Method and principle of vacuum metallisation by evaporation using a Joule effect of premixed elements for forming a homogeneous alloy layer on a substrate or a number of layers of the latter or of other elements in a single vacuum cycle

Abstract

The invention relates to an improvement in the vacuum metallization process by Joule evaporation of premixed elements to form, from a crucible and on a substrate, a homogeneous alloy with a thickness determined by the number of evaporations performed during a vacuum cycle of the evaporation tank, or to create, according to the same principle, successive layers of alloys and other components that form a stratified thickness as desired. This improvement is made to patent application 8809898 and its certificate of addition No. 8811556.

Description

METHOD AND PRINCIPLE OF VACUUM METALLIZATION BY EVAPORATION BY JOULE EFFECT OF PREMIXED ELEMENTS FOR THE PURPOSES OF FORMING A HOMOGENEOUS ALLOY LAYER ON A SUBSTRATE OR SEVERAL LAYERS OF THIS OR OTHER ELEMENTS IN A SINGLE VACUUM CYCLE. The object of the invention is to improve the metallization under vacuum by evaporation by Joule effect of elements pl rfm langées to form from a crucible and on a substrate a homogeneous thickness 11 iage established according to a number of evaporations deJfinies and made during the time of a cycle of setting: e "empty of the tank of -evaporation or to create according to the same principle of the successive layers of alloys of various natures and other components which form a stratified thickness at will This improvement is made to the patent application 8809898 and its certificate of addition N 8811556. One aim of the improvement is, among other things, to obtain a homogeneous layer of chosen thickness in the case of metallization for a specific purpose such as, for example, shielding against electromagnetic fields. 61st tromagn,etics. Indeed, in this particular case, the aim of the shielding being to drain the parasitic electromagnetic fluxes in the very thickness of the metal, it is a question of applying a metallic layer of optimal quality and thickness on a substrate. A method had to be developed to metallize substrates by a system adapted to the very nature of the latter, especially when these substrates are, for example, a thin polymer sheet or a woven network which require a lot handling precautions. It is understood that the metallization of such structures can only be done in a delicate way if one wants to obtain the desired parameters. 4 supported by a research program and resulted in a method and results defined below. The method itself aims at a new direction for the definition of the vacuum metallization of substrates, in this case delicate surfaces by several metals in a single operation, and in a specific case with the aim of add auii uî}_btrat i a facuit t' d t i e bt'in d rech Frch contre i et_ e e ctromagn Jt ic fields. Shielding against ies electromagnetic disturbance fields are known and are part of a choice of Iron-Nickel alloys with high magnetic permeability These shields made from pure iron and nickel must necessarily undergo after machining and shaping a thermal cycle either under cracked ammonia, or under pure, dry hydrogen to avoid oxidation of the latter and to eliminate impurities This treatment followed by controlled cooling is carried out for several hours at temperatures close to 1 n O 00 no longer avoid after this heat treatment, any physical deformation of the shielding which could greatly reduce its effectiveness Vacuum evaporation on a substrate of an Iron-Nickel alloy has been tried but the results obtained have not been sufficiently conclusive. especially since the expensive treatments undergone by this alloy in the foundry to obtain the desired crystalline structure are lost during the evaporation. n The search for an efficient and economical method to obtain high performance shielding results without starting from an alloy already f.orm, was undertaken. To obtain what precedes, the vacuum evaporation must allow a metal deposition in a single operation starting from the different metals chosen and intimately mixed in the state of powder in one or more crucibles At constant vacuum (10- Torr) the surface vapor pressure temperatures of these metals are close only for some of them. By condensing the scale of evaporation temperatures, the following result should be obtained; under