remain on 40～45sccm; Operating air pressure total in the deposition process keeps between 0.5Pa～0.6Pa, and making nano hardness is that 34Gpa, Young's modulus are the high-hard nano-multilayer film of 339GPa;
Wherein the thickness of transition layer TaN is 50-80nm, the multilayer film ReB of alternating deposit
2: the modulation ratio of TaN is 1: 1～7: 1; Phase bed thickness 10～40nm weekly; The cycle of multilayer film is the 20-40 layer, and total bed thickness is 400-700nm.
4. preparation method as claimed in claim 3, wherein said single-sided polishing Si (100) substrate is handled and is referred to: use acetone, ethanol ultrasonic cleaning 15 minutes successively, send into immediately after drying up in the vacuum deposition chamber, then under operating air pressure 6Pa condition, with the Ar of bias voltage-400V
+Sample is cleaned 5min; During deposit film, with purity 99.9% ReB
2Alternately rotate to sputter position and the accurate sputtering time of controlling each target with the TaN target, use Ar equally
+Two target sources of alternating sputtering, the processing parameter in radio-frequency sputtering source: frequency target ReB
2Sputtering power be 50W, the sputtering power of TaN is 110W, target-substrate distance is 6-7cm, substrate bias is-120V.
5. utilize the described ReB of claim 1
2The application of/TaN nano-multilayer film aspect all kinds of blade tools of preparation, die surface strengthening film.
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