A method for the manufacturing of a multi-component target for magnetron sputtering, a set of tools for the manufacturing of a multi-component target for magnetron sputtering, and the sputtering target with its application for the deposition of protective coating

Abstract

A method for manufacturing a multi-component target for magnetron sputtering is that the technological process is conducted using powder materials, the components of which are selected from powders: tungsten (W), in an amount in the range of 69.9 to 84.6 wt%, advantageously 78.4 wt%, boron (B) in an amount in the range of 13.5 to 24.3 wt%, advantageously 15.2 wt% and an intermediate metal, advantageously titanium (Ti), in an amount in the range of 1.7 to 6.4 wt%, advantageously 6,4 wt%, which are placed in a high-energy ball mill in a shielding gas atmosphere, advantageously argon, and then the obtained mixture of powders (5) is compacted in a tool set constructed according to the invention, placed in the vacuum chamber of a spark plasma sintering (SPS) device, where the compacting process is conducted in a sintering temperature from 1600 °C to 1800 °C, advantageously 1650 °C, with a heating rate from 10°C / min to 400 °C / min, over a time of 2 min to 30 min, under a pressure of 30 MPa to 50 MPa, advantageously 32 MPa, in a vacuum of more than 5 x10-2 mbar, advantageously 5 x10-2 mbar, to obtain a multi-component circular magnetron target with a diameter within a range of from 80 mm to 100 mm, advantageously 100 mm. A tool set for the manufacturing of multi-component target placed in a vacuum chamber of the spark plasma sintering (SPS) device, characterised in that graphite sintering tools containing cylindrical punches: lower (1) and upper (2) form with a circular die (3) a feeding chamber with an internal diameter in the range of 80 to 100 mm, advantageously 100 mm for placing a mixture of powders (5). Moreover, the entire tool set has in a horizontal plane, centric in respect to its vertical axis, sequentially placed elements. Proper selection of materials for individual elements of the tool set in the form of graphite and CFRC composite and updated design of the tool set, as well as the use of complete thermal insulation with the use of graphite felt enabled significant reduction of energy demand by the spark plasma sintering device. Multi-component magnetron target, characterized in that it has the form of a circular target with a diameter in the range of 80-100 mm, advantageously 100 mm and contains tungsten (W) in an amount of 69.9 to 84.6 wt%, advantageously 78.4 wt% and boron (B) in an amount from 13.5 to 24.3 wt%, advantageously 15.2 wt% and an intermediate metal, advantageously titanium (Ti), in an amount in the range from 1.7 to 6.4 wt%, advantageously 6.4 wt%.

Description

[0001] A method for the manufacturing of a multi-component target for magnetron sputtering, a set of tools for the manufacturing of a multicomponent target for magnetron sputtering, and the sputtering target with its application for the deposition of protective coating

[0002] The subject of the invention is a method for the manufacturing of a multicomponent target for magnetron sputtering, a set of tools for the manufacturing of a multi-component target for magnetron sputtering, and the sputtering target with its application for the deposition of protective coating based on a material of multi-component magnetron target. The sputtering target manufacturing process is conducted with the application of the High Energy Ball Milling (HEBM) method, the technology of Spark Plasma Sintering (SPS) and the technique of High-Power Impulse Magnetron Sputtering (HiPIMS).

[0003] The invention is particularly applied in the production of large-size forming tools such as dies for extruding profiles and dies for hot forging. The multicomponent magnetron target manufactured according to the method of the invention, in the constructed new tool set for a spark plasma sintering device, is intended for the deposition of thin coatings on a metallic substrate (such as steel) with an HiPIMS method. Therefore, multiple industrial applications include the deposition of thin-layer protective coatings on the working surfaces of mechanical tools, construction elements of machinery, devices and instrument in space technology, computer systems, defence, telecommunications, aeronautical, electronics and power engineering industries.

[0004] The deposition process and characterization of tungsten tantalum diboride (W,Ta)B2 coatings produced by using high-power impulse magnetron sputtering (HiPIMS) from one SPSed target are known from the publication of: R.Psiuk, T.Moscicki, J.Chrzanowska-Gizyhska, L.Kurpaska, J.Radziejewska, P.Denis, D.Garbiec, M.Chmielewski; Mechanical and Thermal Properties of W-Ta-B Coatings Deposited by High-Power Impulse Magnetron Sputtering (HiPIMS); Materials 2023, 16, 664,. Coatings have been produced with Ra<100 nm, where the roughness can be mainly attributed to debris on the surface formed due to arcing. For a pulse duration T = 200 ps and grounded bias (0 V), quite smooth coatings (Ra= 70 nm) can be produced with a deposition rate of 20 nm / min. Furthermore, the deposited coatings are very hard (37 GPa) and are hypothetically fracture-resistant (H / E = 0.109, We= 0.59). The HiPIMS technique can produce crystalline coatings of tungsten diboride at a relatively low temperature of 400°C. Biasing the substrate can change the structure from crystalline to semicrystalline. Changing the duration of the pulses has a significant effect on the amount of boron in the films. The small amount of boron is responsible for obtaining a high hardness of above 37 GPa. Tungsten-tantalum diboride has high thermal stability up to 1000 °C in a vacuum (invariance of the crystal phases), and it can withstand oxidation at 500 °C. Coatings with the properties presented in this paper might be good alternatives to materials that are already used in industries.