well-defined conditions as to the specificity of the vacuum to be obtained, to the temperature of evaporation, to that of the substrate, to the particle size of the covering materials, to the mixture thereof, and to other parameters, the metals should deposit not in stratified layers but form a v-type alloy For this it was also necessary that the conditions required for adhesion to the substrate be met We know that surfaces made of organic polymers (especially flat surfaces) pose problems due to their intrinsic physico-chemical complexity. Moreover, the adhesion between metals and organic matter is not well defined because it is not known whether it is due to the energies of surface, dispersion forces or charge transfers. These surfaces may in some places suffer from micro- cracks In this case, they must be treated beforehand to modify these defects and obtain good adhesion of the thin layer of metallization. To this end, the treatment of delicate substrates is done in a simple way by cold soaking in an adequate solution because all the other usual methods such as by heating at high temperature to separate them from their volatile impurities as well as by other methods including soaking in an acid medium or exposure to ultraviolet rays in the presence of Oxygen (03) which volatilizes the contaminant (for example Co or Co 2) damages the substrates irremediably. In cases where it is desired to form an alloy layer on a substrate, with the aim of forming shielding against electromagnetic fields, it is necessary to create the magnetically permeable metallization as possible. The metallization tests by vacuum evaporation carried out to prove the invention according to the method described below, were carried out with metals forming an alloy with high magnetic permeability applied to a substrate defined as a lattice in woven polymer monofilaments Tests by various laboratories tories to form alloys, for the most part, binary, under vacuum, have been carried out in the past from separate evaporation sources for each deposition material. This system, by Joule effect, has given results, but the control of each separate crucible is complicated and the different densities of metal vapor emitted cause the coverage of the substrate to be unequal due to the random movements of the lighter vaporized elements on the one hand, and the distance between the sources of evaporation on the other hand. On the other hand It is also necessary in certain cases to rigorously control the evaporations by a quartz oscillator Starting directly from the Nickel-Iron alloy, which can be evaporated, in certain cases, quite easily from a crucible, a substrate temperature of about 2000 C is required, totally unsuitable temperature for polymer substrates or other ne not tolerate these temperatures. Sequential evaporations of separated metals have been made. This produces stratified deposits which, in order to form an alloy, must then be annealed at temperatures varying according to the case, but which greatly exceed that which can be tolerated by the substrates defined previously. An arrangement of multiple sources for alloy deposition in constant production by Joule effect under the required conditions does not seem to exist to date nor, a fortiori, from a single source. In addition to the tests described above which were carried out in a vacuum chamber, by the evaporation of the deposition materials by Joule effect, other tests carried out by different institutions by means of vacuum evaporation systems other than by Joule effect (electron beam devices, ion bombardment, ion implantation etc) have been carried out with some success Most of the time this was undertaken to obtain binary alloys, but it must above all be remembered that these tests have punctual results based on theoretical models However, layers of quaternary composition forming a protective alloy are used for a known application which is the electron beam deposition of the M -Cr-Al-Y alloy on the blades of jet engine rotors used in the medium marine (M is either Cobalt, Nickel or Iron) This technology is applied in production in the U S A and U R S S. Other deposits of various alloys are used in microelectronics and for magnetic tapes where high coercivity and memorization are necessary These deposits are made by evaporation and condensation of ultrafine products on cold surfaces in the presence of a high pressure