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  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Definitions

• the present invention relates to an electrically conductive target material of molybdenum oxide, a process for its preparation and a use of the target material.
• MoO x molybdenum oxide
• Sputtering systems such as physical vapor deposition (PVD) coating systems, are used to remove molybdenum oxide-containing layers from the gas phase in a vacuum process.
• PVD physical vapor deposition
• Coating process the layer-forming particles from the (sputtering) target in the gas phase and converted by condensation of these particles - optionally with the supply of oxygen as a reactive gas (“reactive sputtering") - forms a corresponding molybdenum oxide-containing layer on the substrate to be coated out.
• Molybdenum oxide layers the properties of which can optionally be modified by adding doping elements, have interesting optical properties and therefore find particular application in layer structures in optical or opto-electronic applications such as electronic displays.
• Molybdenum oxide layers can be found in JP2013020347, where metallic interconnects within the display of a capacitive touch sensor (English: touch screen) are covered by a light-absorbing layer of MoO x , to unwanted reflections of the metallic
• Light transmittance, etch rate (relevant in subsequent structuring of the deposited layers by means of photolithography in conjunction with a wet-chemical etching process), thermal stability and stability to other chemicals used in the manufacturing process (for example, stability against photoresist developer or remover) depend on the exact stoichiometric composition x of the deposited MoO x layer or the added doping elements.
• MoO x layers are required in which the molybdenum oxide is in a substoichiometric composition, ie the oxide has unoccupied oxygen valences and oxygen vacancies are present in the deposited MoO x layer.
• substoichiometric MoO x layers with an x-range of M0O2.5 to M0O2.98 are of particular importance for such applications because of their electro-optical properties
• oxide-ceramic target materials such as M0O2 targets (US 2006/0165572 A1) or target materials having a substoichiometric composition (DE10 2012 112 739 and EP 0 852 266 A1) are known.
• US 2006/0165572 A1 discloses a target material with at least 99% by weight M0O2. However, this target material contains too little oxygen, in order to be able to deposit MoO x layers with x> 2 without additional oxygen as the reactive gas.
• EP 0 852 266 B1 relates in general to sputtering targets of substoichiometric metal oxides, as the only concrete application example with molybdenum a M0O 2.95 target material is mentioned in Example 16. Specific information on the microstructure of the target and the starting powder used to produce the target material is missing. Obviously, that would be one
• Anhydrous M0O3 powder or a powder mixture with very high (> 90 wt.%) MoO 3 was used.
• a target made of Nb20s powder which was compacted by means of hot pressing at temperatures between 1100-1400 ° C, a holding time of 1 h and an applied pressure of 50 kg / cm 2 . It is completely unclear how these Nb20s process conditions can be transferred to the production of a compact M0O2.95 target, since the melting point of M0O3 is only 795 ° C and therefore the powder would already have completely liquefied in the allegedly used temperature range.
• the oxygen content of a deposited layer is proportional to the oxygen content x of the target material MoO x , it is sensitive to the size, geometry and structural design of the coating system (eg from the distance target substrate or from the position of the vacuum chamber suction or the position of the Ar sputtering gas inlet).
• the coating system eg from the distance target substrate or from the position of the vacuum chamber suction or the position of the Ar sputtering gas inlet.
• the manufacturer of target materials therefore has the additional requirement that the oxygen content of the target material should be as fine as possible over the largest possible concentration range
• Steps or at best continuously (analog) is adjustable.
• the object of the present invention is to develop a target material for the sputtering of MoO x layers, so that high-quality layers with uniform layer thickness and homogeneous composition can be deposited.
• the target material should have the highest possible density in order to ensure good process stability and a low tendency to form particles.
• the target material is also intended for a broad parameter range x, in particular for
• the sub-stoichiometric composition of MoO x be adjustable.
• the target material In order for it to be used in DC (direct current) or in pulsed DC sputtering methods, the target material must also be electrically conductive, ie its specific resistance should be less than 10 ohm cm, or the specific electrical conductivity should be greater 10 S / m Further, a production method of such a molybdenum oxide target material and a use thereof should be provided.
• the oxide ceramic target material according to the invention is electrically conductive. On a macroscopic scale it shows a homogeneous structure, on a microscopic scale it is structured in at least two different molybdenum oxide phases: In addition to a MoO 2 phase with a content of 2-20% by volume, it has a substoichiometric molybdenum oxide phase content of at least 60 Vol% on. The substoichiometric molybdenum oxide phase content is in particular 60-98 vol.%. The substoichiometric molybdenum oxide phase portion is formed by one or more substoichiometric MoO 3 phase (s), where y is in the range of 0.05 to 0.25, respectively.
