Heteroleptic triazenide metal complexes

Abstract

The present invention relates to a compound of formula [M(L C )(L T )(L Z ) whereby the following applies: M = scandium, yttrium, lanthanides, or titanium; C = unsubstituted, mono- or poly-alkyl-substituted cyclopentadienide anion; L T = Triazenide anion (R 1 -N3-R 2 ) - , [where R 1 and R 2 groups are, independently of one another, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms; L Z a)L C Independently of L C or b) selected from the group described in T Independently of L T The present invention also relates to the use of at least one such metal complex for producing a layer on the surface of a substrate consisting of or containing at least one metal M, and for producing electronic components. The present invention also relates to a substrate presenting on its surface a layer consisting of or containing at least one metal M and produced using such a metal complex.

Description

[Background technology]

[0001] Homoleptic and heteroleptic metal complexes exhibiting at least one nitrogen-containing ligand, methods for preparing these metal complexes, and the use of these metal complexes as precursors in chemical vapor deposition processes are known in the art.

[0002] In the field of electrical engineering, particularly in the field of semiconductor technology, there is increasing interest in the production of high-purity layers, for example, containing or consisting of lanthanide (III) oxides, lanthanide (III)-containing mixed oxides, or lanthanide (Ln)-containing III-V compound semiconductors. The deposition of such metal or metal-containing layers on the surface of a substrate can be carried out, for example, by metal-organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), or metal-organic chemical vapor phase epitaxy (MOVPE).

[0003] At this point and below, any indication of the exact stoichiometry of a metal layer, metal film, metal-containing layer, or metal-containing film is disclaimed. The terms layer and film are used synonymously, whereby neither of these words includes any indication as to layer or film thickness.

[0004] Patent Document 1 describes a compound having the general formula Ln(R 1 Cp) m (R 2 -NC(R 4 )=NR 2 ) n and a method for depositing a lanthanide-containing film on a semiconductor substrate using such a precursor, whereby the following applies: Ln = Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; 1 and R 2 are independently selected from the group consisting of H and C1-C5 alkyl chains; R 4=H or Me; m and n range from 1 to 2. Each precursor also has a melting point below about 105°C. Example embodiments are shown only for m=2 and n=1, and therefore only for Ln(III) complexes, which are each represented by R 1 The synthetic procedures presented are primarily directed to precursors, each of which has an N,N'-dialkyl-substituted acetamidinate ligand, R 1 =R 2 = iPr or tBu and R 4 =Me. R 1 =R 2 = iPr and R 4 Further procedures are described for the preparation of complexes with one N,N'-dialkyl-substituted formamidinate ligand each where =H.

[0005] In these Ln(III) complexes with one or two amidinate ligands, especially at least one acetamidinate ligand, the NC(R 4 The carbon contained in the )=N skeleton is undesirable. This is particularly true in the context of the use of these heteroleptic Ln(III) complexes as precursors in chemical vapor deposition processes, since there is a significant risk that the Ln or Ln-containing layers produced will be contaminated by carbon and therefore rendered useless for their intended application, particularly in the semiconductor sector.

[0006] Patent Document 2 is R 1 and R 2 is a hydrocarbon radical of the formula R 1 -N3-R 2and the use of the metal complexes for depositing metals or compounds of metals from the gas phase. For the lanthanide group, two examples are given: [La(tBu-N3-tBu)3] (see Example 10 on page 37) and [Ce(tBu-N3-tBu)3] (see Example 28 on page 52). These homoleptic lanthanide(III) complexes each have a relatively high molecular weight of more than 600 g / mol (approximately 608 g / mol).

[0007] The preparation of homoleptic cerium(III) complexes was carried out by reacting CeCl3 with Li(tBu-N3-tBu), and homoleptic lanthanum(III) complexes was prepared starting from [La(hmds)3] (hmds = hexamethyldisilazide) and tBu-HN3-tBu. Thermogravimetric analysis showed that the products still contained residual traces of hexamethyldisilazide, and the melting process started at a temperature of 103 °C (see page 38).

[0008] The melting temperature of approximately 100°C and the relatively high molecular weight, especially above 600 g / mol, suggest that this lanthanum(III) triazenide complex has a relatively low vapor pressure. Substances with the above-mentioned properties and the low volatility usually associated with them are rather unfavorable for use as precursors in chemical vapor deposition processes (see also claim 21 of Patent Document 2). The reasons for this are manifold: on the one hand, the use of low-volatility substances generally necessitates process conditions in which the quality of the produced metal or metal-containing layer is insufficient for many end uses. In particular, high temperatures are required, the generation of which, unfortunately, requires complex and therefore costly heating systems. The additional equipment effort and increased energy consumption adversely affect the economic and ecological balance of the process. The pyrolysis of homoleptic precursors such as [La(tBu-N3-tBu)3] can also result in increased incorporation of parasitic impurities into the semiconductor layer, for example in the form of carbon, thereby further worsening the layer quality.

[0009] In view of the above, the known precursor materials for chemical vapor deposition processes are classified as unsatisfactory from an ecological and (atomic) economical perspective.

[0010] The present invention therefore aims to overcome these and further drawbacks of the prior art and to provide a metal complex containing a metal relevant to the electrical industry, particularly the semiconductor industry, namely scandium, yttrium, a lanthanide, or titanium, and meeting the requirements imposed on precursor materials for chemical vapor deposition processes. In particular, the metal complex should be characterized by high purity and a relatively high vapor pressure, making it suitable as a precursor for the production of high-quality metal or metal-containing layers. Furthermore, the metal complex should be easily, efficiently, reproducibly, and as cost-effectively as possible, even on an industrial scale, with high purity and good yield. Furthermore, the present invention relates to a method for producing a layer consisting of or containing at least one metal on the surface of a substrate using at least one of the metal complexes presented herein, wherein the metal is scandium, yttrium, a lanthanide, or titanium. Furthermore, the subject of the present invention is a substrate presenting on its surface at least one layer consisting of or containing at least one metal, the metal being as defined above, each layer being produced using at least one of the metal complexes presented herein. Furthermore, a method for producing electronic components using at least one of the metal complexes presented herein should be provided. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] US Patent Application Publication No. 2014 / 0335702 [Patent Document 2] International Publication No. 2019 / 115646 Summary of the Invention

[0012] The problem is solved using the general formula: [M(L C )(L T )(L Z )] (I), [In the formula, i. M is a metal central atom selected from the group consisting of scandium (Sc), yttrium (Y), a lanthanide, and titanium (Ti); ii.L C teeth, - Unsubstituted cyclopentadienide anion (C5H5 - ), - General formula R A Cp - A monoalkyl-substituted cyclopentadienide anion represented by the formula (wherein R A is selected from the group consisting of linear alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms, and - General formula R B R C R D R E R F Cp - A polyalkyl-substituted cyclopentadienide anion represented by the formula (wherein R B , R C , R D , R E , and R F The groups are independently selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 10 carbon atoms, and branched alkyl groups having 3 to 10 carbon atoms, with the proviso that R B , R C , R D , R E , and R F At least two of the groups are not hydrogen (H). and a monoanionic pi donor ligand selected from the group consisting of: iii. L T is represented by the general formula (R 1 -N3-R 2 ) - A triazenide anion represented by the formula (wherein R 1 and R2 groups are independently selected from the group consisting of linear alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms, and iv. L Z teeth, a) Monoanionic π-donor ligand L C Independently of - Unsubstituted cyclopentadienide anion (C5H5 - ), - General formula R A Cp - A monoalkyl-substituted cyclopentadienide anion represented by the formula (wherein R A is selected from the group consisting of linear alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms, and - General formula R B R C R D R E R F Cp - A polyalkyl-substituted cyclopentadienide anion represented by the formula (wherein R B , R C , R D , R E , and R F The groups are independently selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 10 carbon atoms, and branched alkyl groups having 3 to 10 carbon atoms, with the proviso that R B , R C , R D , R E , and R F At least two of the groups are not hydrogen (H). a monoanionic pi donor ligand selected from the group consisting of: or b) General formula (R 1 -N3-R 2 ) - A triazenide anion represented by the formula (wherein R 1 and R 2 The groups may be independently of one another and may be a triazenide anion L Tand independently selected from the group consisting of linear alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms. is] This problem is solved by a metal complex represented by the formula:

[0013] General formula [M(L C )(L T )(L Z )](I) includes both mononuclear and polynuclear metal complexes.

[0014] In the context of the present invention, the term "lanthanide" refers to the group consisting of lanthanum and the 14 elements following lanthanum, with atomic numbers 58 to 71: cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). Together with the lighter lanthanum homologues, scandium (Sc) and yttrium (Y), the lanthanides are referred to as "rare earth metals."

[0015] General formula [M(L C )(L T )(L Z )](I)[where L Z is a monoanionic pi donor ligand], the monoanionic pi donor ligand L C and monoanionic pi donor ligand L Z It should be noted that it can be assumed that the groups are different or identical. C )(L T )(L Z )](I)[where L Z is represented by the general formula (R 1 -N3-R 2 In the metal complex represented by the formula, the triazenide anion L T and Triazenide Anion L Zmay be different or the same.

[0016] R A The radicals may also be selected from the group consisting of linear alkyl radicals having 1 to 9 carbon atoms and branched alkyl radicals having 3 to 9 carbon atoms, more advantageously from the group consisting of linear alkyl radicals having 1 to 8 carbon atoms and branched alkyl radicals having 3 to 8 carbon atoms, even more advantageously from the group consisting of linear alkyl radicals having 1 to 7 carbon atoms and branched alkyl radicals having 3 to 7 carbon atoms, and in particular from the group consisting of linear alkyl radicals having 1 to 6 carbon atoms and branched alkyl radicals having 3 to 6 carbon atoms.