gas From all these methods, (experimental or Nope), none is validly applicable to the surfaces described below. above, whether due to technical, physical or even economic factors, these factors being most often concomitant. The solution adopted for the test program on the network pretreated as described above was therefore vacuum evaporation by Joule effect, in the most classic of vacuum installations which was defined as the most suitable for the project (figure 1 ) The profile of the theoretical model was based on several parameters of which the following are the most important: 1) Formation of one or more metallized layers each comprising several metals to be deposited in order to form, at the time of deposition on a substrate, a alloy, preferably for this specific case, with high magnetic permeability (minimum 2 k A′ of total skin thickness) 2) Choice of premixed metals to be vaporized allowing the most adequate crystalline orientation to obtain this permeability. 3) Choice of metals whose alloy offers a surface with high reflection index. 4) Simultaneous evaporation of all the elements of the premix to obtain the previous points without flaking, staining and fatigue cracking. ) Choice of the particle size of each of the metals to obtain this simultaneous evaporation. 6) Choice of physical parameters (vacuum, temperature,) in function of point 5 above to obtain points 1 and 4 above above. 7) Good adhesion to the substrate of the resulting thin layer and successive layers between them in case of repeated layers similar or different. 8) Imperative maintenance of the dimensional stability of the substrate and its initial stiffness rate by controlling its temperature during the evaporation process. 9) Adequate hourly production for the economic viability of the product. ) Obtaining the required simultaneous evaporation from one or more evaporation sources, each charged with pre-mixed deposition materials and recharging the sources in multiple wells during the same evaporation chamber vacuum cycle . 11) Choice of refractory or metallic or other suitable sources to prevent the elements to be vaporized from combining with The source. Evaporation sources of all sizes and thicknesses have been tried, and tungsten has withstood the best operations, most of the other sources alloying with the elements of the alloy to be obtained. Various deposition substances liable to result in magnetically permeable deposits were used in pre-established proportions and various binary, ternary or quaternary alloys were derived from them. A quaternary alloy was finally selected for the test program whose components are premixed in the following percentages: Nickel (+ / -75%) Copper (+ / 5%), Iron (+ / 18%) and Chromium (+ / - 2 %) All have a crystalline form either with face-centered cubic crystals or with centered crystals (table 9) This choice makes it possible to avoid undesirable anisotropic fluctuations and to create a film close to zero of magnetostriction, whose two main components after evaporation are found in the alloy obtained at a rate of 80% for Nickel and 15% for Iron for a layer thick enough for defined shielding. An economically valid evaporation time has been calculated, which gives a thin layer made of a single evaporation of the mixture or several evaporations of it (skin thickness adequate) for the frequencies involved. A low temperature of the substrate has been maintained without damaging it, which retains its dimensional stability and its initial strength. This low temperature also helps to obtain a good crystal orientation. The substrate was held in place on a cylindrical planetary system iron substrate holder in the horizontal vacuum chamber of the deposition facility by two flexible magnetic ferrite strips which, in addition to holding the substrate in place, can also help with orientation crystal of the elements during their deposition. The evaporation took place under a vacuum approaching 130 Torr in order to narrow the absolute scale of the vapor pressure temperature deltas of each of the deposition materials according to a scheme of chain alloys (Table 9). The four metals were used in the form of ultra-light powders. thin and mixed in the proportions given above A very thin layer of the mixture was spread over the source evaporation (crucible) to obtain the determined coverage. Visualization during the operation showed, at their