• the target material may still have a MoO 3 phase in a proportion of 0-20% by volume.
• production-related impurities such as tungsten (W),
• the oxygen content x of the target material MoO x (and thus the oxygen content of the deposited layer) can be varied very finely and precisely via the quantitative ratio of the coexisting phase components in a broad parameter range of 2.53 ⁇ 2.88, in particular in the economically particularly important range of 2.6 ⁇ 2.8 be set.
• the Mo oxides enumerated herein are those most frequently mentioned in the literature. The existence of further Mo oxides, which are not described or not yet discovered, can not here
• the target material already has sufficient oxygen content for many applications, so that the addition of additional oxygen to the coating process is not absolutely necessary.
• the coating process can thus be carried out with pure inert gas process gas (usually argon).
• pure inert gas process gas usually argon.
• Oxygen content of the deposited molybdenum oxide layer is slightly less than the oxygen content of the target material used. This is due to the fact that in the sputtering process, where the sputtering target is split into its atomic constituents such as molybdenum atoms, radicals and ions,
• the multi-phase target material is used in a reactive sputtering process, it offers advantages over the target materials known in the art.
• the oxygen additionally required is generally significantly lower, since the oxygen content of the target material can be set much more accurately for the desired composition in the layer over a large parameter range.
• the disadvantages of reactive sputtering are less pronounced at lower oxygen partial pressure and therefore occur
• M0O2 and the substoichiometric MoO3 -y phases contribute to the aforementioned advantageous properties of the target material.
• M0O2 is characterized by a very high electrical conductivity of 1.25 x 10 6 S / m compared to other molybdenum oxide phases.
• substoichiometric Mo03- y phases also each have a very high electrical conductivity (monoclinic M04O11: 1, 25 x 10 6 S / m), or electrically semi-conductive (data for electrical conductivity: M017O47:> 2000 S / m; Mo 8 0 2 3: 83 S / m, M018O52: 0.4 S / m, Mo 9 0 2 6: 27 S / m).
• Sub-stoichiometric MoO 3 -y phases especially M 4 O 11, also have very good sintering properties, thereby promoting sintering of the starting powder used into a compact component even at low temperatures.
• Both M0O2 and the substoichiometric Mo03- y phases also have a low partial vapor pressure.
• the vapor pressure is an important process parameter in the coating process, a low vapor pressure contributes to the stability of the coating process.
• M0O3 optionally present in the target material according to the invention has a high relative oxygen content and thus helps in the realization of Target materials with very low oxygen sub stoichiometry (ie a MoOx target material with x near 3).
• M0O3 has an orthorhombic structure characteristic of M0O3.
• M0O3 also refers to a substoichiometric molybdenum oxide MoC-y with very few
• MoO 2, 96 which has an ortho-MoMo moiety and has a few oxygen vacancies in comparison to the exactly stoichiometric MoO 3, is also understood to be MOO 3.
• the degree of reduction of the molybdenum oxide can be estimated from the intensity ratio of the two Raman pitch oscillations (wagging vibrations) at 285 and 295 cm -1 (see Phys. Chem. Chem. Phys., 2002, 4, 812-821).
• M0O3 is also characterized by good sintering properties, in
• M0O3 has a high vapor pressure and tends to sublimate at temperatures as low as 700 ° C, which has a detrimental effect on the manufacturing or compaction process. Furthermore, there is a risk that M0O3 will selectively sublime during use of the sputtering target in the coating process, thus changing the phase composition of the target during operation. For these reasons, M0O3 should therefore be avoided in the target material whenever possible.
• the proportion of MoO 3 phase is ⁇ 1 vol.%.
• M0O3 is particularly preferably present in the target material at most in traces and is in particular undetectable in the target material. Preference is given predominantly to a substoichiometric molybdenum oxide of
• the substoichiometric Molybdänoxid- phase content of the target material is according to a development of at least 85 vol.%, It is in particular in the range of 85-98 vol.%.