[0017] General formula R B R C R D R E R F Cp - The polyalkyl-substituted cyclopentadienide anion represented by the formula (I) is at least doubly alkyl-substituted. It may also be triply, quadruply, or even penta-alkyl-substituted. In particular, in the latter case, R B , R C , R D , R E , and R F In this case, the monoanionic π-donor ligand is, in the simplest case, the 1,2,3,4,5-pentamethylcyclopentadienide anion, and R B =R C =R D =R E =R F = Methyl applies (C5Me5 - ;Cp * ).

[0018] R B , R C , R D , R E , and R FThe groups may also be selected, independently of one another, from the group consisting of hydrogen (H), linear alkyl groups having 1 to 9 carbon atoms, and branched alkyl groups having 3 to 9 carbon atoms, more advantageously from the group consisting of hydrogen (H), linear alkyl groups having 1 to 8 carbon atoms, and branched alkyl groups having 3 to 8 carbon atoms, even more advantageously from the group consisting of hydrogen (H), linear alkyl groups having 1 to 7 carbon atoms, and branched alkyl groups having 3 to 7 carbon atoms, in particular from the group consisting of hydrogen (H), linear alkyl groups having 1 to 6 carbon atoms, and branched alkyl groups having 3 to 6 carbon atoms, with the proviso that in each case R B , R C , R D , R E , and R F At least two of the groups are not hydrogen (H).

[0019] R 1 Groups and R 2 The radicals may also be selected independently from the group consisting of linear alkyl radicals having 1 to 9 carbon atoms and branched alkyl radicals having 3 to 9 carbon atoms, advantageously from the group consisting of linear alkyl radicals having 1 to 8 carbon atoms and branched alkyl radicals having 3 to 8 carbon atoms, more advantageously from the group consisting of linear alkyl radicals having 1 to 7 carbon atoms and branched alkyl radicals having 3 to 7 carbon atoms, and even more advantageously from the group consisting of linear alkyl radicals having 1 to 6 carbon atoms and branched alkyl radicals having 3 to 6 carbon atoms.

[0020] The metal complexes of formula I presented herein can be advantageously produced reproducibly by a simple, atom-efficient, and relatively inexpensive synthesis, i.e., in high purity and in good to very good yields, as well as good space-time yields, which meet the requirements for precursor materials for chemical vapor deposition processes, i.e., on a commercial scale. The compounds of formula I can be applied in essentially all chemical vapor deposition (CVD) processes. In particular, these processes are MOCVD, MOVPE, and ALD processes.

[0021] [M(L C )(L T )(L Z The preparation of metal complexes of type (I) is carried out starting from anhydrous metal(III) halides and alkali metal cyclopentadienides in aprotic polar solvents, in particular ethers such as THF or Et O. The metal(III) halides, in particular metal(III) chlorides, are advantageously present as THF adducts, generated in situ, if applicable.

[0022] The terms "in situ preparation" and "in situ production" respectively mean that the starting materials necessary for the synthesis of the compound thus produced and the intermediate thus produced, respectively, are reacted in a solvent or solvent mixture with the appropriate stoichiometry, and the product formed is not thereby isolated. Rather, the solution or suspension containing the intermediate produced in situ is further used directly, i.e., without isolation and / or further purification.

[0023] The product of the first salt metathesis reaction, e.g., [(EtCp)2YCl], can be advantageously reacted directly, i.e., without isolation and / or purification, with lithium triazenide to give the desired product of formula I, e.g., [(EtCp)2Y(tBu-N3-tBu)]. For this step, it is particularly advantageous to select an aprotic, nonpolar solvent, e.g., toluene. The lithium halide, particularly LiCl, formed as the only by-product can then be quantitatively or nearly quantitatively separated by easy and rapid filtration and / or decantation and / or centrifugation steps. Removal of the solvent is followed by equally easy and rapid purification of the crude product by distillation and / or sublimation.

[0024] The compound of formula I is 1 According to H NMR spectroscopy, they are usually obtained with a purity of at least 97%, advantageously greater than 97%, particularly greater than 98% or 99%. This is due to the fact that after isolation and purification of each metal complex of formula I, impurities may still be present due to volatile organic compounds, particularly due to the organic solvents used as part of the synthesis. Experience has shown that this type of impurity is not critical for the use of the metal complexes described herein in chemical vapor deposition processes. In other words, the quality of the deposited metal layer or metal-containing layer is usually not impaired by this type of impurity.

[0025] In the context of this invention, the terms "high purity" and "ultra-pure" refer to a total content of impurities based on unwanted metals, unwanted metalloids, atmospheric oxygen, and water of less than 1 ppm, ideally less than 100 ppb. In the semiconductor industry, this level of purity is referred to as electronic grade. Potential impurities of the above types, i.e., based on volatile organic compounds, especially based on organic solvents used as part of the synthesis, are not taken into account in this purity specification.

[0026] The yield of the metal complexes of formula I presented herein is generally 70% or higher. When this process is carried out on an industrial scale, the target compound is advantageously obtained in comparable yield and purity.

[0027] It is surprising that the metal complexes of formula I described herein exist without solvent after simple purification steps, i.e., distillation or sublimation. In other words, metal complexes of formula I, such as [(EtCp)Sc(tBu-N3-tBu)2] and [(EtCp)2Y(tBu-N3-tBu)], are not obtained in the form of solvent adducts and solvent adducts of these metal complexes, respectively. This is particularly advantageous in terms of their use as precursors for producing high-purity metal or metal-containing layers, especially by chemical vapor deposition processes. The fact that the metal complexes of formula I exist without solvent is surprising, especially since, in the case of lanthanide cations, the small ratio between charge and radius usually leads to a high coordination number. The general formula (R X -NC(R Y )=NR Z ) - While two cyclopentadienide anions and one amidinate anion of the formula (see US Pat. No. 5,629,299) can adequately shield the coordination sphere of the Ln(III) cation (see US Pat. No. 5,629,299), this is not expected for the ligand regime consisting of, for example, two cyclopentadienide anions and one triazenide anion, since the triazenide anion exhibits a relatively sharp bite angle, especially compared to the amidinate anion.

[0028] The [M(L C )(L T )(L Z )](I) type metal complexes are characterized by heteroleptic complex design and have the general formula (R 1 -N3-R 2 ) -The skeleton of the triazenide ligand advantageously exhibits only nitrogen, and the skeleton of the anionic N-donor ligand is formed by two alkyl R 1 and R 2 The nitrogen-containing backbone clearly reduces the risk that exists as part of the chemical vapor deposition process of producing contaminated (especially carbon) and therefore quality-defective layers. Furthermore, the incorporation of the desired elements, especially nitrogen, into the produced layers is promoted, i.e., the incorporation rate of the desired elements is improved. It has been found that this risk can be further reduced by the choice of the two terminal alkyl groups. Thus, when the complex [(EtCp)2Sc(tBu-N3-tBu)] is used as a precursor material in a MOVPE process, the [(MeCp)2Sc(R 1 -N3-R 2 )][where R 1 =R 2 Even lower carbon incorporation rates were observed when using complexes with less sterically demanding and carbon-poor triazenide ligands such as [wherein i =Me or Et or iPr].

[0029] As presented here, the general formula [M(L C )(L T )(L Z A further important advantage of the complex type represented by (I) is the possibility to form a variety of different, particularly customized precursors in a very simple manner, since, on the one hand, the ligand regime is variable, i.e., a) the cyclopentadienide ligand L C , triazenide ligand L T , and the cyclopentadienide ligand L Z or b) a cyclopentadienide ligand L C , triazenide ligand L T , and triazenide ligand L Z On the other hand, the three ligands L C , L T , and L ZEach of these is a residue R A , R B , R C , R D , R E , R F , R 1 , and R 2 This is particularly advantageous in view of the different process conditions to which the precursor material may be exposed, for example, depending on the choice of deposition process. Thus, customized and application-specific optimized precursors can each be produced with relatively little effort, i.e., by simply changing the ligand regime and / or the three ligands L C , L T , and L Z The metal-containing cations can be formed by varying the substitution pattern of the cyclopentadienide ligand(s) and triazenide ligand(s). Therefore, optimization can be performed for application in, for example, MOCVD processes, ALD processes, or MOVPE processes. In this context, it should be noted that the synthetic route outlined above can be advantageously followed essentially independently of the desired metal center and ligand regime. In other words, both the metal center and the ligand sphere of the metal center can be varied over a wide range, particularly by modifying the substitution pattern of the cyclopentadienide ligand(s) and triazenide ligand(s), without the need for substantial changes to the synthetic protocol. Rather, only minor modifications, if any, to the synthetic protocol are required, for example, in the form of changing the solvent and / or adjusting the temperature.

[0030] It is particularly advantageous that the metal complexes of formula I presented herein typically have relatively low melting temperatures, typically below 100°C, or below 95°C, or below 90°C, e.g., about 80°C for [(MeCp)Sc(tBu-N3-tBu)] or about 40°C for [(EtCp)Y(tBu-N3-tBu)]. Furthermore, metal complexes can also be formed having molecular weights of less than 600 g / mol, advantageously up to 595 g / mol, and particularly less than 595 g / mol. Complexes of formula I (where M = Sc, Y, or Ti) can also have molecular weights of, for example, less than 550 g / mol or less than 500 g / mol, e.g., in the range of 350 g / mol to 550 g / mol. This, combined with the low melting temperatures, advantageously results in relatively high vapor pressures for the metal complexes described herein.