evaporation temperature checked with an optical pyrometer, clear and continuous evaporation of the elements without "drizzle". Examination of the substrates after different metallization times did not indicate a coverage of these preferably by one of the metals rather than others. At the first examinations the results indicated that a homogeneous magnetically permeable alloy was obtained and that it represents the desired alloy m (table 10). The method and the resulting results as described in the preceding paragraphs and which relate to the vacuum evaporation metallization of a substrate by several powdered metals premixed in a single evaporation source are adaptable to many other substrates for other apps. The gratings metallized under vacuum according to this process during the test program were subjected to rigorous tests at the Ecoie Nationale Supérieure des Mines de Paris Department Surface and Tribology Sophia Antipolis (CEMEF). The equipment used _ A JEOL JSM 35 CF scanning microscope paired with a dispersive energy analysis spectrometer by TRACOR 5500 x-rays. The edition of the tests follows (Tables from 1 to 7). Object of the test - 1) Analysis of the metallized side of the network and the composition of the resulting alloy. 2) Analysis of the opposite side of the network to determine the components of filaments and finish. 3) Checking the sample holder to define impurities residuals on it. 4) Analysis of the residual mixture of the 4 basic elements in the crucibles (sources of evaporation). ) Evaluation of the differentials obtained and of the results. The aforementioned analyzes have, in addition to the four elements of the alloy, made it possible to detect in particular titanium, zinc, a excess copper, calcium, chlorine, phosphorus, and some other substantive elements They were eliminated by the established differential analyzes In fact, these elements come from ent, either of the pretreatment layer of the filtering network, or of the composition of the filaments of the latter (titanium), or of the sample holder and also of the enclosure (chlorine and zinc) and are found in identical proportions, whether the source of evaporation ration (crucible) either in molybdenum or in tungsten. The alloy itself is well composed of the four basic elements used during the vacuum evaporation process. The quantitative values ​​are as follows for the overall surface area of ​​the sample of the filter network tested: % weight Test % weight in the prevaporization mixture Cr 1 02% 2% Fe 16 71% 18% Ni 78 81% 76% Cu 3 47% 4% The quantitative analysis is subject to variations of the order of + / - 3% for the weight percentages These variations are inversely proportional to the weights of the components. It should be noted that neither the tungsten nor the molybdenum forming the sources of evaporation used, are found on the substrate and that Ni and Fe are not found either in these sources whereas these are the two elements which usually try to associate with them This would seem to prove that the formation of vapor of the four elements present in the source is at the start of a surface tension which prevents a such association at the source. During the global surface test during the scanning of the substrate by the bombardment of particles on the non-metallized side of the network under analysis, significant deformations and castings of material could be noticed visually on the screen of the micro- scope (Figure 2). On the other hand, the metallized side under analysis did not suffer from any deformation on any part of its surface This seems to indicate a perfect evacuation of the electromagnetic charges to which this surface was subjected and a total protection of the underlying material Even during the punctual analysis, when the electron bombardment was focused on the equivalent of a diameter of less than one micron, only a notch of this size appeared on the metallized surface without any deformation of underlying material (Figure 3). To complete the analyzes obtained by the TRACOR 5500, an analysis by ESCA erosion spectrometry (XPS) still in the enclosure of the Ecole des Mines, was put in place. The results read as follows: The deposits are made up of Ni, Fe, Cu, Cr The substrate is made of polyester, polyamide and carbonaceous polyamide The peaks analyzed are as follows (the bond energies are indicated for information in parentheses) : Ni 2 P 1 / 