[0005] In the article: T.Moscicki, R.Psiuk, H.Slominska, N.Levintant-Zayonts, D.Garbiec, M.Pisarek, P.Bazamik, S.Nosewicz, J.Chrzanowska-Gizynska; Influence of over stoichiometric boron and titanium addition on the properties of RF magnetron sputtered tungsten borides; Surface & Coatings Technology 390(2020) 125689, (W,Ti)B2 films with different stoichiometric ratio Ti / W deposited on silicon and 304 stainless steel by radio frequency magnetron sputtering are presented. The coatings were deposited from spark plasma sintered targets obtained from the mixture of pure boron, tungsten and titanium powders. It is shown that during the spark plasma sintering process using over stoichiometric boron and low content of titanium change the WB2 to WB4phase with almost no secondary phases. Subsequently, the impact of titanium content on the films’ properties is investigated systematically, including the chemical and phase composition, crystalline structure, surface and cross-section morphology. Simultaneously, nano-indentation and ball-on-disk tribometer tests are performed to analyse the hardness and tribological properties of the films. Moreover, the deposited films with titanium content of 3.6 and 5.5 at.% are formed in zone T of Thornton's Structural Zone Model. In opposite to 01-WB2 magnetron sputtered coatings, they are hard, nanocomposite, and more flexible. The results show that the addition of titanium is changing the film structure from nanocrystalline columnar to an amorphous, very dense and compact structure with the addition of TiB2 phase. That films are simultaneously hard (H >37.5 GPa), have high hardness to effective Young's modulus ratio values (H / E >0.1) and have elastic recovery (We>60%) appropriate for tough and crack-resistant materials. The presented (W,Ti)B2 films exhibit also tribological and corrosion properties better than unalloyed coatings.

[0006] In the publication: D.Garbiec, M.Wisniewska, R.Psiuk, P.Denis, N.Levintant-Zayonts, V.Leshchynsky, R.Rubach, T.Moscicki; Zirconium alloyed tungsten borides synthesized by spark plasma sintering; Published online: 25 February 2021, samples of tungsten borides (WBX; x=2.5 or 4.5) with increasing substitution of tungsten by zirconium from 0 to 24 at.% were synthesized for the first time by spark plasma sintering. The influence of the process parameters, mainly the holding time (2.5-30 min), on the properties of W-Zr-B compounds was studied. The main conclusions are: • The boron and zirconium content influence the densification behaviour. The increase in the zirconium content caused a decrease in the density of the SPSed samples. • With an increasing holding time (>9 min), two stages of reactive spark plasma sintering were observed, and hence WB4 phase decomposition to WB2+2B occurred. • A rapid heating rate (400 °C / min), short holding time (2.5 min), zirconium doping and small boron over stoichiometric (B at. / (W+Zr) at. = 4.5) with spark plasma sintering process conducted at the relatively high sintering temperature of 1800 °C (higher than the temperature limit of the WB4 presence) lead to the formation of the microstructure containing the WB4 phase.

[0007] The friction and wear test results reveal the formation of a boron-based film which seems to play the role of a solid lubricant. The properties of the obtained materials mean that W-Zr-B compounds may be competitive in the future with currently used materials such as tungsten carbide-cobalt cemented carbides. Due to the high electrical conductivity, hardness, wear resistance and also relatively simple and fast synthesis method, the developed material can be used in many fields of industry.

[0008] The properties of tungsten diboride and its solid solutions with chromium, molybdenum, rhenium and zirconium in the form of spark plasma sintered bulk samples and magnetron sputtered coatings were synthesized and characterized in the publication: T.Moscicki, R.Psiuk, J.Radziejewska, M.Wisniewska, D.Garbiec; Properties of Spark Plasma Sintered Compacts and Magnetron Sputtered Coatings Made from Cr, Mo, Re and Zr Alloyed Tungsten Diboride; Coatings 2021, 11, 1378. Various concentrations of transition metal elements, ranging from 0.0 to 24.0 at.%, on a metals basis, were made. Spark plasma sintering was used to manufacture these refractory compounds from the pure elements. The elemental and phase purity of both samples (sintered compacts and coatings) were examined using energy-dispersive X-ray spectroscopy and X-ray diffraction. Furthermore, microindentation was used to measure the Vickers hardness under an applied load of 2 N for bulks and 0.1 N for coatings, respectively. The main observations are: • X-ray diffraction results of SPS-ed compacts indicate that the solubility limit is below 8 at.% for molybdenum, rhenium and zirconium and below 16 at.% for chromium. Above this limit, both diborides (W,TM)B2 are created. • The addition of transition metal causes the decrease of density and increase of hardness and electrical conductivity of sintered compacts. • Deposited coatings Wi-xTMxBy (TM = Cr, Mo, Re, Zr; x = ~0.2; y = 1.7-2.0) are homogenous, smooth and hard. The highest hardness for W-Cr-B2 coatings measured under the load 10 g was 50.4 ± 4.7 GPa. Deposited films have relatively high fracture toughness. As an example, for WB2 coatings alloyed with zirconium, it was K|C= 2.1 1 MPa m1 / 2. The connection of very high hardness with high fracture toughness places these coatings in a group of novel materials with improved mechanical properties.

[0009] The PL 236488 (Bl) patent also shows a method for making a collapsible target for a magnetron, comprising the step of making a shaped piece (1) of a first material and an insert of a second material (2) at least partially coinciding with the plasma etch channel (3) of the magnetron. The shaped piece (1) of the first material and at least one recess (4, 4a, 4b) are made to partially overlap the plasma etching channel (3). An insert of the second material (2) is made by introducing powdered material into this recess (4, 4a, 4b) and the material is then consolidated by a glow discharge in the working gas.

[0010] Description of the invention PL 219259 (Bl) relates to a target for the production of transparent ZnlrSiO semiconductor films by physical vapour deposition and a method for producing such a target.

[0011] The target for the production of transparent ZnlrSiO semiconductor films by the physical vapour deposition method is characterized by consisting of at least one sequence of Ir / Zn / Si / Ir films, where the Ir film is always the first and last film and the thickness of the individual films is selected in the way that the total atomic composition of the target is 50 ± 5% I, 25 ± 2.5% Zn, 25 ± 2.5% Si, and its total thickness is greater than 5 pm. The ZnlrSiO semiconductor films deposition method by the method of physical vapour deposition is firstly done by cathode sputtering of one-component Zn, Ir, Si targets with a purity of 5 N to form the multilayer structure containing at least one deposited sequence of Ir / Zn / Si / Ir films on the metallic substrate. Secondly, the structure is annealed at a temperature of <400 °C for at least 30 min in an inert gas flow or under a vacuum.

[0012] Polish patent PL 221077 (Bl) describes the method of thin film deposition in a multi-target magnetron sputtering system, in particular, intended for the production of single-component or multi-component films or multi-layer films.