• the proportion of MoO 2 phase is preferably in the range of 2-15 vol.%. In an advantageous embodiment, the proportion of MoCfe phase
• the substoichiometric MoO 3 -y phase (s) present in addition to the MoO 2 phase and the optional MoCh phase can in particular be Mo 4 On
• M04O11 can be present both as ⁇ -oxide in a monoclinic crystal structure (low-temperature form) and as y-oxide with rhombic crystal structure (high-temperature form).
• M017O47, M05O14, M018O52 are also called Magneli phases.
• the binary phase diagram of the molybdenum-oxygen system is shown in FIG.
• Target material (substoichiometric molybdenum oxide phase content in the range of 85-98 vol.%, Mo0 2 ratio in the range of 2-15 vol.%) Both high electrical conductivity and a high density could be achieved. Excellent properties, in particular with regard to achievable density, can be achieved with target materials which consist of at least 45% by volume of the substoichiometric phase M04O11.
• the determination of the volume fractions of the different molybdenum oxide phases and the density of the target material are based on a
• one or more dopants with a total mole fraction of not more than 20 mol% may additionally be present in the target material.
• dopant is referred to a metal or oxide present, different from molybdenum metal; the proportion of a single dopant in the target material is between 0.5 mol% and 20 mol%.
• the molar amounts are based on the amount of - optionally oxidized - metal and not on the amount of any metal oxide.
• the dopant is used for the targeted modification of the layer produced with the target material and is clearly, even alone due to its mole fraction of at least 0.5 mol% distinguishable from the previously mentioned production-related impurities whose typical concentration is in the range of at most 1000 ppm.
• Substance levels of up to 20 mol% of the dopant is present in much higher concentrations than, for example, in semiconductor electronics.
• X-ray fluorescence analysis RAA
• EDX detector energy-dispersive X-ray spectroscopy
• SEM scanning electron microscope
• ICP-MS inductively coupled plasma mass spectrometry
• metals from the group of tantalum, niobium, titanium, chromium, zirconium, vanadium, hafnium, tungsten can be selected.
• Tantalum (Ta), niobium (Nb) or a mixture of niobium and tantalum are preferred dopants with which the etching rate of the deposited layers can be modified without adversely affecting the electro-optical properties.
• Pure molybdenum oxide layers usually have too high an etching rate. The etching rate of the deposited layer decreases with increasing proportion of tantalum or niobium.
• the dopant is preferably present in the target material in an oxide-bound manner.
• a molybdenum oxide target material with oxide-bound dopant is usually preferable to a target material in which the dopant is present as a metallic admixture, since the electrical conductivity of the metal usually significantly (one to several orders of magnitude) differs from the electrical conductivity of the various molybdenum oxides.
• Such a target material with greatly different electrical conductivity tends to arcen or form particles during the coating process and is suitable for the
• the oxide-bound dopant can with the molybdenum oxides a
• the dopant may also be at least partially present as a separate oxide phase, which is embedded in the form of domains in the remaining Molybdänoxid- target material.
• the oxide phase can be formed at least proportionally by stoichiometric or substoichiometric oxides of the dopant and / or mixed oxides of the dopant with molybdenum.
• the dopant can at least partially be present as a separate phase of tantalum oxide, in particular of Ta20s-y with 0 ⁇ y ⁇ 0.05.
• the dopant may be at least partly present as a separate phase of niobium oxide, particularly from Nb20s- y 0 y 0.05.
• Molybdenum oxide phase fraction formed as a matrix in which the other phases are embedded.
• the substoichiometric molybdenum oxide phase fraction traverses the target material in a continuous, percolating network in which island-shaped regions (domains) with the further molybdenum oxide phases (M0O2, optionally M0O3) or, if appropriate, domains with dopants are formed.
• domains are recognizable as surfaces. This percolating microstructure positively influences the electrical conductivity of the target.
• the domains typically have an extent of the order of 100 pm, but with a larger proportion of M0O3, the Mo03-phase domains can also be slightly larger (with an extent of up to 300 pm).
• a cohesive, percolating network can be formed by the various substoichiometric molybdenum oxide phases together, but also by the quantitatively highest substoichiometric molybdenum oxide phase alone, in particular by M04O11.
• the three-dimensional structure of the target material is essentially isotropic, i. there is no directional dependence of the material properties.
• target materials with a high relative density in particular with a relative density of at least 95%, in particular of at least 98%, can be achieved.
• the relative density of the target material is at least 99%.
• the relative density of the target material is at least 99.5%.