2 2 P 3 / 2 ( 873-855 e V) Fe 2 P 1 / 2 2 P 3 / 2 ( 723-710 e V) Cu 2 P 1 / 2 2 P 3 / 2 ( 954 -934 e V) Cr 2 P 1 / 2 2 P 3 / 2 ( 536-577 e V) O is ( 531 e V) C 1 S ( 287 e V) The surface of the network used for the analysis is part of the same sample as that used for the TRACOR 5500 analysis The analyzes were performed with the aluminum K O< line. As in this case, the Auger peaks of Nickel are superimposed on the 2 P 3 / 2 peaks of iron, a two::i;m z series of analyzes has therefore been carried out with the Kôr line of magnesium. In this case, the peaks of iron are no longer disturbed and it was possible to evaluate the sensitivity factor corresponding to Fe 2 P 1 / 2, the only iron peak measurable with the Aluminum source. Each sample is eroded by means of an Argon ion beam (4 Ke V, 3 u A) & scanning on a square of 8 mm side Dendant about 90 minutes This erosion is stopped at regular intervals ties to allow the acquisition of the spectra (the acquisition is done on a surface of approximately 8 mm The surface under the peaks, after removal of the background noise, is then measured and used for the calculation of the atomic concentrations These concentrations are calculated from given sensitivity coefficients in the XPS (X-ray Photoelectronic Spectrometry) manual. The results read as follows: The thickness of the metallic monolayer analyzed, evaluated from 30 to 50 nanometers, is determined from the concentration profiles of Nickel and Carbon, by comparison with profiles obtained for layers of the same thickness of Ni Cr / Si O 2. For this first layer which can remain unique according to need, the Nickel-Iron concentration is homogeneous over the entire thickness of the deposit whereas that of Chrome is less so as well as that of Copper which tends towards a maximum at the layer interface. metal ic-substrate. The atomic concentrations of the 6 elements (Ni, Fe, Cu, Cr, O C) are reported in Table 11 In Table 12, these concentrations ments are reported without taking into account carbon or oxygen An integration of these values ​​over the total thickness of the layer gives the following percentages which are much more accurate than those obtained by the Tracor 5500. Cr: 2% Fe: 18% Ni: 76% Cu: 4% C: (known as "pollution") disappear during O: the first 5 minutes of erosion). These percentages are those of the elements starting from the pre-mixture. vaporization However for a greater layer thickness of the alloy thus formed, by successive evaporations for example, a reduction in the percentage of Nickel in favor of that of iron will appear, as we will see below below, Copper and ie Chrome undergoing only slight decreases We are moving towards a sought-after alloy of composition 80% Ni / 15% Fe / + Cu + Cr. Samples for additional tests treated by successive additive evaporations on substrates made of lattice in all respects identical to that used for all the previous tests were created according to the following mode: constant vacuum 10 Torr constant weight of 0.15 grs of pre-mixed metallization in the calibrated tungsten crucible. constant amperage of 14 A. constant evaporation time of 120 seconds. From these preparations three samples were retained, one metallized twice successively, the other three times successively and the last four times successively. The samples were subjected to an analysis with the TRACOR 5500 Spectrometer at the Ecole des Mines The plot is clear and perfectly defines the peaks of the various elements The weight percentages obtained for the sample subjected to four successive evaporations read: 3.52 %Cr 14.24% Fe 77.92% Ni 4.33% Cu previously analyzed (tables 1 to 7). These samples, also studied by ESCA erosion, give the following results: The little Cu-Cr heterogeneity visible for the first thin layer evaporated directly on the substrate (tables 11 and 12), disappears to show perfect homogeneity for the following successive layers. can see that the parameters of the crystal lattices of one layer on the other create an optimal epitaxy given their identity and the constant crystalline orientation thus created The "vapor-atoms" resulting from the multi-element evaporation receive from the substrate a " bonding call" and slide along the receiving surface until a finite moment where they unite together in islands totally adsorbed among the atoms of this surface. At this finite moment, they become solid by a process of exothermic