[0013] The method of thin film deposition in a multi-target magnetron sputtering system is conducted in one technological cycle, as a result of the deposition of at least one layer of the target material and / or reaction products of the target material with the reactive gas fed through the inlets (W) to the vacuum chamber (K). The process is conducted through the sputtering process of at least one target (T) and its deposition on the substrates (PD) placed on the stage (ST). During the application of at least one target material layer to the substrates (PD), the control system (S) is controlling power supplied from the power supply (Zl, Z2, Z3, ..., Zn ) to at least one pulse magnetron (Ml, M2, M3, ..., Mn ). In the meantime, the working time of each magnetron (Ml, M2, M3, ..., Mn ) is individually set by a separate switching circuit using a control system (S) equipped with a microprocessor controller.

[0014] From the European patent EP 2417279 "Target based on molybdenum and production method with thermal projection of a target" invention is known. It relates to a process for developing a target intended for use in vacuum deposition processes, in a neutral or reactive atmosphere by cathodic sputtering assisted with a magnetic field, sputtering or an ion source. The invention relates particularly to a target of nominal thickness, comprising at least one compound based on molybdenum. The target has a lamellar microstructure, an oxygen rate lower than 1000 ppm, preferably lower than 600 ppm, and especially preferably lower than 450 ppm. Moreover, it is characterized by an electrical resistance of less than 5 times, preferably 3 times, and especially preferably twice of theoretical electrical resistance of the compound.

[0015] Polish patent PL 211827 (Bl) reveals the method of producing thin films of TiO2and a titanium target. The stable rutile structure of the nanocrystalline thin film is obtained directly by magnetron sputtering on the microelectronics.

[0016] A method of producing thin films of TiO2on substrates from a target with a diameter of 100 mm and a thickness of 3 mm made of titanium in the form of a disc, where the target is sputtered with the use of a magnetron. The circular titanium metal target, constituting the cathode, is placed on a circular spacer, which is made of a flame-retardant and electrically conductive material with a thickness of 0.5 mm to 3 mm and a diameter of not more than 5 mm. Next, the process of ion bombardment and additionally by limiting heat dissipation to the system cathode cooling, the target is heated to a temperature of at least 773 K and the target material is applied on the substrate heated to a temperature above 370 K in a reactive oxygen atmosphere with pressure below 10'1Pa. The working surface of the target is plasma treated before the target spraying process.

[0017] The publication of the CN 11573172 (A) patent application also shows a ceramic target material as well as the preparation method and application thereof.

[0018] The ceramic target material is prepared from the following raw materials in percentage by mole: 89-96% of zirconium oxide, 2-10% of scandium oxide, 0.5-4% of yttrium oxide and 0.1-3% of other rare earth oxides. A traditional zirconium oxide material is optimized and modified based on multi-element rare earth synergistic doping. The marine environment corrosion resistance is improved. The invention also provides a preparation method which comprises the following steps: carrying out ball milling, drying, calcining and granulating on the raw materials to obtain the granulated powder, carrying out pre-pressing, secondary pressurizing and glue discharging on the granulated powder to obtain a ceramic target material green compacts, and finally calcining the green compacts to obtain the ceramic target material. According to the preparation method, the introduction of impurities such as Cl and S can be avoided fundamentally, the preparation method is more suitable for batch industrial production, and the obtained novel zirconia-based thermal barrier coating material can have excellent high-temperature phase stability in a simulated marine environment.

[0019] A method of preparation of ITO ceramic targets is known from the description of the CN 113735568 (A) Chinese patent application.

[0020] The invention provides a preparation method for an ITO (indium tin oxide) ceramic target material, which comprises the following steps: performing wet ball-milling mixing on I Ch powder and SnO2 powder with a purity of 99.99% according to the mass ratio of (90-97):(10-3), and adding a small amount of organic additive in the ball-milling process to obtain ITO slurry with good flowing property; allowing ITO slurry to be subjected to spray granulation to obtain spherical ITO granulation powder; pressing obtained ITO granulation powder to obtain an ITO green compacts with a regular shape; carrying out cold isostatic secondary pressing on the ITO green compact; degreasing the ITO green compact subjected to cold isostatic pressing at low temperature to remove the organic additive; and finally carrying out hot isostatic pressing sintering on the degreased ITO green compact to prepare the ITO target material with high density and low resistivity. In the hot isostatic pressing treatment process, low-carbon steel is selected as a sheath, stainless steel is used as an isolation material to prevent the sheath from reacting with the target material and facilitating its later removement. According to the method, the sintering temperature and the sintering time required in the ITO target material preparation process are effectively reduced, the problem that the production period of a traditional normal-pressure sintering process is too long is solved, and the method plays a crucial role in improving the production efficiency of the target material.

[0021] The cylindrical ceramic sputtering target and its manufacturing apparatus and manufacturing method are known from the publication JP 2019183285 (A) of the Japanese patent application. The invention provides a cylindrical ceramic sputtering target including a cylindrical substrate, a cylindrical ceramic target material, and a solder for bonding the cylindrical substrate and the cylindrical ceramic target material. The dial gauge is placed at a position of an inner side 7 mm from both ends of the cylindrical ceramic target material. The reading of the dial gauge is measured by rotating the cylindrical ceramic sputtering target once with a position of an outer side 15 mm from each of both ends of the cylindrical ceramic target material on an outer peripheral surface of the cylindrical substrate as a fulcrum. In the cylindrical ceramic sputtering target, the difference between the maximum and minimum readings of the dial gauge is 1.0 mm or less at any measurement point. The apparatus and method for producing the same are also provided. The cylindrical ceramic sputtering target of the present invention can form a uniform thin film up to the life end by sputtering. A solution according to the invention concerns a method of manufacturing, in a constructed new tool set of a Spark Plasma Sintering (SPS) device of a multi-component magnetron target intended for the manufacturing of a protective coating based on the material used to create the target, with the method of High-Power Impulse Magnetron Sputtering (HiPIMS).