[0031] Thermogravimetric analysis (TGA) of selected metal complexes represented by Formula I, particularly the complexes [(EtCp)Sc(tBu-N-tBu)] and [(EtCp)Sc(tBu-N-tBu)] (see Figures 1 and 2), revealed that the transition of these precursor compounds into the gas phase occurs at relatively low temperatures. This transition also advantageously occurs without decomposition. Consequently, when complexes of the type presented herein are used as precursors in chemical vapor deposition processes, the targeted decomposition of each precursor can be advantageously achieved at relatively low process temperatures. Overall, therefore, better availability of the precursor in the gas phase is achieved, ultimately resulting in increased incorporation of the desired elements. Furthermore, the targeted decomposition at relatively low process temperatures favorably influences layer growth. Consequently, the layers produced are of high quality in terms of their purity, their composition, and their morphology.

[0032] In the context of the present invention, the term "high quality layer" refers to the purity, composition, in particular the content and morphology of each metal M of the layer produced by the process of chemical vapor deposition.

[0033] For example, AlScN layers were fabricated using the complex [(EtCp)Sc(tBu-N-tBu)] as a precursor in an MOVPE process. The AlScN layers were deposited, for example, on the surface of a gallium nitride (GaN) substrate. The growth temperature was typically in the range of 900°C to 1,200°C, and the internal temperature of the bubbler (also known as a vapor pressure saturator in German) was generally about 50°C to about 100°C. Surprisingly, even at relatively low internal temperatures of the bubbler within the above range, sufficiently high precursor vapor pressures were observed. A commonly selected range of molar flow rates was achieved by setting the hydrogen flow rate (carrier gas) equivalent to the flow rate determined for the precursor. Layer growth rates within the expected range were achieved. Depending on the growth conditions selected in each case, particularly the selected substrate, bubbler internal temperature, and process temperature, the produced AlScN layers contained scandium in a proportion of at least about 10 atomic percent, i.e., the scandium incorporation rate was at least about 10 atomic percent. Consequently, the scandium content was at least comparable to the value of about 10% recently reported by Streicher et al. for AlScN layers (Phys. Status Solidi RRL 2023, 17, 2200387). This layer was obtained by an MOCVD process using bis(methylcyclopentadienyl)scandium chloride ([(MeCp)ScCl]) at a growth temperature of 900 °C.

[0034] Surprisingly, when using the complex presented here [(EtCp)Sc(tBu-N-tBu)], the scandium incorporation rate was found to be independent of the growth temperature, unlike the known precursor [(MeCp)ScCl], which was also used by the inventors under identical process conditions.

[0035] The atomic composition of the fractions of the AlScN layers produced in the context of the present invention was determined in each case by high-resolution transmission electron microscopy (HRTEM) combined with energy-dispersive X-ray analysis (EDXA) on a scanning transmission electron microscope (STEM).

[0036] In summary, the general formula [M(L C )(L T )(L Z It can be stated that metal complexes represented by [M(L)](I) can be prepared in good to very good yields and with high purity even on an industrial scale by simple methods. The heteroleptic variable complex design, which forms at least one ligand with a nitrogen-based carbon-free framework (triazenide ligand), allows the formation of a variety of different metal complexes, each advantageously customized and optimized for specific applications. C )(L T )(L Z It is particularly advantageous that the metal complexes of the type (I) described herein fulfill all the requirements imposed on precursor materials for chemical vapor deposition processes and are therefore particularly well-suited for use in processes of this type. It is particularly advantageous that the intricate design of the compounds of formula I results in both enhanced incorporation of desired elements into the layers produced and reduced incorporation of undesired elements, such as carbon. Advantageously, the use of these complexes can be carried out at ideal process temperatures, thereby producing high-quality metal and metal-containing layers. For example, the layers comprise or consist of lanthanide-containing III-V compound semiconductors or Ln oxides. Overall, from an (atomic) economic and environmental standpoint, the use of complexes of the type presented herein in chemical vapor deposition processes is particularly advantageous.

[0037] In an advantageous embodiment of the metal complexes described herein, the lanthanide is i. La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; or ii. La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, and Lu; or iii. La, Ce, Pr, Nd, Eu, Gd, Er, Yb, and Lu is selected from the group consisting of:

[0038] In particular, the lanthanide is selected from the group consisting of La, Ce, Nd, Eu, Er, and Lu.

[0039] According to another embodiment of the metal complex provided herein, i. Monoanionic π-donor ligand L C but, - Unsubstituted cyclopentadienide anion (C5H5 - ), - General formula R A Cp - [In the formula, R A the group is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, - General formula R B R C R D R E R F Cp - [In the formula, R B , R C , R D , R E , and R F groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; However, R B , R C , R D , R E , and R F at least two of the groups are not hydrogen (H) being selected from the group consisting of: and / or ii. Triazenide anion L T R 1 and R 2 At least one of the groups is selected from the group consisting of linear alkyl groups having 1 to 6 carbon atoms and branched alkyl groups having 3 to 6 carbon atoms. It is expected that:

[0040] In addition, the monoanionic pi donor ligand L C is the general formula R B R C R D R E R F Cp - [In the formula, R B , R C , R D , R E , and R F The groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, with the proviso that R is not hydrogen (H). B , R C , R D , R E , and R F at least two of the groups are identical].

[0041] In this case, the pi donor ligand L C For example, Me4Cp - , or Me(Et)2Cp - , or Et2Cp - , or Et2(iBu)Cp - , or Me5Cp - (Cp * )

[0042] Furthermore, the monoanionic pi donor ligand L C is the general formula R B R C RD R E R F Cp - [In the formula, R B , R C , R D , R E , and R F The groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, with the proviso that R B , R C , R D , R E , and R F Exactly two, or exactly three, or exactly four, or exactly five of the groups are not hydrogen (H), advantageously R B , R C , R D , R E , and R F Exactly two or exactly five of the groups are not hydrogen (H).

[0043] In this case, the pi donor ligand L C For example, Me2Cp - , Me(Et)Cp - , Et2Cp - , Me(iPr)Cp - , Et(iPr)Cp - , iPr2Cp - , Me(iBu)Cp - , Et(iBu)Cp - , iBu2Cp - , Me(sBu)Cp - , Et(sBu)Cp - , and sBu2Cp - Alternatively, the bi-donor ligand L is an anion selected from the group consisting of C For example, Me4Cp - , or Me(Et)2Cp - , or Et2(iBu)Cp -, or Me5Cp - (Cp * ) may also be used.

[0044] According to a further advantageous embodiment of the metal complex presented here, the ligand L Z is a monoanionic pi donor ligand, i. Monoanionic π-donor ligand L C or monoanionic pi-donor ligand L Z is selected, or ii. Monoanionic π-donor ligand L C and monoanionic pi donor ligand L Z But independently of each other, - Unsubstituted cyclopentadienide anion (C5H5 - ), - General formula R A Cp - [In the formula, R A the group is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, - General formula R B R C R D R E R F Cp - [In the formula, R B , R C , R D , R E , and R F groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; However, R B , R C , R D , RE , and R F at least two of the groups are not hydrogen (H) being selected from the group consisting of It is expected that:

[0045] In an alternative or complementary embodiment, the triazenide anion L T R 1 and R 2 At least one of the groups is selected from the group consisting of straight chain alkyl groups having 1 to 6 carbon atoms and branched alkyl groups having 3 to 6 carbon atoms.

[0046] According to further embodiments of the metal complexes presented herein, the triazenide anion L T R 1 Groups and R 2 The radicals are selected independently from one another from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

[0047] Ligand L Z is a monoanionic pi donor ligand, i. Monoanionic π-donor ligand L C or monoanionic pi-donor ligand L Z is selected, or ii. Monoanionic π-donor ligand L C and monoanionic pi donor ligand L Z But independently of each other, General formula R B R C R D R E R F Cp - [In the formula, R B , R C , R D , R E , and R Fgroups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; However, R is not hydrogen (H). B , R C , R D , R E , and R F at least two of the groups are identical being selected from the group consisting of It can also be assumed.

[0048] In this case, the pi donor ligand L C and / or the pi donor ligand L Z For example, Me4Cp - , Me(Et)2Cp - , Et2Cp - , Et2(iBu)Cp - , and Me5Cp - (Cp * ) is selected from the group consisting of

[0049] moreover, i. Monoanionic π-donor ligand L C or monoanionic pi-donor ligand L Z is selected, or ii. Monoanionic π-donor ligand L C and monoanionic pi donor ligand L Z But independently of each other, General formula R B R C R D R E R F Cp - [In the formula, R B , R C , R D , R E , and R FThe groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and their isomers, in particular from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, with the proviso that R B , R C , R D , R E , and R F Exactly two, or exactly three, or exactly four, or exactly five of the groups are not hydrogen (H), advantageously R B , R C , R D , R E , and R F Polyalkyl-substituted cyclopentadienide anions represented by the formula: Exactly two or exactly five of the groups are not hydrogen (H) being selected from the group consisting of can be assumed.