• a compact target material with a high relative density is important for the quality of the deposited layers, as less dense
• target materials Due to their higher porosity, target materials lead to a more unstable and difficult-to-control deposition process (target materials with too low a relative density are at risk of lightning discharges or "ares", which as a rule lead to undesirable particle formation in the which lead thin layer). Target materials with too low a relative density also tend to absorb water or other impurities, which can also lead to a more difficult to control coating process.
• the determination of the relative density is carried out by means of digital image analysis on the basis of light microscopic image recordings of the metallographic cut, in which the relative area fraction of the pores (ie area fraction of the pores relative to the examined total area) is evaluated. The density is calculated as an arithmetic mean of three such
• the electrical conductivity of the target material is preferably at least 10 S / m.
• the electrical conductivity can be measured by means of commercially available devices by transport measurement, for example a four-point measurement. With a higher electrical conductivity, the deposition rate and the process stability can be increased, as well as the costs for the coating process can be reduced.
• Target material between 71, 4 and 74.5 at.%, In particular between 72 and 74 at:%.
• the oxygen content may e.g. with the help of an EDX detector
• the invention also relates to a manufacturing method of the above-described target material.
• a molybdenum oxide-containing powder or a molybdenum oxide-containing powder mixture having an oxygen content adapted to the desired target material is used.
• a preferred starting powder is a powder mixture of M0O2 and M0O3, optionally supplemented with small amounts of substoichiometric molybdenum oxides such as in particular M04O11. Both oxides, M0O2 and M0O3, are readily available, inexpensive and thermodynamically stable under ambient conditions, easy to handle raw materials.
• Substochio metric oxides can be prepared by reducing MoO 3 powder in an appropriate atmosphere such as H 2 O.
• the starting powders are weighed in an appropriate proportion to obtain a powder mixture having a total oxygen content corresponding to the oxygen content of the desired target material.
• the powders are then ground dry and mixed thoroughly in a mixing chamber.
• the milling process can be carried out with the addition of grinding balls to crush agglomerates and lumps of particles and to accelerate the mixing process.
• the optional dopant can be admixed as a correspondingly weighed metal powder or appropriately weighed metal oxide powder before the grinding process of the molybdenum oxide-containing powder mixture.
• tantalum or niobium oxide powder With tantalum or niobium as dopant, the use of a tantalum oxide or niobium oxide powder (Ta2Ü5 or Nb20s) has the advantage that these powders are available in a finer particle size than the corresponding metal powders and thus a more homogeneous distribution of the dopant in the target material can be achieved.
• the powder mixture obtained preferably has an average particle size with a diameter of less than 150 ⁇ m.
• the Malvern laser diffraction in laser diffraction, particle size distributions by measuring the angular dependence of the intensity of scattered light of a laser beam, which is a dispersed
• Particle sample penetrates, determined) are used.
• the powder mixture thus produced is filled in a mold, for example in a graphite mold, and then compacted, wherein the compression step can be carried out using pressure and / or temperature, in particular pressure and temperature.
• Suitable compaction methods are, for example, spark plasma sintering (SPS), hot pressing, hot isostatic pressing or press sintering.
• SPS spark plasma sintering
• hot pressing hot isostatic pressing or press sintering.
• the compaction takes place in particular at temperatures between 600 and 900 ° C and pressing pressures between 15 and 110 MPa.
• compression takes place by means of pressure and temperature, the heat being generated internally by an electric current conducted through the powder mixture.
• SPS is characterized by high heating and cooling rates and short process times.
• the compression takes place by means of SPS at temperatures between 600 and 750 ° C and pressing pressures between 15 and 45 MPa in a vacuum or inert gas atmosphere (eg argon) instead.
• the compression is also carried out via pressure and temperature, wherein the heat is supplied from outside via a heated mold.
• the compression takes place by means of
• Hot pressing at temperatures between 650 and 850 ° C and at pressures between 15 and 80 MPa in a vacuum or inert gas atmosphere (e.g., argon).
• compaction is likewise effected via pressure and temperature.
• Preferred process parameters are temperatures between 650 and 900 ° C and pressures between 60 and 110 MPa.
• the compaction of the powder usually takes place in a sealed capsule.
• press sintering the powder or the powder mixture is pressed into a green compact and this is then sintered by heat treatment below the melting temperature in a suitable sintering atmosphere.
• the starting powders in a solid phase reaction or depending on the chemical composition and
• Process conditions also liquid phase reactions, or multi-phase reactions (e.g., solid-liquid) in a multi-phase (in the sense of Herkomponent) target material converted.