[0022] The essence of the solution according to the invention, which is a method for manufacturing of a multi-component target for magnetron sputtering using the method of High Energy Ball Milling (HEBM), technology of Spark Plasma Sintering (SPS) and technique of High-Power Impulse Magnetron Sputtering (HiPIMS), consists of the technological process being conducted using powder materials, the components of which are selected from among the following powders: tungsten (W), in an amount in the range of 69.9 to 84.6 wt%, advantageously 78.4 wt%, boron (B) in an amount in the range of 13.5 to 24.3 wt%, advantageously 15.2 wt% and an intermediate metal, advantageously titanium (Ti), in an amount in the range of 1.7 to 6.4 wt%, advantageously 6.4 wt%, which are placed in a high-energy ball mill in a shielding gas atmosphere, advantageously argon, and then the obtained mixture of powders (5) is compacted in a tool set constructed according to the invention, placed in the vacuum chamber of a Spark Plasma Sintering (SPS) device, where the compacting process is conducted in a sintering temperature from 1600 °C to 1800 °C, advantageously 1650 °C, with a heating rate from 10 °C / min to 400 °C / min, over a time of 2 min to 30 min, under a pressure of 30 MPa to 50 MPa, advantageously 32 MPa, in a vacuum of more than 5 x 1 O’2mbar, advantageously 5 x 1 O'2mbar, to obtain a multicomponent circular magnetron target with a diameter within a range from 80 mm to 100 mm, advantageously 100 mm.

[0023] It is advantageous when the powder material containing tungsten (W) in an amount in the range of 66.5 to 83.1 wt%, advantageously 74.1 wt% and boron (B) in an amount in the range of 13.3 to 23.1 wt%, advantageously 14.3 wt% is doped with an intermediate metal, advantageously zirconium (Zr) in an amount in the range of 3.2 to 11.6 wt%, advantageously 11 .6 wt%.

[0024] It is advantageous when the powder material containing tungsten (W) in an amount in the range of 60.3 to 80.3 wt%, advantageously 66.4 wt% and boron (B) in an amount in the range of 12.8 to 21.0 wt%, advantageously 12.9 wt% is doped with an intermediate metal, advantageously tantalum (Ta) in an amount in the range of 6.2 to 20.7 wt%, advantageously 20.7 wt%.

[0025] It is advantageous when the powder material containing tungsten (W) in an amount in the range of 59.9 to 80.1 wt%, advantageously 66.1 wt% and boron (B) in an amount in the range of 12.8 to 20.9 wt%, advantageously 12.8 wt% is doped with an intermediate metal, advantageously rhenium (Re) in an amount in the range of 6.4 to 21.1 wt%, advantageously 21.1 wt%.

[0026] Moreover, it is advantageous if the powder material containing tungsten (W) in an amount in the range of 66.1 to 83.0 wt%, advantageously 73.6 wt% and boron (B) in an amount in the range of 13.3 to 23.0 wt%, advantageously 14.3 wt% is doped with an intermediate metal, advantageously molybdenum (Mo) in an amount in the range of 3.4 to 12.1 wt%, advantageously 12.1 wt% .

[0027] It is moreover advantageous if the powder material containing tungsten (W) in an amount in the range of 69.6 to 84.4 wt%, advantageously 77.9 wt% and boron (B) in an amount in the range of 13.5 to 24.2 wt%, advantageously 15.1 wt% is doped with an intermediate metal, advantageously chromium (Cr) in an amount in the range of 1.9 to 7.0 wt%, advantageously 7.0 wt%.

[0028] A tool set for the manufacturing of multi-component target placed in a vacuum chamber of the spark plasma sintering (SPS) device, characterised in that graphite sintering tools containing cylindrical punches: lower and upper form with a cylindrical die a feeding chamber with an internal diameter in the range of 80 to 100 mm, advantageously 100 mm for placing a mixture of powders. Moreover, the entire tool set has in a horizontal plane, centric in respect to its vertical axis, sequentially placed elements, where: the lower punch on its frontal upper surface has an upper carbon fibre reinforced carbon (CFRC) composite spacer with a thickness in the range of 5 to 10 mm, advantageously 5 mm, over which a circular upper graphite spacer is placed, with a thickness in the range of 5 to 10 mm, advantageously 5 mm and on it the circular upper graphite film is placed, which adheres from the bottom to the powder mixture, covered from above with a circular lower graphite film, over which the following are placed in sequence: circular lower graphite spacer with a thickness, advantageously 5 mm, and on it the lower carbon composite (CFRC) spacer with a thickness advantageous 5 mm, which is in contact with the lower surface of the upper punch, whereas to the lower frontal surface of the lower punch and to the upper frontal surface of the upper punch coaxially placed conical intermediate elements: lower and upper, which adapt the nominal diameters of the electrodes in the SPS device to the nominal external diameter of the punches: lower and upper, and additionally on external frontal surfaces of the conical intermediate elements there are axially placed carbon composite (CFRC) plates: lower and upper with a thickness in the range from 5 to 10 mm, advantageously 10 mm. Moreover, in the vertical axis of the tool set a centric hole is made, passing through the upper and lower carbon composite (CFRC) spacer, lower and upper punches, lower and upper conical intermediate element and lower and upper carbon composite (CFRC) plate, which enables a constant measurement of the powder mixture compaction temperature using a pyrometer, whereas the internal surface of the die is covered with a graphite film and for complete thermal insulation, the external surface of the die is covered with graphite felt.

[0029] Multi-component magnetron target characterized in that it has the form of a circular with a diameter in the range of 80-100 mm, advantageously 100 mm and contains tungsten (W) in an amount of 69.9 to 84.6 wt%, advantageously 78.4 wt% and boron (B) in an amount from 13.5 to 24.3 wt%, advantageously 15.2 wt% and an intermediate metal, advantageously titanium (Ti), in an amount in the range from 1.7 to 6.4 wt%, advantageously 6.4 wt%.

[0030] It is advantageous when the target contains tungsten (W) in an amount from 66.5 to 83.1 wt%, advantageously 74.1 wt% and boron (B) in an amount from

[0031] 13.3 to 23.1 wt%, advantageously 14.3 wt% and an intermediate metal, advantageously zirconium (Zr), in an amount in the range from 3.2 to 11.6 wt%, advantageously 11.6 wt%.