[0050] In this case, the pi donor ligand L C and / or the pi donor ligand L Z For example, Me2Cp - , Me(Et)Cp - , Et2Cp - , Me(iPr)Cp - , Et(iPr)Cp - , iPr2Cp - , Me(iBu)Cp - , Et(iBu)Cp - , iBu2Cp - , Me(sBu)Cp - , Et(sBu)Cp - , and sBu2Cp - Alternatively, the pi donor ligand L is selected from the group consisting of C and / or the pi donor ligand L Z For example, Me4Cp - , or Me(Et)2Cp - , or Et2(iBu)Cp - , or Me5Cp - (Cp * ) may also be used.

[0051] In yet another variant of the metal complexes described herein, L Z is a monoanionic pi donor ligand, and the monoanionic pi donor ligand L C and monoanionic pi donor ligand L Z are assumed to be identical.

[0052] According to a further advantageous embodiment of the metal complex presented herein, the ligand L Z is represented by the general formula (R 1 -N3-R 2 ) - [Wherein, triazenide anion L Z R 1 and R 2 at least one of the groups is selected from the group consisting of a linear alkyl group having 1 to 6 carbon atoms and a branched alkyl group having 3 to 6 carbon atoms.

[0053] In another advantageous embodiment, the ligand L Z is represented by the general formula (R 1 -N3-R 2 ) - [Wherein, triazenide anion L Z R 1 Groups and R 2 The groups may be independently of one another and may be a triazenide anion L T and independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers, particularly selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

[0054] In a further variant of the metal complex presented here, L Z is represented by the general formula (R 1 -N3-R 2 ) - [Wherein, triazenide anion L T and Triazenide Anion L Zare identical to each other.

[0055] According to yet another embodiment of the metal complex provided herein, i. Triazenide anion L T R 1 Groups and R 2 The groups are identical, and / or ii. L Z is represented by the general formula (R 1 -N3-R 2 ) - [Wherein, triazenide anion L Z R 1 Groups and R 2 The groups are the same. It is expected that:

[0056] In yet another advantageous embodiment of the metal complexes described herein, the central metal atom M is selected from the group consisting of Sc, Y, La, Ce, Nd, Eu, Er, Lu, and Ti, A. Ligand L Z is a monoanionic pi donor ligand, i. Monoanionic π-donor ligand L C or monoanionic pi-donor ligand L Z is selected, or ii. Monoanionic π-donor ligand L C and monoanionic pi donor ligand L Z But independently of each other, - Unsubstituted cyclopentadienide anion (C5H5 - ), - General formula R A Cp - [In the formula, R A a monoalkyl-substituted cyclopentadienide anion represented by the formula: wherein the group is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; - General formula R BR C R D R E R F Cp - [In the formula, R B , R C , R D , R E , and R F groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; However, R is not hydrogen (H). B , R C , R D , R E , and R F at least two of the groups are identical is selected from the group consisting of and Triazenide Anion L T R 1 Groups and R 2 groups are independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl; or B. Ligand L Z is represented by the general formula (R 1 -N3-R 2 ) - [In the formula, i. Two triazenide anions L T and L Z One of the R 1 and R 2 The groups are independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. or ii. Triazenide anion L T R 1 and R 2 group, and the triazenide anion L Z R 1 and R 2groups are each independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl; and and Monoanionic pi-donor ligand L C but, - Unsubstituted cyclopentadienide anion (C5H5 - ), - General formula R A Cp - [In the formula, R A a monoalkyl-substituted cyclopentadienide anion represented by the formula: wherein the group is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; - General formula R B R C R D R E R F Cp - [In the formula, R B , R C , R D , R E , and R F groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; However, R is not hydrogen (H). B , R C , R D , R E , and R F at least two of the groups are identical being selected from the group consisting of It is expected that:

[0057] According to variant A, for example, the pi donor ligand L C and / or the pi donor ligand L Z But Cp - (C5H5 -), MeCp - (MeC5H4 - ), EtCp - (EtC5H4 - ), iPrCp - (iPrC5H4 - ), iBuCp - (iBuC5H4 - ), sBuCp - (sBuC5H4 - ), tBuCp - (tBuC5H4 - ), Et2Cp - (Et2C5H3 - ), and Me5Cp - (Cp * , C5Me5 - It can also be assumed that the triazenide ligand L is selected from the group consisting of T For example, (Me-N-Me) - , (iPr-N3-iPr) - , (iPr-N3-tBu) - , (tBu-N3-tBu) - , and (iBu-N3-iBu) - may be selected from the group consisting of:

[0058] According to variant B, the triazenide ligand L T and / or triazenide ligand L Z For example, (Me-N-Me) - , (iPr-N3-iPr) - , (iPr-N3-tBu) - , (tBu-N3-tBu) - , and (iBu-N3-iBu) - The monoanionic pi donor ligand L may be selected from the group consisting of: C For example, Cp - (C5H5 - ), MeCp - (MeC5H4 - ), EtCp - (EtC5H4 - ), iPrCp - (iPrC5H4 - ), iBuCp -(iBuC5H4 - ), sBuCp - (sBuC5H4 - ), tBuCp - (tBuC5H4 - ), Et2Cp - (Et2C5H3 - ), and Me5Cp - (Cp * , C5Me5 - ) is selected from the group consisting of

[0059] According to further embodiments of the metal complexes described herein, the metal complexes have a structure represented by Formula I.1, or Formula I.2, or Formula I.3, or Formula I.4, or Formula I.5, or Formula I.6, or Formula I.7, or Formula I.8, or Formula I.9, or Formula I.10, or Formula I.11: [ka] JPEG2026507955000003.jpg182130 It has.

[0060] According to another advantageous embodiment of the metal complexes described herein, the metal complexes are evaporable without decomposition or sublimable without decomposition.

[0061] This is particularly advantageous, since the incorporation rate of each metal M is increased, especially due to the transition of the metal complexes into the gas phase without decomposition. The incorporation rate of nitrogen is also increased. The layers produced are of high quality in terms of their purity, their composition, and their morphology. Overall, this property of the metal complexes particularly favorably influences the (atomic) economic and ecological balance of the process. For further details on the advantages of the transition of the precursor compounds into the gas phase without decomposition, please refer to the information above on this point.

[0062] According to a further advantageous alternative or complementary variant, the molecular weight of the metal complex is less than 600 g / mol, advantageously at most 595 g / mol, in particular less than 595 g / mol.

[0063] In comparison, the two homoleptic Ln(III) triazenide complexes (Ln=La or Ce) described in US Pat. No. 5,629,999 each have a molecular weight of over 600 g / mol (approximately 608 g / mol).

[0064] The generally relatively small molecular weight of the metal complexes described herein of formula I, advantageously at most 595 g / mol, in particular less than 595 g / mol, advantageously facilitates a particularly (energy) efficient transfer of the metal complex into the gas phase.

[0065] Metal complexes of formula I, where M = Sc, Y, or Ti, may have molecular weights of less than 550 g / mol or less than 500 g / mol, for example, in the range of 350 g / mol to 550 g / mol. Thus, for the previously depicted Y(III) compounds of formula I.1, the molecular weight is between 400 g / mol and 450 g / mol, i.e., about 431 g / mol, and for the previously depicted Sc(III) complexes of formula I.2, the molecular weight is between 350 g / mol and 400 g / mol, i.e., about 360 g / mol.

[0066] Furthermore, this challenge i. consisting of at least one metal M; the at least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium; or ii. contains at least one metal M; At least one metal M is selected from the group consisting of scandium, yttrium, the lanthanides, and titanium. a layer on the surface of a substrate, particularly a semiconductor substrate, - a compound of general formula [M(L C )(L T )(LZ )](I) ] at least one metal complex represented by the formula or - a compound of general formula [M(L C )(L T )(L Z )] (I) and an aprotic nonpolar solvent. The problem is solved by a method for manufacturing using

[0067] Thereby, the method comprises the following steps: A. - formation of at least one metal complex according to one or more of the above embodiments, or - forming a solution comprising at least one metal complex according to one or more of the above embodiments and an aprotic non-polar solvent; and B. i. consists of at least one metal M; or ii. Contains at least one metal M depositing a layer onto the surface of the substrate using at least one metal complex formed in step A as a precursor compound. Includes:

[0068] The above [M(L C )(L T )(L Z )](I) type, or at least one metal complex of the general formula [M(L C )(L T )(L Z The resulting solution containing at least one metal complex represented by (I) 1Due to the high purity of these metal complexes (measured by H NMR spectroscopy), of at least 97%, preferably more than 97%, in particular more than 98% or 99%, they are particularly well suited as precursor compounds or solutions containing precursor compounds for producing high-quality layers on the surface of substrates. The layers thus consist of at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides are, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium. Furthermore, the aforementioned metal complexes of general formula I and solutions containing at least one such metal complex are suitable for producing high-quality layers containing at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides are, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium.

[0069] In the context of the present invention, the terms "high purity" and "ultra-pure" refer to a total content of impurities based on undesired metals, undesired metalloids, atmospheric oxygen, and water of less than 1 ppm, ideally less than 100 ppb. In the semiconductor industry, such a level of purity is called electronic grade. Potential impurities based on volatile organic compounds, in particular organic solvents used as part of the synthesis, are not taken into account in this purity specification. With respect to this type of impurity, the purity of the metal complex represented by formula I is usually at least 97%, advantageously greater than 97%, and in particular greater than 98% or 99%.

[0070] The deposition of each scandium, yttrium, lanthanide (lanthanide is, for example, La, Ce, Nd, Eu, Er, or Lu) or titanium layer, or the deposition of a layer containing at least one of the aforementioned metals, can be carried out by a CVD process, for example, an MOCVD process, an MOVPE process, or an ALD process.