condensation and the multiple islets unite with each other, even as they form, to create a layer of homogeneous thickness. The initial "bonding" of the "vapor-atoms" is probably initiated by their kinetic energy whatever the temperature of the substrate Adsorption penetration actually creates an atomic weld at the interface point of layers made of identical alloys or a "continuity" epitaxy. The weight percentages defined by integration on the thicknesses obtained for 3 and 4 successive evaporations of 120 seconds each are Ni 80 / 81%, Fe 14 / 15%, Cu 3%, Cr 2%. These results confirm those obtained with TRACOR 5500, namely an increase in the weight percentage of Nickel compared to that of iron which tends towards the desired percentages for the alloy deposit (80% Ni / 15% Fe) + others. The thicknesses obtained show a progression of increment of these per evaporation layer of the order of 80% of the thickness of the previous layer (tables 13 and 14). Additional tests were undertaken, the purpose of which was to define curves representative of volume increments and metallization thicknesses. For this purpose, 3 cm 2 of each of the 3 samples were coated with a two-component resin of hardness equal to that of the substrate. Two of the three samples referenced under the numbers 22 and 23 and representing respectively the parts subjected to three and four successive evaporations were finally selected. Blades formed by Cryo-ultramicrotomy and ultramicrotomy were observed under a CM 12 Philips type electron microscope at 100 Ke V at the joint center of Applied Microscopy of the Faculty of Sciences of the University of Nice To compensate for crushing and tearing that can occur during the cuts of the blades, each sample was cut in a number n of times three blades of different cutting directions A) from bottom up Bl from top to bottom and C) laterally (Figure 4). An average is then established according to: (A+A'+)+(B+ 3 '+)+ 2 (C+C'+) layer thickness. 4 n The layer thicknesses obtained by this method are read as follows: 1) sample layer thickness 22 = 225 nm, 2) sample layer thickness 23 = 405 nm. By joining the thicknesses evaluated during the previous analyzes for a single evaporation and for two successive evaporations & those obtained above, we obtain the curve of the table 15. We can notice that at each additional thickness we get an increment almost equal to the thickness of the previous layer. This was verified up to four successive evaporations. All of the studies and their results made it possible to undertake the manufacture of a system for alternating the tensioning of the crucibles, with dosing and automatic filling of the latter to maintain continuous metallization in the chamber under constant vacuum. "continuous" evaporation composed in fact of successive evaporations without stopping time, makes it possible to obtain on the same substrate(s) by reciprocating winding systems or continuous planetary, the thicknesses required for defined shielding, for example in the case of protection against electromagnetic fields (figure 1) The layers formed by successive evaporations in the same enclosure under constant vacuum by the method which is one of the subjects of the invention allow by the dosing system and filling of the crucible(s) at each of the successive close energizations, to alternate or to create different alloy layers at each of the evaporations, one or more of these layers can be at the start of a single metal or other materials for the purpose of creating a stratification of multi-layers of chosen thicknesses on the substrate for the required properties. It is also possible to alternate 2 or 3 evaporated layers of the same alloy to several components, this resulting confit, as we have seen, in a homogeneous alloy thickness, and to follow this with an evaporation of insulating, refractory or another and so on with the desired variances. In the method chosen to carry out the implementation of the principles of the invention (FIG. 1), the Joule effect evaporation system comprises an evaporation chamber (1) provided with a door (14) through which a planetary assembly or an epicyclic system made up of a cradle (7) which holds two planet carrier crowns (2) whose planets (8) are the substrate carriers, the cradle being provided with rollers & friction (6) whose one is rotated by a motor (8), the planetary system being ensured by the