[0032] It is advantageous when the target contains tungsten (W) in an amount from

[0033] 60.3 to 80.3 wt%, advantageously 66.4 wt% and boron (B) in an amount from

[0034] 12.8 to 21.0 wt%, advantageously 12.9 wt% and an intermediate metal, advantageously tantalum (Ta), in an amount in the range from 6.2 to 20.7 wt%, advantageously 20.7 wt%.

[0035] It is advantageous when the target contains tungsten (W) in an amount from

[0036] 59.9 to 80.1 wt%, advantageously 66.1 wt% and boron (B) in an amount from 12.8 to 20.9 wt%, advantageously 12.8 wt% and an intermediate metal, advantageously rhenium (Re), in an amount in the range from 6.4 to 21.1 wt%, advantageously 21.1 wt%.

[0037] Moreover, it is advantageous if the target contains tungsten (W) in an amount from 66.1 to 83.0 wt%, advantageously 73.6 wt% and boron (B) in an amount from 13.3 to 23.0 wt%, advantageously 14.3 wt% and an intermediate metal, advantageously molybdenum (Mo), in an amount in the range from 3.4 to 12.1 wt%, advantageously 12.1 wt%.

[0038] It is moreover advantageous if the target contains tungsten (W) in an amount from 69.6 to 84.4 wt%, advantageously 77.9 wt% and boron (B) in an amount from 13.5 to 24.2 wt%, advantageously 15.1 wt% (w / w) and an intermediate metal, advantageously chromium (Cr), in an amount in the range from 1.9 to 7.0 wt%, advantageously 7.0 wt%.

[0039] The use of a multi-component magnetron target according to the invention manufactured using the method according to the invention in the tool set according to the invention, for the deposition of a protective thin film based on the material constituting the magnetron target, on surfaces of large-size elements, in particular on working surfaces of metal forming tools, where the magnetron target with a diameter of 80 to 100 mm, advantageously 100 mm is used, which is placed on the magnetron head and subjected to the process of high- power impulse magnetron sputtering in a process chamber with the use of an industrial magnetron corresponding to the diameter of the target, advantageously 4-inch, for depositing from the magnetron target protective thin coatings on a metal substrate, advantageously steel.

[0040] The high impulse power magnetron stuttering is conducted in three stages, where in the first stage the magnetron target is heated with electric heaters with a current I = 160 A, over a time t = 30 min, at the pressure of p = IxlO’4mbar in the process chamber, afterwards in the second stage ion etching is conducted in a 100% argon atmosphere at the pressure of p = 5x1 O'1mbar, with impulse polarisation with a negative voltage in the range of U = -600 V to -800 V, frequency f = 2 kHz, duty cycle A = 90% and the stabilised current value of I = 4 A, further in the third stage the protective coating is deposited in a 100% argon atmosphere, at a pressure of p = 1.2x1 O'2mbar, with a supply with voltage bias Ubias=-50 V, using the High-Power Impulse Magnetron Sputtering (HiPIMS) with the following parameters: the period is T = 1000 ps, the frequency of impulses is f = 1 kHz in short time intervals t = 30 ps, whereas the coating deposition time is t = 90 min at a deposition temperature of 350 °C.

[0041] The use of the solution presented in the invention enables the following technical and utility effects:

[0042] - innovative design of a tool set with elements made of graphite and CFRC composite enables the manufacturing of a target with a higher diameter, up to 100 mm in a conventional Spark Plasma Sintering (SPS) device, in which elements with a diameter of up to 80 mm are commonly manufactured, which currently occurs for most of SPS equipment installed globally;

[0043] - manufacturing of magnetron targets with a diameter of 100 mm provides the ability to deposit from these targets, through High-Power Impulse Magnetron Sputtering, of protective thin coatings on large metal, in particular steel, substrates e.g., on working surfaces of hot forging or extruding tools;

[0044] - using a large diameter (100 mm) target enables faster deposition of thin coatings on large surfaces, in particular on working surfaces of large-size metal forming tools;

[0045] - the target manufactured according to the invention enables further mechanical treatment in a grinding process, to ensure the disc meets the required dimensions and surface quality;

[0046] - proper selection of materials for individual elements of the tool set in the form of graphite and CFRC composite and updated design of the tool set, as well as the use of complete thermal insulation with the use of graphite felt enabled a significant reduction of energy demand by the spark plasma sintering device;

[0047] - the use of prepared multi-component target with high quality: high density, low brittleness, and also high uniformity of the chemical composition over the entire volume of the target, enables limiting the number of magnetron targets and thus decreases the number of magnetrons used in the process of deposition of a coating using high-power impulse magnetron sputtering. In the proposed solution according to the invention for the deposition of a protective coating on a circular area with a diameter of 100 mm one target is used with a previously established composition: Wo.76Tio.24B2.5 instead of two, used in the traditional process of deposition of this type of a coating, performed with separate, currently available on the market targets, that is, a W2B5 target and a Ti target. In this process with the use of a developed target with a composition of Wo.76Tio.24B2.5 the two-fold reduction of the number of magnetron plasma sources needed to ensure the uniformity of the plasma environment in the required process volume is possible;

[0048] - during industrial deposition of the coatings the uniformity of the plasma environment in a large space of the process chamber is ensured;

[0049] - the high-power impulse magnetron sputtering technique enables significant lowering of the coating deposition process temperature, that is, in the case of a Wo.76Tio.24B2.5 coating from 500°C (using a DC or RF generator) to 350°C;

[0050] - the possibility of producing using the magnetron target according to the invention of a protective coating in the form of a thin film with a high hardness of 20-40 GPa, appropriate elastic properties, and the fracture toughness of 1.5-3 MPa m1 / 2depending on the parameters of deposition and the doped transitional element, surface roughness of 10-80 nm and high thermal stability at a high temperature up to 600°C;

[0051] - solution according to the invention constitutes a basis for developing a technological process and to develop a technology of protective thin coating deposition, from the manufacturing of a target to the deposition of coating on surfaces, in particular on large-size elements. The subject of the solution is addressed mainly to the manufacturers of tools for metals forming and / or users of these tools, e.g., dies for extruding aluminium profiles and dies for hot forging. The deposited thin films on working surfaces of tools are characterised by high hardness (20-40 GPa), resistance to cracking and thermal shocks;

[0052] - the possibility of commercialisation and industrial-scale deployment of a new product in the form of a magnetron target with a diameter up to 100 mm for deposition of high-quality thin protective coating on surfaces, in particular of large-size elements, manufactured in an energy-efficient process technology, safe for the natural environment.