[0071] The substrate can be, for example, a corundum foil or a thin metal foil, which itself can be part of a component and / or can already be provided with a semiconductor layer, for example a layer made of a III-V semiconductor such as gallium nitride (GaN).

[0072] In one embodiment of the method described herein, the substrate is a wafer. The wafer may comprise or consist entirely of one or more synthetic materials such as silicon, silicon carbide, germanium, gallium nitride, gallium arsenide, indium phosphide, glass such as SiO2, and / or silicone. Furthermore, the wafer may have one or more wafer layers, each having a surface. The production of a layer consisting of at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides are, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, or the production of a layer containing at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides are, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, may be realized on the surface of one or more wafer layers. The layer containing at least one metal may be a Ln2O3 layer, for example, or may also be a layer containing or consisting of a mixed oxide of two lanthanides.

[0073] Furthermore, this issue appears to be i. consisting of at least one metal M; the at least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium; or ii. contains at least one metal M; At least one metal M is selected from the group consisting of scandium, yttrium, the lanthanides, and titanium. A substrate presenting at least one layer, A metal layer consisting of at least one metal M or a layer containing at least one metal M, - a compound of general formula [M(L C )(L T )(L Z )](I) ] at least one metal complex represented by the formula or - a compound of general formula [M(L C )(L T )(L Z )] (I) and an aprotic nonpolar solvent. Manufactured using This is solved by the substrate.

[0074] The above [M(L C )(L T )(L Z )](I) type, or at least one metal complex of the general formula [M(L C )(L T )(L Z Due to the high purity of these metal complexes, the solutions used, which contain at least one metal complex of formula (I), are particularly well suited as precursor compounds or precursor compound-containing solutions for producing high-quality layers on the surface of a substrate.

[0075] The definition of the term "high purity" is stated in the context of a method for producing a layer consisting of or containing at least one metal M on the surface of a substrate.

[0076] The deposition of each scandium, yttrium, lanthanide (lanthanide is, for example, La, Ce, Nd, Eu, Er, or Lu) or titanium layer, or the deposition of a layer containing at least one of the aforementioned metals, can be carried out by a CVD process, for example, an MOCVD process, an MOVPE process, or an ALD process.

[0077] The substrate may be, for example, a corundum foil or a thin metal foil, and may itself be part of a component and / or may already be provided with a semiconductor layer, for example a layer made of a III-V semiconductor such as gallium nitride (GaN).

[0078] In one embodiment of the substrate described herein, the substrate is a wafer. The wafer may comprise or consist entirely of one or more synthetic materials such as silicon, silicon carbide, germanium, gallium nitride, gallium arsenide, indium phosphide, glass such as SiO2, and / or silicone. Furthermore, the wafer may have one or more wafer layers, each having a surface. The production of a layer consisting of at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides are, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, or the production of a layer containing at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides are, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, may be realized on the surface of one or more wafer layers. The layer containing at least one metal may be a Ln2O3 layer, for example, or may also be a layer containing or consisting of a mixed oxide of two lanthanides.

[0079] Furthermore, this challenge - a compound of general formula [M(L C )(L T )(L Z )](I) ] at least one metal complex represented by the formula or - a compound of general formula [M(L C )(L T )(L Z )] (I) and an aprotic nonpolar solvent. The problem is solved by a method for manufacturing an electronic component, in particular an electronic semiconductor component, using

[0080] Thereby, the method comprises the following steps: A. - a compound of the general formula [M(L C )(L T )(L Z )] (I) the formation of at least one metal complex represented by the formula or - a compound of general formula [M(L C )(L T )(L Z 2. Formation of a solution comprising at least one metal complex of formula (I) and an aprotic non-polar solvent; B. i. consists of at least one metal M; or ii. Contains at least one metal M Deposition of a layer onto the surface of a substrate; and C. Completion of electronic components, especially electronic semiconductor components Includes:

[0081] The electronic components, in particular electronic semiconductor components, are for example detectors, photoelements, semiconductor diodes, lasers, electronic switching elements, in particular field effect transistors or high electron mobility transistors or fibre optic emitters or fibre optic sensors.

[0082] The above [M(L C )(L T )(L Z )](I) type, or at least one metal complex of the general formula [M(L C )(L T )(L Z Due to the high purity of these metal complexes, the solutions used, which contain at least one metal complex of formula (I), are particularly well suited as precursor compounds or precursor compound-containing solutions for producing high-quality layers on the surface of a substrate.

[0083] The definition of the term "high purity" is stated in the context of a method for producing a layer consisting of or containing at least one metal M on the surface of a substrate.

[0084] The deposition of each scandium, yttrium, lanthanide (lanthanide is, for example, La, Ce, Nd, Eu, Er, or Lu) or titanium layer, or the deposition of a layer containing at least one of the aforementioned metals, can be carried out by a CVD process, for example, an MOCVD process, an MOVPE process, or an ALD process.

[0085] The substrate may be, for example, a corundum foil or a thin metal foil, and may itself be part of a component and / or may already be provided with a semiconductor layer, for example a layer made of a III-V semiconductor such as gallium nitride (GaN).

[0086] In one embodiment of the method described herein, the substrate is a wafer. The wafer may comprise or consist entirely of one or more synthetic materials such as silicon, silicon carbide, germanium, gallium nitride, gallium arsenide, indium phosphide, glass such as SiO2, and / or silicone. Furthermore, the wafer may have one or more wafer layers, each having a surface. The production of a layer consisting of at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides are, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, or the production of a layer containing at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides are, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, may be realized on the surface of one or more wafer layers. The layer containing at least one metal may be a Ln2O3 layer, for example, or may also be a layer containing or consisting of a mixed oxide of two lanthanides.

[0087] Further features, details, and advantages of the invention will become apparent from the claims and from the following description of embodiments and drawings. [Brief explanation of the drawings]

[0088] [Figure 1] 1 is a graph showing the TGA curve and SDTA curve (differential thermal analysis curve performed simultaneously with TGA measurement; synchronous differential thermal analysis) of the metal complex [(EtCp)Sc(dbt)], where dbt = di-tert-butyltriazenide anion, prepared according to Example 3.1. [Figure 2] 1 is a graph showing TGA and SDTA curves of the metal complex [(EtCp)Sc(dbt)2], where dbt = di-tert-butyltriazenide anion, prepared according to Example 4. [Figure 3] 1 is a graph showing the TGA and SDTA curves of the known complex [(MeCp)2ScCl]2. DETAILED DESCRIPTION OF THE INVENTION

[0089] The TGA curves shown in Figures 1 and 2 were recorded from two metal complexes of general formula I, and for both complexes the following applies: M = Sc, L C =EtCp - , and L T =(tBu-N3-tBu) - Furthermore, for the first metal complex, L Z =L C applies, and for the second metal complex, L Z =L T applies.

[0090] For comparison purposes, the TGA curve of the known precursor material [(MeCp)ScCl] is shown in Figure 3. This Sc(III) complex was prepared according to the procedure set out in WO 2018 / 086730.

[0091] On the x-axis, the temperature in °C is plotted in each case for both the TGA and SDTA measurements, with the relevant numerical values ​​indicated above the x-axis.

[0092] For TGA measurements, the left y-axis, on which the initial weight in mg is plotted, and the second y-axis (from the left; not shown in Figure 3) on which the remaining mass in % is plotted are also important. The right y-axis, in relation to SDTA measurements, plots the difference in heat flow in mW.

[0093] The TGA curves presented in Figures 1 and 2 show that both the Sc(III) complex [(EtCp)Sc(dbt)] and the Sc(III) complex [(EtCp)Sc(dbt)] can be evaporated at low temperatures, i.e., around 200°C, advantageously without decomposition. The low melting temperatures of these compounds can be seen from their associated SDTA curves: about 10°C for the complex [(EtCp)Sc(dbt)] and about 45°C for the compound [(EtCp)Sc(dbt)].

[0094] In contrast, the TGA curve shown in Figure 3 reveals that the known Sc(III) precursor [(MeCp)ScCl] unfortunately does not exhibit evaporation without decomposition. The melting temperature of this known complex is approximately 160 °C.

[0095] Based on the fact that the Sc(III) complexes [(EtCp)Sc(dbt)] and [(EtCp)Sc(dbt)] can be produced in high purity even on a commercial scale and can be evaporated without decomposition (the latter even at relatively low temperatures of around 200 °C), these complexes have been identified as precursors for producing high-quality scandium or scandium-containing layers, such as AlScN layers, in chemical vapor deposition (CVD) processes, in particular on semiconductor substrates. This has been confirmed, for example, by using the complex [(EtCp)Sc(dbt)] in MOVPE processes. Information on this point has been provided previously.

[0096] [(EtCp)2Y(dbt)], [(MeCp)2Sc(dbt)], [(EtCp)2Sc(dbt)], [(EtCp)Sc(dbt)2], [(Cp)2Ti(pbt)], [ (iPrCp)(EtCp)Eu(dbt)], [(iPrCp)Lu(dbt)2], [(tBuCp)Er(dmt)(dpt)], [(Et2Cp)La(dbt)2], [(Cp * Procedure for the synthesis of [(MeCp)Ce(dmt)], [(iPrCp)(MeCp)Nd(dibt)]

[0097] Thereby the following applies: Cp = cyclopentadienide anion, C5H5 - ;MeCp = methylcyclopentadienide anion, MeC5H4 - ;EtCp = ethylcyclopentadienide anion, EtC5H4 - ;Et2Cp = diethylcyclopentadienide anion, Et2C5H3 - ;iPrCp = isopropylcyclopentadienide anion, iPrC5H4 - ;tBuCp = tert-butylcyclopentadienide anion, tBuC5H4 - ;Cp * = 1,2,3,4,5-pentamethylcyclopentadienide anion, C5Me5 - ;dmt = dimethyltriazenide anion, (Me-N3-Me) - ; dpt = diisopropyl triazenide anion, (iPr-N3-iPr) - ; pbt = isopropyl-tert-butyltriazenide anion, (iPr-N3-tBu) - ;dbt = di-tert-butyltriazenide anion, (tBu-N3-tBu) - ;dibt = diisobutyltriazenide anion (iBu-N3-iBu) - .