chain (15) and its tensioner ( 16). In the center of the planetary assembly a plate (9) serves as a platform. form to the evaporation sources or crucibles (4) each supplied with current by the nickel-plated copper electrodes (5) which comprise a common neutral to the crucibles and a phase inlet Q: separated by crucible to allow precise adjustment of each of them Series of buckets (11) with their pouring spouts (13) move forward or backward on manual or automatic control along rails (10) provided with cams (12) which regulate the filling of the crucibles (4) before each power-up evaporation of these according to the choice of the alloy or other material to be deposited and the sequence to be followed This takes place as described during an unloading cycle, the cups being pre-dosed before the closure of the door (14) The number of buckets per crucible allows an equal number of successive evaporations for this crucible and the method allows the use of a large number of crucibles. The pouring spouts (13) have the desired length and are at a sufficient distance from the crucibles (4) during evaporation not to create disturbances to the evaporation cones (17) It is clear that a substrate formed from rolled up material such as polymer sheet, can be treated in the same way, the substrate unwinding from a reel on one side of the vacuum chamber (1) to be rolled up on the other side, after having passed over two fine and parallel rollers between which the surface to be treated unrolls, which slowly scrolls above the systems of crucibles (4) and their measuring cups (11). nvaquiav lu Iv lop Qj 0)à T = suolle-a)l io'o N 6 ap O *'ib 41 005 '2 uol Dla Jjo 3 i Uz T 5 uo TV Ja;l ic'ON Bap O'Ob ^ A O O og 2 UO Ti Da J 1 ? 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GOLD TL MA N: KA KB P KA OF -R LA 7 FE W CL}E OR PD LA PEAK LISTINE ENERE AREA EL AND i NE 1 2 001 14 E 5 P KA OR ZR LA- _.314:56167 S KA OR MO LA? 3 2 853 5 ? 7 PD LA 4 6 401 85 e FE KA 7 4 E 3665 NI KA S 8 2 E 6 758 NI KP E,"QLE CES Ili,ES DE PFRIS _ CEMEF à: TUE Il-OCT-Ee Cursr: O ocokev = O:OI < 4: O ooo: o c OL È '1 d 2; Or Ccole des / " 1, of Pars 13:3 I O 000 VFS 64 e TOWARDS FIE DOOR EC:HAI:I:LLON i 240 TABLE 5 :it * '1 :.l hi :'1:: " Z:l}r'"'l: eJ, ii tt il,': ' N / , @, ,,, ''r j ' ', i a O oeeaVFS 1024 10 _ 40 O RE 5 IDU ON CRUCIBLE MO 2 MMX 2 MM-BOTTOM TABLE 6 t O m II 8 lvalefûvi L n s 9 a Vú v.0 Of' o O;:i=loi -1 b L 6 ' E OOOMI T BO' tb OT O po o l-n 3 26 'LL - 'E'LL, ) 1, 'T 6 ú O '; b 66 '0 GL'0 N-IN t 2 'h,b 3 'b'b; 3-0;f' IQS TIO'-T59:j ES E,5 ,'G ILS'O O' O 1 le O T SSO-O)1- a 3;',;l 'IU OldJ V Z 'l)1 > luawa 13 2 = s Uo Tll Jl; 1 O'ON '(SGE AI O O '52 U Oll:a -io D i Jd Z L? - / + Sb 2 350 '0 _ / ' O f 10 b O " O NZ-r S _ / , -', ',I ' 3 SSO '_ O- / zLOSGL 'O A f 9 - / ' _ú Z SEO'O - / + 8 úE 91 '0a - / + lIS;t E 20 O - / + 2 l SSOO; I 91 Urlg J I,e' 911 BJ-?18 'u 113 06- 0=pbs-143 saaabaa O'SE A>1 O-SZ sts Aieuto S 3 alpi Wpures 14 d Vt t b M 1=^ 3r O;T B, 'O 86 ' O06O 000 I 510 ' I bb OI 600 O Zt-n 3 6 L'G 8 LB' r O oo'1 L 20 ' L 66 ' O 3 úS'I) >-' N I"-úT OL'EI ISL'O OTO'I S Tb-t c-I',l, I-a' t 2 T'0 úT')', 9 'I '1 2 SO' I Ta C Cl C)O IJ YS M %': )V Id -' o' le ltuawa 13 = suolle tale 1 l ' N ap 00 '0# AI 00 'q 52 ỏ' Jài: lo j-' 6 bl - / + 185,2,00 'O- / * b 1600 'O -n 3 OES Ci S O ' 189 O 10 C-'O -;TE-B 28 '0)I-;N L Oa - / + 8019 I L 02 'c JO -,'t 6519 I'0,-a- bwl - / o 291 6 SOO'0 - / + 92100 '0-D sluno 3 fa N 01 le j-, * la uawal 3 03 '3 q = pbs-lq 5 saa, I 6 a,l o O o' A , O ',2 s 1 SÀI UV ESéI p- epue 55 QNDJ-WW 2 XWW 2 M 13 Sn 3, 3 ns n Oli 53 Y o Nlo_±wwzxww M i 3 sn 138 s nc I-53 ?A O o - * 70 10 @ çllQd ap lit W i Qp j O 7) I;1J D 0-E,Z O O T 960 t = Sb "' l,i I: t l 0 o t 2 t HI FH FH "W ':)P D:)1 oo GO ' Cr I> A:1000 0:zt 4 > Ilaloo Ulc l f 33-Id 3 't I 533 Dl) 0 =,c-1 c 00 O -4 c 1 sIn 3 4, ;Eld L-- 1 SPC 3-loj 3 * DE' OT 6 r-HJú-G;: ,N INCAT It CNS REA'TTVES A SOXS VDL EVAPORATION OF EI 1 *S P S S Eleent Atomn. Nb Wt I Dens ( 2 Cf) Fusion Rul. Gr / cm C C Struct Const- Crist Network Crist Conduct. ( _-m)-i t Skin thickness ( S) 6 a X- z1 K Hz IM 7 z Ni 28 58.69 8.9 1455 2730 Ce C 3.5167 1.3 x Il Fe 26 55.85 7. 