[0053] The subject of the invention was presented more closely on example implementations and on a drawing, which presents a diagram of the tool set of a device for Spark Plasma Sintering (SPS) in an axial cross-section.

[0054] A method for manufacturing a multi-component target for magnetron sputtering with a tool set is illustrated in examples 1-7:

[0055] Example 1

[0056] A powder material, containing: tungsten (W) in an amount of 78.4 wt% and boron (B) in an amount of 15.2 wt% doped with titanium (Ti) in an amount of 6.4 wt% is mixed in a high-energy ball mill in an atmosphere of argon, and then the obtained mixture of powders 5 is compacted in the constructed tool set, placed in a vacuum chamber of a spark plasma sintering (SPS) device, where the compaction process is conducted at a sintering temperature of 1650°C with a heating rate of 10°C / min, over a time of 2 min under a pressure of 30 MPa, in a 5x 10'2mbar vacuum, to obtain a multi-component circular target, with a diameter of 100 mm, for high-power impulse magnetron sputtering.

[0057] Example 2

[0058] The prepared powder material, containing tungsten (W) in an amount of 74.1 wt% and boron (B) in an amount of 14.3 wt% doped with zirconium (Zr) in an amount of 11.6 wt% is subjected to the process of mixing in a high-energy ball mill and afterwards processed as in example 1.

[0059] Example 3

[0060] The prepared powder material, containing tungsten (W) in an amount of 66.4 wt% and boron (B) in an amount of 12.9 wt% doped with tantalum (Ta) in an amount of 20.7 wt% is subjected to the process of mixing in a high-energy ball mill and afterwards processed as in example 1.

[0061] Example 4

[0062] The prepared powder material, containing tungsten (W) in an amount of 66.1 wt% and boron (B) in an amount of 12.8 wt% doped with rhenium (Re) in an amount of 21.1 wt% is subjected to the process of mixing in a high-energy ball mill and afterwards processed as in example 1.

[0063] Example 5

[0064] The prepared powder material, containing tungsten (W) in an amount of 73.6 wt% and boron (B) in an amount of 14.3 wt% doped with molybdenum (Mo) in an amount of 12.1 wt% is subjected to the process of mixing in a high-energy ball mill and afterwards processed as in example 1.

[0065] Example 6 The prepared powder material, containing tungsten (W) in an amount of 77.9 wt% and boron (B) in an amount of 15.1 wt% doped with chromium (Cr), in an amount of 7.0 wt% is subjected to the process of mixing in a high-energy ball mill and afterwards processed as in example 1.

[0066] Example 7

[0067] Procedure as in examples 1 to 6, only the compaction process is conducted in a sintering temperature of 1800 °C, with a heating rate of 400 °C / min, over a time of 30 min, under a pressure of 50 MPa, in a 5x 1 O'2mbar vacuum, to obtain a multicomponent circular target with a diameter of 100 mm, for impulse magnetron sputtering.

[0068] A tool set for the manufacturing of multi-component target placed in a vacuum chamber of the Spark Plasma Sintering (SPS) device, has a graphite sintering tools containing cylindrical punches: lower 1 and upper 2 form with a cylindrical die 3 a feeding chamber with an internal diameter in the range of 80 to 100 mm, advantageously 100 mm for placing a mixture of powders 5. Moreover, the entire tool set has in a horizontal plane, centric in respect to its vertical axis, sequentially placed elements, where: the lower punch 1 on its frontal upper surface has an upper carbon fibre reinforced carbon (CFRC) composite spacer 6 with a thickness in the range of 5 to 10 mm, advantageously 5 mm, over which a circular upper graphite spacer 8 is placed, with a thickness in the range of 5 to 10 mm, advantageously 5 mm and on it the circular upper graphite film 10 is placed, which adheres from the bottom to the powder mixture 5, covered from above with a circular lower graphite film 11, over which the following are placed in sequence: circular lower graphite spacer 9 with a thickness, advantageously 5 mm, and on it the lower carbon composite (CFRC) spacer 7 with a thickness advantageous 5 mm, which is in contact with the lower surface of the upper punch 2, whereas to the lower frontal surface of the lower punch 1 and to the upper frontal surface of the upper punch 2 coaxially placed conical intermediate elements: lower 12 and upper 13, which adapt the nominal diameters of the electrodes in the SPS device to the nominal external diameter of the punches: lower 12 and upper 13, and additionally on external frontal surfaces of the conical intermediate elements 12 and 13 there are axially placed carbon composite (CFRC) plates: lower 14 and upper 15 with a thickness in the range from 5 to 10 mm, advantageously 10 mm. Moreover, in the vertical axis of the tool set a centric hole is made, passing through the upper 6 and lower 7 carbon composite (CFRC) spacer, lower 1 and upper 2 punches, lower 12 and upper 13 conical intermediate element and lower 14 and upper 15 carbon composite (CFRC) plate, which enables a constant measurement of the powder mixture compaction temperature using a pyrometer, whereas the internal surface of the die 3 is covered with a graphite film 16 and for complete thermal insulation, the external surface of the die 3 is covered with graphite felt 4.

[0069] Example implementations of a multi-component magnetron target acc. to the invention were presented in the examples 8-13 below, whereas the creation of a protective coating based on a material constituting the multi-component magnetron disc was described in examples 14-15.