[0098] Materials and Methods All reactions were carried out under a protective gas atmosphere by conventional Schlenk techniques. The starting materials and solvents used had a degree of purity pa.

[0099] All nuclear magnetic resonance spectroscopy measurements were carried out on a Bruker AV II 300 type instrument. 1 H NMR and 13 C NMR spectra were calibrated to the relevant residual proton signals of the solvent (C6D6) as an internal standard: 1 H: 7.16 ppm(s); 13 C: 128.0 ppm (tr). Chemical shifts are given in ppm and refer to the δ scale. All signals are abbreviated according to the splitting pattern of these signals: s (singlet), t (triplet), q (quartet), or m (multiplet). The coupling between two nuclei A and B via an n bond is expressed in hertz (Hz). n J AB Coupling constants of the form

[0100] Infrared spectra are typically measured on a Bruker Alpha ATR-IR spectrometer. Absorption bands are expressed in wavenumbers (cm -1 ) and intensities are represented by the following abbreviations: w (weak), m (medium), s (strong). Spectra were always normalized to the band with the strongest intensity.

[0101] Thermogravimetric analyses were performed on a Mettler Toledo TGA / DSC3+STAR system, whereby combined SDTA measurements were performed alongside each TGA measurement. Samples were measured in aluminum oxide, aluminum, or sapphire crucibles, depending on the method and the state of agglomeration. Samples were heated to the final temperature at defined heating rates between 5 and 25 K / min, respectively. The evaluation of the obtained spectra was performed using Mettler Toledo's STARe software.

[0102] Example 1.1: Preparation of [(EtCp)2Y(dbt)] starting from YCl3 [ka] 5.0 g of YCl3 (25.6 mmol) was added to 150 mL of THF at -60 °C and stirred for 3 days after warming to room temperature. A solution of EtCpLi (56.3 mmol) in 50 mL of THF was added dropwise to the resulting colorless suspension at 0 °C within 4 hours. The reaction mixture became completely clear upon melting at room temperature and was stirred at room temperature for 16 hours. The solvent was removed under vacuum. 50 mL of toluene was added to the resulting residue, and the resulting suspension was filtered. The filter cake was washed three times with 20 mL of toluene each time. The filtrate was diluted with 50 mL of toluene and cooled to 0 °C. 4.2 g of Li(dbt) (25.6 mmol) was then added in portions. The reaction mixture was first heated to room temperature and then heated to boiling point for 3 hours. The resulting suspension was filtered. The solvent of the filtrate was removed under vacuum, and the crude product was distilled under vacuum at 180 °C. The product was obtained as a colorless oil which slowly solidified to a colorless solid at room temperature. Yield: 75% (6.0 g; 19.3 mmol).

[0103] Example 1.2: Preparation of [(EtCp)2Y(dbt)] starting from [(EtCp)2YCl] [ka] To 90.5 g of (EtCp)2YCl (291 mmol) in 600 mL of n-hexane, 47.5 g of Li(dbt) (291 mmol) was added portionwise over a period of 2 hours at 0°C. The reaction mixture was stirred at 0°C for 2 hours and then at room temperature for 16 hours. The reaction mixture was then heated to boiling point for 3 hours. The resulting suspension was filtered, and the filter cake was washed three times with 50 mL of n-hexane each time. The solvent of the filtrate was removed under vacuum, and the crude product was distilled under vacuum at 180°C. The product was obtained as a colorless oil, which slowly solidified at room temperature. Yield: 78% (98 g; 227 mmol).

[0104] Melting temperature: about 40℃;1 1H NMR (300 MHz; C6D6): δ = 1.14 (t, 3 J HH = 7.6 Hz, 6H, CH2CH3), 1.20 (s, 18H, C(CH3)3), 2.45 (q, 3 J HH = 7.6 Hz, 4H, CH2CH3), 5.96 (m, 4H, CH arom. ), 6.02 (m, 4H, CH arom. ) ppm; 13 13C NMR (75 MHz; C6D6): δ = 16.4 (s, 2C, CH2CH3), 23.3 (s, 2C, CH2CH3), 30.2 (s, 6C, C(CH3)3), 56.8 (s, 1C, C(CH3)3), 56.9 (s, 1C, C(CH3)3), 110.2 (s, 1C, CH arom. ), 110.2 (s, 1C, CH arom. ),110.7 (s, 1C CH arom. ), 110.7 (s, 1C, CH arom. ),130.3 (s, 1C, C arom. quaternary ) ppm; IR (substance): wavenumber = 3064 (w), 2965 (m), 2928 (w), 2897 (w), 2867 (w), 1471 (w), 1459 (w), 1382 (w), 1357 (m), 1318 (w), 1278 (s), 1248 (m), 1202 (s), 1043 (w), 1027 (m), 911 (w), 854 (m), 764 (s), 665 (w), 619 (s), 554 (w), 487 (w), 465 (w), 426 (w) cm -1 .

[0105] Example 2: Preparation of [(MeCp)Sc(dbt)] [ka] 7.35g of [ScCl3 * [3THF] (20 mmol) was suspended in 50 mL of THF. A solution of MeCpK (40 mmol) in 100 mL of THF was added dropwise at room temperature within 1 hour. The reaction mixture was then stirred at room temperature for 16 hours. The solvent was removed under vacuum, and 50 mL of toluene was added to the residue. The resulting suspension was filtered, and the filter cake was washed three times with 20 mL of toluene each time. The filtrate was concentrated to a volume of approximately 30 mL and cooled to 0 °C. Then, 3.2 g of Li(dbt) (20 mmol) was added portionwise. After melting, 5 mL of THF was added, and the reaction mixture was stirred at room temperature for 16 hours. The resulting suspension was filtered, the solvent of the filtrate was removed under vacuum, and the crude product was distilled under vacuum at 150 °C. The product was obtained as a yellowish solid. Yield: 66% (5 g; 13.3 mmol).

[0106] Melting temperature: about 80°C (estimated); 1 H NMR (300 MHz; C6D6): δ = 1.23 (s, 18H, C(CH3)3), 1.98 (s, 6H, cp-CH3), 5.82 (m, 4H, CH arom. ), 6.89 (m, 4H, CH arom. ) ppm; 13 C NMR (75 MHz; C6D6): δ = 15.7 (s, 2C, cp-CH3), 30.4 (s, 6C, C(CH3)3), 57.3 (s, 2C, C(CH3)3), 110.3 (s, 2C, CH arom. ), 113.5 (s, 2C, CH arom. ), 121.4 (s, 1C, C arom. quaternary ) ppm; IR (matter): wavenumber = 2965 (m), 2925 (w), 2898 (w), 2864 (w), 1469 (w),1454 (w), 1383 (w), 1354 (m), 1283 (s), 1243 (m), 1201 (s),1047 (m), 932 (w), 842 (m), 773 (s), 618 (s), 555 (w), 493 (m), 469 (m), 436 (w), 425 (w) cm -1 .

[0107] Notes for Example 2: The synthesis of [(MeCp)2Sc(dbt)] can be carried out analogously to Example 1.2 starting from [(MeCp)2ScCl].

[0108] Example 3.1: [ScCl * Preparation of [(EtCp)2Sc(dbt)] starting from [(EtCp)2Sc(dbt)] [ka] 206.6 g of [ScCl3 * [(EtCp)2ScCl] (562 mmol) was added portionwise as a solid to a solution of EtCpK (1.12 mol) in 900 mL of THF at 0 °C within 3 h. The reaction mixture was subsequently stirred at room temperature for 2 h and then heated to boiling point for 5 h. The solvent was removed under vacuum, and 500 mL of n-hexane was added to the residue. The resulting suspension was hot filtered, and the residue was washed three times with 100 mL of n-hexane each. The filtrate was concentrated to a volume of approximately 250 mL and stored at 0 °C overnight. Subsequently, crystalline [(EtCp)2ScCl] was separated from the mother liquor by decantation, and the residue was dried under vacuum (yield: 75%, 127 g, 477 mmol). The yield of [(EtCp)2ScCl] could be further increased by further crystallization from the mother liquor.

[0109] 73 g of [(EtCp)2ScCl] (273 mmol) was dissolved in 500 mL of n-hexane in a 1 L flask. Then, 44.6 g of Li(dbt) (273 mmol) was added in portions at 0 °C. After melting, the Li(dbt) was stirred at room temperature for 16 h. The resulting suspension was heated to the boiling point for 3 h and then hot filtered. The solvent of the filtrate was removed by distillation. The residue was distilled (under dynamic vacuum, i.e., approximately 1 * 10 -3 mbar, 155°C) gave [(EtCp)Sc(dbt)] in the form of a yellow oil. Yield: 73% (80 g; 201 mmol).