87 1539 2740 o: 2.8606 1.o x 107 Cr 24 52.01 7.19 1890 2500 o C 2.8787 3.8 x 107 Cu 29 63.64 8.96 1083 2600 CFC 3.6080 5.8 x 10 Successive evaporations (C) and estimated formations of intermediate alloys. C at 10-4 Torr c at 10 Tr Ni 1535 1580 Fe 1207 1490 1630 Cr 1430 Cu 1032 ( 1032) % at start lx 102 2 x 102 0.18 4.40 0.014 0.14 0.35 0.011 1.00 O 2.6 0.85 2.1 Percentages of the mixture and the resulting alloy. % mixture % alloy (containment leakage and impurities) Notes 1) CC = face centered cubic CC = centered cubic 2) The alloy obtained has a relative permeability of = 2 x 104 and the skin thickness reads 0.037 (60 Hz ) 0.092 ( 1 K Hz) 0.0029 ( 1 ml Hz) 3) To avoid coosants to combine with the source of tungsten (w) the composition must not have more than 1 / 3 of soft iron (unless of 20 p p of carbxne) TABLE 9 1 ic X 100 Network permab i lity curve 6 UIJ J ú 3 -0 r, E Q (j <l 1 2 3 A 5 6 7 induct ion maqc Cèt ic, 17 auss TABLE 10 0.081 0.066 8x10 1 i i 1 day 1) 1 Evap Oct 88 / W 2 30 min 94 N o Wdon CXPS CONCENTRATION PROFILE) Evap Oct 88 why you 00. TABLE 11 / W 2 30 min N 4. C (CA o) + oh -t. *-I CI C 10) + O+ c + in enosio TABLE 12 CONCENTRATION PROFILE (XPS) pmrc at. EO.00. *000- W M 40.00 20.00. 0.00X; F.C (A lo) IC AC 1) c + ± +r 3 EVAP 2 min / W C, C>x io 1 -o H-f f-+ i sin erosion CONCENTRATION PROFILE TABLE 13 23 / 4 EVAP 2 m in / W 0.00. in ero Dsion CONCENTRATION PROFILE (XPS) TABLE 14 pow C at. + t- (x Ps) pure at. t 100 00. 60.00. 60.00 00 K4; + F -j C.(eW-j Ca-C>) + O -j c i-j C iiffi deposit thickness nm 0. 0 1 (esca) 2 Evap: 0.15 grs t: 120 s A:14 n evap. DMRET'7-1 o Z _ co O T' I D TABLE 15 n ELEVEND I CA T I O Ni ES 1) Evaporation by Joule effect in a vacuum chamber, of several deposition materials chosen according to a process characterized by the fact that these materials, preferably metals in powder or in fine granules, are first intimately mixed together, then placed in an evaporation source or crucible, and brought to a point of vapor pressure which causes them to evaporate simultaneously to deposit on a substrate in the form of a homogeneous alloy with a high index of reflection of its surface and with good crystalline orientation. 2) Evaporation according to claim 1) characterized in that it can be done from several crucibles in depending on the surface to be covered. Evaporation according to claims 1) and 2) characterized by the D fact that the resulting deposit is made on a substrate maintained at low temperature so that the latter, if it is fragile, does not suffer damage and retains good stability dimensional the. 4) Evaporation according to claims 1) and 2) allowing in using a low substrate temperature to obtain a improved crystal orientation. ) 1 Evaporation according to claims 1) and 2) characterized by the fact that the substrate is held by flexible bands, magnetized to also help the crystal orientation of the alloy to be deposited. 6) Vacuum evaporation process by Joule plus effect particularly according to claims 1) and 2), characterized by the fact that during the same vacuum cycle of the chamber, of evaporation, several identical evaporations are made successively to increase the thickness of the deposit and to obtain a layer whose thickness can be defined in advance and this layer forms a homogeneous alloy deposit. 7) Joule plus vacuum evaporation process preferably according to claims 1) and 2), characterized by the fact that during the same vacuum cycle of the evaporation chamber, several non-identical or partially identical evaporations are made successively to form layers of variable thicknesses separated according to choice by layers of other materials and even to form layers totally different from each other, all forming thus a final layer stratified according to the desired variances. Vacuum evaporation process by Joul'e effect pref 6 rabily according to claims 1) and 2), character-ized in that the results described in claims 6) and 7) are obtained by using, in the vacuum evaporation chamber, a system of pouring cups previously dosed with mat-riau:- or mixtures of materials to be evaporated allowing a choice of successive fillings alternating with the energizing of the crucibles according to amperages chosen according to the material or materials to be evaporated successively, the vacuum itself being m 6 me, if necessary, increases or decreases for the same reasons. Evaporation process according to claims 8) and 9) and preferably also according to claims 1) and 2) characteristics by the fact that successive evaporations of materials selected by crucible form layers in parallel bands of different composition on the same substrate.