[0070] Example 8

[0071] Multi-component magnetron target has the form of a circular target with a diameter of 100 mm, which contains tungsten (W) in an amount of 78.4 wt% and boron (B) in an amount of 15.2 wt% as well as an intermediate metal - titanium (Ti) in an amount of 6.4 wt%.

[0072] Example 9

[0073] Multi-component magnetron target has the form of a circular target with a diameter of 100 mm, which contains tungsten (W) in an amount of 74.1 wt% and boron (B) in an amount of 14.3 wt% as well as an intermediate metal - zirconium (Zr) in an amount of 11.6 wt%.

[0074] Example 10

[0075] Multi-component magnetron target has the form of a circular target with a diameter of 100 mm, which contains tungsten (W) in an amount of 66.4 wt% and boron (B) in an amount of 12.9 wt% as well as an intermediate metal - tantalum (Ta) in an amount of 20.7 wt%.

[0076] Example 11

[0077] Multi-component magnetron target has the form of a circular target with a diameter of 100 mm, which contains tungsten (W) in an amount of 66.1 wt% and boron (B) in an amount of 12.8 wt% as well as an intermediate metal - rhenium (Re) in an amount of 21.1 wt%.

[0078] Example 12

[0079] Multi-component magnetron target has the form of a circular target with a diameter of 100 mm, which contains tungsten (W) in an amount of 73.6 wt% and boron (B) in an amount of 14.3 wt% as well as an intermediate metal - molybdenum (Mo) in an amount of 12.1 wt%.

[0080] Example 13

[0081] Multi-component magnetron target has the form of a circular target with a diameter of 100 mm, which contains tungsten (W) in an amount of 77.9 wt% and boron (B) in an amount of 15.1 wt% as well as an intermediate metal - chromium (Cr) in an amount of 7.0 wt%. Example 14

[0082] An example of the use of the multi-component target for the deposition of a protective coating on the surfaces of tools for the metals forming based on the material constituting the multi-component magnetron target using the method according to the invention, in a tool set presented as follows:

[0083] Circular magnetron target with a diameter of 100 mm and placed in the magnetron head and subjected to the process of high-power impulse magnetron sputtering in a process chamber with the use of a 4-inch industrial magnetron corresponding to the diameter of the target for depositing from the magnetron target of a protective thin coating on a steel substrate, whereas the high-power impulse magnetron sputtering is conducted in three stages, where in the first stage the magnetron target is heated with electric heaters with a current I = 160 A, over a time t = 30 min, at the pressure in the process chamber p = 1 x 1 O'4mbar, afterwards in the second stage ion etching is conducted in a 100% argon atmosphere at the pressure of p = 5x 10'1mbar, with impulse polarisation with a negative voltage in the range of U = -600 V to -800 V, frequency f = 2 kHz, duty cycle A = 90% and stabilised current value of I = 4 A, further in the third stage the protective coating is deposited in a 100% argon atmosphere, at a pressure of p = 1.2 1 O’2mbar, with a supply with voltage bias Ubias=-50 V, using the High-Power Impulse Magnetron Sputtering (HiPIMS) with the following parameters: the period is T = 1000 ps, the frequency of impulses is f = 1 kHz in short time intervals t = 30 ps, whereas the coating deposition time is t = 90 min at a deposition temperature of 350°C.

[0084] Example 15

[0085] The process of creating a protective thin coating based on the material constituting the multi-component magnetron target, as shown in examples 8 to 13, was conducted by high-power impulse magnetron sputtering in three stages, as presented in example 14.

Claims

Claims1. A method for manufacturing a multi-component target for magnetron sputtering using High-Power Impulse Magnetron Sputtering (HiPIMS) with the application of High Energy Ball Milling (HEBM) and the Spark Plasma Sintering (SPS) technology characterized in that the technological process is conducted using powder materials, the components of which are selected from powders: tungsten (W), in an amount in the range of 69.9 to 84.6 wt%, advantageously 78.4 wt%, boron (B) in an amount in the range of 13.5 to 24.3 wt%, advantageously 15.2 wt% and an intermediate metal, advantageously titanium (Ti), in an amount in the range of 1.7 to 6.4 wt%, advantageously 6,4 wt%, which are placed in a high- energy ball mill in a shielding gas atmosphere, advantageously argon, and then the obtained mixture of powders (5) is compacted in a tool set constructed according to the invention, placed in the vacuum chamber of a spark plasma sintering (SPS) device, where the compacting process is conducted in a sintering temperature from 1600°C to 1800°C, advantageously 1650°C, with a heating rate from 10°C / min to 400°C / min, over a time of 2 min to 30 min, under a pressure of 30 MPa to 50 MPa, advantageously 32 MPa, in a vacuum of more than 5x1 O'2mbar, advantageously 5xl0’2mbar, to obtain a multi-component circular magnetron target with a diameter within a range of from 80 mm to 100 mm, advantageously 100 mm.

2. A method according to claim 1, characterised in that the powder material containing tungsten (W) in an amount in the range of 66.5 to 83.1 wt%, advantageously 74.1 wt% and boron (B) in an amount in the range of 13.3 to 23.1 wt%, advantageously 14.3 wt% is doped with an intermediate metal, advantageously zirconium (Zr) in an amount in the range of 3.2 to 11.6 wt%, advantageously 11.6 wt%.

3. A method according to claim 1, characterised in that the powder material containing tungsten (W) in an amount in the range of 60.3 to 80.3 wt%, advantageously 66.4 wt% and boron (B) in an amount in the range of 12.8 to 21.0 wt%, advantageously 12.9 wt% is doped with an intermediate metal, advantageously tantalum (Ta) in an amount in the range of 6.2 to 20.7 wt%, advantageously 20.7 wt%.

4. A method according to claim 1, characterised in that the powder material containing tungsten (W) in an amount in the range of 59.9 to 80.1 wt%, advantageously 66.1 wt% and boron (B) in an amount in the range of 12.8 to 20.9 wt%, advantageously 12.8 wt% is doped with an intermediate metal, advantageously rhenium (Re) in an amount in the range of 6.4 to 21.1 wt%, advantageously 21.1 wt%.