[0110] Example 3.2: Preparation of [(EtCp)Sc(dbt)] starting from [(EtCp)ScCl] [ka] To 70 g of [(EtCp)2ScCl] (262 mmol) in 600 mL of n-hexane, 42.8 g of Li(dbt) (262 mmol) was added portionwise over a period of 2 hours at 0°C. The reaction mixture was stirred at 0°C for 2 hours, followed by 16 hours at room temperature. The reaction mixture was then heated to boiling point for 3 hours. The resulting suspension was filtered, and the filter cake was washed three times with 50 mL of n-hexane each. The solvent of the filtrate was removed under vacuum. The residue was distilled (under dynamic vacuum, i.e., approximately 1 * 10 -3 mbar, 155°C) gave [(EtCp)Sc(dbt)] in the form of a yellow oil. Yield: 81% (82 g; 212 mmol).

[0111] Melting temperature: about 10℃; 1 H NMR (300 MHz; C6D6): δ = 1.13 (t, 3 J HH = 7.6 H, 6H, CH2CH3), 1.24 (s, 18H, C(CH3)3), 2.37 (q, 3 J HH = 7.6 H, 4H, CH2CH3), 5.89 (m, 8H, CH arom. ) ppm; 13 C NMR (75 MHz; C6D6): δ = 16.4 (s, 2C, CH2CH3), 23.8 (s, 2C, CH2CH3), 30.4 (s, 6C, C(CH3)3), 57.4 (s, 1C, C(CH3)3), 110.4 (s, 4C, CH arom. ), 112.1 (s, 4C, CH arom. ),128.6 (s, 2C, C arom, quaternary ) ppm.

[0112] Example 4: [ScCl * Preparation of [(EtCp)Sc(dbt)2] starting from [3THF] [ka] 7.35g of [ScCl3 * [3THF] (20 mmol) was suspended in 50 mL of THF. A solution of EtCpK (20 mmol) in 100 mL of THF was added dropwise at room temperature within 1 hour. The reaction mixture was then stirred at room temperature for 16 hours. The solvent was removed under vacuum, and 50 mL of toluene was added to the residue. The resulting suspension was filtered, and the filter cake was washed three times with 20 mL of toluene each time. The filtrate was concentrated to a volume of approximately 30 mL and cooled to 0 °C. Subsequently, 6.4 g of Li(dbt) (20 mmol) was added portionwise. After melting, 5 mL of THF was added, and the reaction mixture was stirred at room temperature for 16 hours. The resulting suspension was filtered, the solvent of the filtrate was removed under vacuum, and the crude product was distilled under vacuum at 150 °C. The product was obtained as a yellowish solid. Yield: 73% (6.6 g; 14.6 mmol).

[0113] Melting temperature: about 45℃; 1 H NMR (300 MHz; C6D6): δ = 1.18 (t, 3 J HH= 7.6 H, 3H, CH3), 1.31 (s, 36H, NC(CH3)3), 2.55 (q, 3 J HH = 7.6 Hz, 2H, CH2), 6.28 (s, 4H, CpH) ppm.

[0114] Example 5: Preparation of [CpTi(pbt)] starting from [CpTiCl] [ka] To 10.68 g of [CpTiCl] (50 mmol) in 150 mL of n-hexane, 7.46 g of Li(pbt) (50 mmol) is added portionwise over a period of 2 hours at 0 °C. The reaction mixture is stirred at 0 °C for 2 hours and then at room temperature for 16 hours. The reaction mixture is then heated to boiling point for 3 hours. The resulting suspension is filtered, and the filter cake is washed three times with 50 mL of n-hexane each time. The solvent of the filtrate is removed under vacuum. Distillation of the residue gives [(Cp)Ti(pbt)].

[0115] From the successful synthesis according to Example 1.2 and Example 3.2, it can be concluded that the reaction of [CpTiCl] with Li(pbt) leads to the desired target compound [(Cp)Ti(pbt)], similar to Example 1.2 and Example 3.2.

[0116] According to Example 1.2, the compound [(EtCp)Y(dbt)] was obtained starting from [(EtCp)YCl] and Li(dbt). Similarly, according to Example 3.2, the complex [(EtCp)Sc(dbt)] was obtained starting from [(EtCp)ScCl] and Li(dbt) in practically the same yield and purity as the complex [(EtCp)Y(dbt)].

[0117] If the titanium(III) complex [CpTiCl], instead of [(EtCp)YCl] or [(EtCp)ScCl], is reacted with Li(pbt) in analogy to Example 1.2 or Example 3.2, [(Cp)Ti(pbt)] is obtained, since Ti 3+ Complex, Y 3+ complexes, and Sc 3+ This is because the complexes behave chemically similarly.

[0118] The yield and purity of [(Cp)Ti(pbt)] achieved by this example are similar or identical to those obtained by the syntheses of [(EtCp)Y(dbt)] (Example 1.2) and [(EtCp)Sc(dbt)] (Example 3.2) above.

[0119] Example 6: Preparation of [(iPrCp)(EtCp)Eu(dbt)] starting from [(iPrCp)(EtCp)EuCl] [ka] To 19.4 g of [(iPrCp)(EtCp)EuCl] (50 mmol) in 150 mL of n-hexane, 8.16 g of Li(dbt) (50 mmol) is added portionwise over a period of 2 hours at 0 °C. The reaction mixture is stirred at 0 °C for 2 hours and then at room temperature for 16 hours. The reaction mixture is then heated to boiling point for 3 hours. The resulting suspension is filtered, and the filter cake is washed three times with 50 mL of n-hexane each time. The solvent of the filtrate is removed under vacuum. Distillation of the residue gives [(iPrCp)(EtCp)Eu(dbt)].

[0120] From the successful synthesis according to Example 1.2 and Example 3.2, it can be concluded that the reaction of [(iPrCp)(EtCp)EuCl] with Li(pbt) leads to the desired target compound [(iPrCp)(EtCp)Eu(dbt)], analogously to Example 1.2 and Example 3.2.

[0121] According to Example 1.2, the compound [(EtCp)Y(dbt)] was obtained starting from [(EtCp)YCl] and Li(dbt). Similarly, according to Example 3.2, the complex [(EtCp)Sc(dbt)] was obtained starting from [(EtCp)ScCl] and Li(dbt) in practically the same yield and purity as the complex [(EtCp)Y(dbt)].

[0122] If the europium(III) complex [(iPrCp)(EtCp)EuCl], instead of [(EtCp)YCl] or [(EtCp)ScCl], is reacted with Li(pbt) in analogy to Example 1.2 or Example 3.2, [(iPrCp)(EtCp)Eu(dbt)] is obtained, since the Eu(iPrCp) complex intended as the starting material here is 3+ Lanthanide(III) complexes such as the Y complex 3+ complexes and Sc 3+ This is because they behave chemically similar to complexes.

[0123] The yield and purity of [(iPrCp)(EtCp)Eu(dbt)] achieved by this example are similar or identical to those obtained by the syntheses of [(EtCp)Y(dbt)] (Example 1.2) and [(EtCp)Sc(dbt)] (Example 3.2) above.

[0124] Example 7: Preparation of [(iPrCp)Lu(dbt)2] starting from [(iPrCp)LuCl2] [ka] To 17.65 g of [(iPrCp)LuCl2] (50 mmol) in 150 mL of n-hexane, 16.32 g of Li(dbt) (100 mmol) is added portionwise over a period of 2 hours at 0 °C. The reaction mixture is stirred for 2 hours at 0 °C, followed by 16 hours at room temperature. The reaction mixture is then heated to boiling point for 3 hours. The resulting suspension is filtered, and the filter cake is washed three times with 50 mL of n-hexane. The solvent of the filtrate is removed under vacuum. Distillation of the residue gives [(iPrCp)Lu(dbt)2].

[0125] From the successful synthesis according to Example 1.2 and Example 3.2, it can be concluded that the reaction of isopropylcyclopentadienyllutetium dichloride [(iPrCp)LuCl] with Li(pbt) similar to Example 1.2 and Example 3.2, but with a molar ratio of [(iPrCp)LuCl]:Li(pbt) of 1:2, leads to the desired target compound [(iPrCp)Lu(dbt)].

[0126] According to Example 4, the compound [(EtCp)2Y(dbt)] was obtained starting from [(EtCp)2YCl] and Li(dbt), with a molar ratio of the starting materials of 1:1. Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt), with practically the same yield and purity as the complex [(EtCp)2Y(dbt)].

[0127] If the lutetium(III) complex [(iPrCp)LuCl], instead of [(EtCp)YCl] or [(EtCp)ScCl], is reacted with Li(pbt) in a molar ratio of [(iPrCp)LuCl]:Li(pbt) of 1:2, analogously to Example 1.2 or Example 3.2, then [(iPrCp)Lu(dbt)] is obtained, since the Lu(pbt) complex intended here as the starting material 3+ Lanthanide(III) complexes such as the Y complex 3+ complexes and Sc 3+ This is because they behave chemically similar to complexes.

[0128] The yield and purity of [(iPrCp)Lu(dbt)] achieved by this example are similar or identical to those obtained by the syntheses of [(EtCp)Y(dbt)] (Example 1.2) and [(EtCp)Sc(dbt)] (Example 3.2) above.

[0129] Example 8: Preparation of [(tBuCp)Er(dmt)(dpt)] starting from [(tBuCp)ErCl] [ka] To 17.97 g of [(tBuCp)ErCl2] (50 mmol) in 150 mL of n-hexane, 3.95 g of Li(dmt) (50 mmol) is added portionwise over a period of 2 hours at 0 °C. Subsequently, 6.76 g of Li(dpt) (50 mmol) is added portionwise over a period of 2 hours at 0 °C. The reaction mixture is stirred for 2 hours at 0 °C and then at room temperature for 16 hours. The reaction mixture is then heated to boiling point for 3 hours. The resulting suspension is filtered, and the filter cake is washed three times with 50 mL of n-hexane. The solvent of the filtrate is removed under vacuum. Distillation of the residue gives [(tBuCp)Er(dmt)(dpt)].