• the resulting reactions are similar to a comproportionation: M0O3 is reduced to various substoichiometric Mo oxides (for example, M018O52, M0O4O11, ...) while M0O2 is oxidized to various substoichiometric Mo oxides.
• M0O3 contained in the powder mixture is degraded, ie the volume fraction of the MoO 3 phase is significantly reduced.
• readily available M0O3 can be used as a powder, but it is - depending on the process control - in the finished compact Targeted target only to a very limited extent or no longer detectable, since it is converted to substoichiometric Mo oxides.
• the proportion of M0O3, which has a rather disadvantageous effect in the target material as described above, can thus be reduced or completely avoided.
• a metallic dopant such as tantalum or niobium is oxidized due to the usually high affinity (oxide formation enthalpy ⁇ /) of the dopant to oxygen in a solid state reaction, usually completely to the respective metal oxide (in the case of Ta to Ta2Ü5 or in the case of Nb to Nb20s).
• the dopant may also be at least partially present in the target material as substoichiometric oxide (for example Ta 2 O 5- y with 0 ⁇ y ⁇ 0.05 or Nb 2 05- y with 0 ⁇ y ⁇ 0.05) or as
• Molybdenum mixed oxide (tantalum-molybdenum mixed oxide or niobium-molybdenum mixed oxide) are present. After compacting, a mechanical
• Post-processing for example by cutting tools, to the desired final geometry or for surface preparation (setting a desired roughness of the surface) done.
• the target material according to the invention is preferably used for gas-phase deposition of molybdenum oxide-containing layers by means of a DC (direct current) sputtering or DC sputtering process
• DC sputtering or DC sputtering
• the sputtering target connected to the cathode and an anode are used (usually the housing of the coating system and / or shielding in the
• the DC sputtering process or pulsed DC sputtering process is carried out in a noble gas atmosphere, in particular an argon gas atmosphere, preferably non-reactive without additional supply of oxygen. Due to the already mentioned oxygen depletion during the coating process, the deposited layers have a slightly lower oxygen content than the one used
• Target material the exact oxygen content of the deposited layers depends on the size and constructive design of the individual
• Target material can also be sputtered reactively with delivery of at most 20 vol.% Oxygen. Since the oxygen content of the target material in one set wide parameter range, and the target material for each application can be adjusted individually according to the amount of supplied oxygen is usually relatively low. The disadvantages of reactive sputtering (hysteresis effects, potential inhomogeneities of the deposited layer) therefore have less effect.
• Fig. 1 Binary phase diagram of the system molybdenum-oxygen
• Fig. 2 Raman reference spectrum 1 (M0O2), where the intensity (number)
• Fig. 3 Raman reference spectrum 2 (M04O11).
• Fig. 4 Raman reference spectrum 3 (presumably M018O52).
• FFiigg .. 55 Raman reference spectrum 4 (substoichiometric molybdenum oxide of unknown composition, but not M05O14, M08O23, or M09O26).
• Fig. 6 Raman reference spectrum 5 (M0O3).
• Fig. 7 Raman reference spectrum 6 (Ta20s).
• FFiigg. 88 : a Raman mapping microstructure of a third
• FIG. 9 shows a Raman-mapping microstructure of a fourth.
• FIG. 10 shows a Raman-mapping microstructure of a fifth.
• Example 1
• the obtained Mo oxide powder has an oxygen content of 73.1 at.%. It is placed in a graphite mold with the dimensions 260 x 240 mm and a height of 50 mm and in a hot press under vacuum at a pressure of 45 MPa, a temperature of 750 ° C and a holding time of 120 min. compacted.
• the compacted component shows a relative density (pore determination on metallographic ground) of 96% and has a MoO 2 phase with a fraction of 10% by volume, a MoO 3 phase with a fraction of 7% by volume and a substoichiometric molybdenum oxide phase fraction of 83 vol.% On.
• the substoichiometric molybdenum oxide phase fraction is predominantly formed by Mo 4 On.
• Graphite mold with a diameter of 70 mm and a height of 50 mm and placed in a Spark plasma sintering plant (SPS) under vacuum at a pressure of 40 MPa, a temperature of 775 ° C and a holding time of 120 min. compacted.
• the compacted component has a relative density of 98%. It consists of a MoO 2 phase with a content of 2.7% by volume and a substoichiometric molybdenum oxide phase content of a total of 97.3% by volume. A Mo03 phase could not be detected.