5. A method according to claim 1, characterised in that the powder material containing tungsten (W) in an amount in the range of 66.1 to 83.0 wt%, advantageously 73.6 wt% and boron (B) in an amount in the range of 13.3 to 23.0 wt%, advantageously 14.3 wt% is doped with an intermediate metal, advantageously molybdenum (Mo) in an amount in the range of 3.4 to 12.1 wt%, advantageously 12.1 wt%.

6. A method according to claim 1, characterised in that the powder material containing tungsten (W) in an amount in the range of 69.6 to 84.4 wt%, advantageously 77.9 wt% and boron (B) in an amount in the range of 13.5 to 24.2 wt%, advantageously 15.1 wt% is doped with an intermediate metal, advantageously chromium (Cr) in an amount in the range of 1.9 to 7.0 wt%, advantageously 7.0 wt%.

7. A tool set for the manufacturing of multi-component target placed in a vacuum chamber of the spark plasma sintering (SPS) device, characterised in that graphite sintering tools contain cylindrical punches: lower (1) and upper (2) form with a cylindrical die (3) a feeding chamber with an internal diameter in the range of 80 to 100 mm, advantageously 100 mm for placing a mixture of powders (5), moreover the entire tool set has in a horizontal plane, centric in respect to its vertical axis, sequentially placed elements, where: the lower punch (1) on its frontal upper surface has an upper carbon fibre reinforced carbon (CFRC) composite spacer (6) with a thickness in the range of 5 to 10 mm, advantageously 5 mm, over which a circular upper graphite spacer (8) is placed, with a thickness in the range of 5 to 10 mm, advantageously 5 mm and on it the circular upper graphite film (10) is placed, which is adheres from the bottom to the powder mixture (5), covered from above with a circular lower graphite film (11), over which the following are placed in sequence: circular lower graphite spacer (9) with a thickness, advantageously 5 mm, and on it the lower carbon composite (CFRC) spacer (7) with a thickness advantageous 5 mm, which is in contact with the lower surface of the upper punch (2), whereas to the lower frontal surface of the lower punch (1) and to the upper frontal surface of the upper punch (2) coaxially placed conical intermediate elements: lower (12) and upper (13), which adapt the nominal diameters of the electrodes in the SPS device to the nominal external diameter of the punches: lower (12) and upper (13), and additionally on external frontal surfaces of the conical intermediate elements (12 and 13) there are axially placed carbon composite (CFRC) plates: lower (14) and upper (15) with a thickness in the range from 5 to 10 mm, advantageously 10 mm, moreover in the vertical axis of the tool set a centric hole is made, passing through the upper (6) and lower (7) carbon composite (CFRC) spacer, lower (1) and upper (2) punches, lower (12) and upper (13) conical intermediate element and lower (14)and upper (15) carbon composite (CFRC) plate, which enables a constant measurement of the powder mixture compaction temperature using a pyrometer, whereas the internal surface of the die (3) is covered with a graphite film (16), whereas for complete thermal insulation the external surface of the die (3) is covered with graphite felt (4).

8. Multi-component magnetron target, characterized in that it has the form of a circular target with a diameter in the range of 80 - 100 mm, advantageously 100 mm and contains tungsten (W) in an amount of 69.9 to 84.6 wt%, advantageously 78.4 wt% and boron (B) in an amount from 13.5 to 24.3 wt%, advantageously 15.2 wt% and an intermediate metal, advantageously titanium (Ti), in an amount in the range from 1.7 to 6.4 wt%, advantageously 6.4 wt%.

9. A target in accordance with claim 7, characterised in that it contains tungsten (W) in an amount from 66.5 to 83.1 wt%, advantageously 74.1 wt% and boron (B) in an amount from 13.3 to 23.1 wt%, advantageously 14.3 wt% and an intermediate metal, advantageously zirconium (Zr), in an amount in the range from 3.2 to 11.6 wt%, advantageously 11.6 wt%.

10. A target in accordance with claim 7, characterised in that it contains tungsten (W) in an amount from 60.3 to 80.3 wt%, advantageously 66.4 wt% and boron (B) in an amount from 12.8 to 21.0 wt%, advantageously 12.9 wt% and an intermediate metal, advantageously tantalum (Ta), in an amount in the range from 6.2 to 20.7 wt%, advantageously 20.7 wt%.11.A target in accordance with claim 7, characterised in that it contains tungsten (W) in an amount from 59.9 to 80.1 wt%, advantageously 66.1 wt% and boron (B) in an amount from 12.8 to 20.9 wt%, advantageously 12.8 wt% and an intermediate metal, advantageously rhenium (Re), in an amount in the range from 6.4 to 21.1 wt%, advantageously 21.1 wt%.

12. A target in accordance with claim 7, characterised in that it contains tungsten (W) in an amount from 66.1 to 83.0 wt%, advantageously 73.6 wt% and boron (B) in an amount from 13.3 to 23.0 wt%, advantageously 14.3 wt% and an intermediate metal, advantageously molybdenum (Mo), in an amount in the range from 3.4 to 12.1 wt%, advantageously 12.1 wt%.

13. A target in accordance with claim 7, characterised in that it contains tungsten (W) in an amount from 69.6 to 84.4 wt%, advantageously 77.9 wt% and boron (B) in an amount from 13.5 to 24.2 wt%, advantageously 15.1 wt% (w / w) and an intermediate metal, advantageously chromium (Cr), in an amount in the range from 1.9 to 7.0 wt%, advantageously 7.0 wt%.

14. The use of a multi-component magnetron target according to claims 8 to 13 manufactured using the method, in the tool set according to claims 1 to 7, for the deposition of a protective thin film based on the material constituting themagnetron target, on surfaces of large-size elements, in particular on working surfaces of metal forming tools, where the magnetron target with a diameter of 80 to 100 mm, advantageously 100 mm is used, which is placed in a magnetron head and subjected to the process of high-power impulse magnetron sputtering in a process chamber with the use of an industrial magnetron corresponding to the diameter of the target, advantageously 4-inch, for depositing from the magnetron target of a protective thin coating on a metal substrate, advantageously steel.

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