• SPS Spark plasma sintering plant
• the compacted component has a relative density of 95.6%.
• the resulting target material has a MoO 2 phase of 10.3 vol.%, A MoCh phase of 19.2 vol.%, Substoichiometric molybdenum oxides of 1
• FIG. 5 shows the Raman spectrum of this substoichiometric molybdenum oxide.
• the microstructure shows areas with M0O2 phase, areas with Mo03 phase and areas with Ta205 phase; these different phases are embedded like islands in a cohesive network formed by the substoichiometric molybdenum oxides M04O11, M018O52 and the substoichiometric molybdenum oxide of unknown composition.
• Example 4 differs from Example 3 by a variation of
• the powder batch preparation is carried out as in Example 3.
• the powder mixture is placed in a graphite mold with the dimensions 260 x 240 mm and a height of 50 mm and in a hot press under vacuum at a pressure of 40 MPa, a temperature of 750 ° C and a holding time of 240 min. compacted.
• the compacted component has a relative density of 97% up.
• the target material obtained has a MoO 2 phase with a content of 8.1% by volume, a MoO 3 phase with a content of 5.5% by volume, substoichiometric molybdenum oxides with a content of altogether 85% by volume and a Ta 2 ⁇ D5 phase with a proportion of 1.4% by volume.
• the majority of the substoichiometric molybdenum oxides is M04O11 with a share of 59.1 vol.%. 9 shows the Raman mapping microstructure of the target material.
• Example 5 differs from Examples 3 and 4 by a variation of the hot pressing parameters, the powder batch production is carried out as in Example 3.
• the powder mixture is placed in a graphite mold with the dimensions 260 x 240 mm and a height of 50 mm and in a hot press under vacuum at a pressing pressure of 40 MPa, a temperature of 790 ° C and a holding time of 120 min. compacted.
• the compacted component has a relative density of 99.7%.
• the target material obtained has a MoO 2 phase with a content of 5.7% by volume, substoichiometric molybdenum oxides with a content of 91.9% by volume and Ta 2 O 5 phase with a content of 2.4% by volume.
• An M0O3 phase is undetectable.
• Dry cutting process (diamond wire saw, band saw, etc.) cut, cleaned by means of compressed air, then warm and conductive (C-doped) in
• Phenolic resin embedded, sanded and polished Since at least the M0O3 Phase content is water-soluble, a dry preparation is important. The resulting cut was subsequently analyzed by light microscopy.
• Raman spectra are obtained from the backscattered radiation transmitted through an optical grating (300 lines / mm, spectral resolution: 2.6 cm -1 ) wave-dispersive, and by means of a CCD detector (1024 x 256 pixel multiChannel CCD, spectral range: 200-1050 nm) are recorded.With a microscope objective with 10-fold magnification and numerical aperture NA of 0.25, which For the purpose of focusing the laser beam from the Raman spectrometer, a theoretical measuring point size of 5.2 pm 2 was obtained The excitation energy density (3 mW / pm 2 ) is chosen to be small enough to avoid phase changes in the sample In the case of molybdenum oxides, excitation radiation is limited to a few microns (in the case of pure M0O3 it is about 4 pm, but since a mixture of different phases is analyzed, this is an exact indication the penetration depth is not possible). This became the measuring point
• Raman signal averaged over 4s acquisition time yielding a good signal-to-noise ratio.
• evaluation software Horiba LabSpec 6 evaluation software Horiba LabSpec 6
• a two-dimensional representation of the surface composition of the sample was created, from which the domain size, area proportions, etc. of the different phases can be determined quantitatively.
• reference spectra are recorded on previously synthesized reference samples or reference spectra on larger homogenous sample areas, taking care to ensure that a reference spectrum corresponds exactly to a metal oxide phase.
• Each measurement point is then assigned a color which corresponds to a metal oxide phase, with only the phase with the highest weighting factor c being used for the color assignment
• the magnitude of the weighting factor a determines the brightness of the measuring point This procedure is justified insofar as the spectrum of one measuring point can generally be clearly assigned to a single metal oxide phase.
• volume data of the individual molybdenum oxide phases therefore add up to 100% alone without the pore volume.
• the determination of the relative density is carried out by means of digital image analysis of light microscopic image recordings of the metallographic cut, in which the relative area fraction of the pores is determined. This was done after

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