[0130] From the successful synthesis according to Example 1.2 and Example 3.2, it can be concluded that the reaction of tert-butylcyclopentadienyl erbium dichloride [(tBuCp)ErCl] with lithium salts Li(dmt) and Li(dpt) similarly to Example 1.2 and Example 3.2, but with a molar ratio of [(tBuCp)ErCl]:lithium salt of 1:2, leads to the desired target compound [(tBuCp)Er(dmt)(dpt)].

[0131] According to Example 1.2, the compound [(EtCp)2Y(dbt)] was obtained starting from [(EtCp)2YCl] and Li(dbt), with a molar ratio of the starting materials of 1:1. Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt), with practically the same yield and purity as the complex [(EtCp)2Y(dbt)].

[0132] If the erbium(III) complex [(tBuCp)ErCl], instead of [(EtCp)YCl] or [(EtCp)ScCl], is reacted with Li(dmt) and Li(dpt) in a manner analogous to Example 1.2 or Example 3.2, but in a molar ratio of [(tBuCp)ErCl]:lithium salt of 1:2, [(tBuCp)Er(dmt)(dpt)] is obtained, since the Er complex intended here as the starting material 3+ Lanthanide(III) complexes such as the Y complex 3+ complexes and Sc 3+ This is because they behave chemically similar to complexes.

[0133] The yield and purity of [(tBuCp)Er(dmt)(dpt)] achieved by this example are similar or identical to those obtained by the syntheses of [(EtCp)Y(dbt)] (Example 1.2) and [(EtCp)Sc(dbt)] (Example 3.2) above.

[0134] Example 9: Preparation of [(Et2Cp)La(dbt)2] starting from [(Et2Cp)LaCl2] [ka] To 16.55 g of [(Et2Cp)LaCl2] (50 mmol) in 200 mL of n-hexane, 16.32 g of Li(dbt) (100 mmol) is added portionwise over a period of 2 hours at 0 °C. The reaction mixture is stirred for 2 hours at 0 °C, followed by 16 hours at room temperature. The reaction mixture is then heated to boiling point for 3 hours. The resulting suspension is filtered, and the filter cake is washed three times with 50 mL of n-hexane each time. The solvent of the filtrate is removed under vacuum. Distillation of the residue gives [(Et2Cp)La(dbt)2].

[0135] From the successful synthesis according to Example 1.2 and Example 3.2, it can be concluded that the reaction of diethylcyclopentadienyllanthanum dichloride [(EtCp)LaCl] with lithium salt Li(dbt) similar to Example 1.2 and Example 3.2, but with a molar ratio of [(EtCp)LaCl]:lithium salt of 1:2, leads to the desired target compound [(EtCp)La(dbt)].

[0136] According to Example 1.2, the compound [(EtCp)2Y(dbt)] was obtained starting from [(EtCp)2YCl] and Li(dbt), with a molar ratio of the starting materials of 1:1. Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt), with practically the same yield and purity as the complex [(EtCp)2Y(dbt)].

[0137] If the lanthanum(III) complex [(EtCp)LaCl], instead of [(EtCp)YCl] or [(EtCp)ScCl], is reacted with Li(dbt) in a similar manner to Example 1.2 or Example 3.2, but in a molar ratio of [(EtCp)LaCl]:lithium salt of 1:2, [(EtCp)La(dbt)] is obtained, since the La 3+ Lanthanide(III) complexes such as the Y complex 3+ complexes and Sc 3+ This is because they behave chemically similar to complexes.

[0138] The yield and purity of [(EtCp)La(dbt)] achieved by this example are similar or identical to those obtained by the syntheses of [(EtCp)Y(dbt)] (Example 1.2) and [(EtCp)Sc(dbt)] (Example 3.2) above.

[0139] Example 10: [(Cp * )(MeCp)CeCl] * Preparation of (MeCp)Ce(dmt)] [ka] 19.5 g of [(Cp * To [(MeCp)CeCl] (50 mmol), 3.95 g of Li(dmt) (50 mmol) is added portionwise at 0° C. over a period of 2 hours. The reaction mixture is stirred at 0° C. for 2 hours, followed by 16 hours at room temperature. The reaction mixture is then heated to boiling point for 3 hours. The resulting suspension is filtered, and the filter cake is washed three times with 50 mL of n-hexane. The solvent of the filtrate is removed under vacuum. Distillation of the residue gives [(Cp * )(MeCp)Ce(dmt)] is obtained.

[0140] From the successful synthesis according to Example 1.2 and Example 3.2, [(Cp * )(MeCp)CeCl] with Li(dmt) to give the desired target compound [(Cp * )(MeCp)Ce(dmt)] is obtained.

[0141] According to Example 1.2, the compound [(EtCp)Y(dbt)] was obtained starting from [(EtCp)YCl] and Li(dbt). Similarly, according to Example 3.2, the complex [(EtCp)Sc(dbt)] was obtained starting from [(EtCp)ScCl] and Li(dbt) in practically the same yield and purity as the complex [(EtCp)Y(dbt)].

[0142] Instead of [(EtCp)2YCl] or [(EtCp)2ScCl], the cerium(III) complex [(Cp * )(MeCp)CeCl] is reacted with Li(dmt) in analogy to Example 1.2 or Example 3.2 to give [(Cp * )(MeCp)Ce(dmt)] is obtained because the starting material intended here is Ce 3+ Lanthanide(III) complexes such as the Y complex 3+ complexes and Sc 3+ This is because they behave chemically similar to complexes.

[0143] This embodiment achieves [(Cp * The yield and purity of [(EtCp)Y(dbt)] (Example 1.2) and [(EtCp)Sc(dbt)] (Example 3.2) obtained above are similar or identical to those obtained by the synthesis of [(EtCp)Y(dbt)] (Example 1.2) and [(EtCp)Sc(dbt)] (Example 3.2) above.

[0144] Example 11: Preparation of [(iPrCp)(MeCp)Nd(dibt)] starting from [(iPrCp)(MeCp)NdCl] [ka] To 18.3 g of [(iPrCp)(MeCp)NdCl] (50 mmol) in 200 mL of n-hexane, 8.16 g of Li(dibt) (50 mmol) is added portionwise over a period of 2 hours at 0 °C. The reaction mixture is stirred for 2 hours at 0 °C, followed by 16 hours at room temperature. The reaction mixture is then heated to boiling point for 3 hours. The resulting suspension is filtered, and the filter cake is washed three times with 50 mL of n-hexane. The solvent of the filtrate is removed under vacuum. Distillation of the residue gives [(iPrCp)(MeCp)Nd(dibt)].

[0145] From the successful synthesis according to Example 1.2 and Example 3.2, it can be concluded that the reaction of [(iPrCp)(MeCp)NdCl] with Li(dibt) leads to the desired target compound [(iPrCp)(MeCp)Nd(dibt)], analogously to Example 1.2 and Example 3.2.

[0146] According to Example 1.2, the compound [(EtCp)Y(dbt)] was obtained starting from [(EtCp)YCl] and Li(dbt). Similarly, according to Example 3.2, the complex [(EtCp)Sc(dbt)] was obtained starting from [(EtCp)ScCl] and Li(dbt) in practically the same yield and purity as the complex [(EtCp)Y(dbt)].

[0147] If the neodymium(III) complex [(iPrCp)(MeCp)NdCl], instead of [(EtCp)YCl] or [(EtCp)ScCl], is reacted with Li(dibt) in analogy to Example 1.2 or Example 3.2, [(iPrCp)(MeCp)Nd(dibt)] is obtained, since the Nd intended as starting material here 3+ Lanthanide(III) complexes such as the Y complex 3+ complexes and Sc 3+ This is because they behave chemically similar to complexes.

[0148] The yield and purity of [(iPrCp)(MeCp)Nd(dibt)] achieved by this example are similar or identical to those obtained by the syntheses of [(EtCp)Y(dbt)] (Example 1.2) and [(EtCp)Sc(dbt)] (Example 3.2) above.

[0149] The invention is not limited to one of the above-described embodiments, but can be modified in many ways.

[0150] The present invention provides a compound of the formula [M(L C )(L T )(L Z ) ) whereby the following applies: M = scandium, yttrium, lanthanides, or titanium; L C = unsubstituted cyclopentadienide anion, mono- or poly-alkyl-substituted cyclopentadienide anion; L T = Triazenide anion (R 1 -N3-R 2 ) - [In the formula, R 1 and R 2 are each independently a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms; L Z a)L C Independently of L C or b) selected from the group described in T Independently of L T The compound is selected from the group described in

[0151] A further subject of the present invention is the use of at least one such metal complex for producing, on the surface of a substrate, a layer consisting of or containing at least one metal M, and for producing electronic components. The present invention further relates to a substrate presenting on its surface a layer consisting of or containing at least one metal M and produced using such a metal complex.

[0152] As presented here, the general formula [M(L C )(L T )(L Z Metal complexes of the formula [M(L)](I) can be prepared in good to very good yields and with high purity, even on an industrial scale, by simple procedures. Surprisingly and advantageously, these compounds exist without solvent after isolation and purification of these compounds by distillation or sublimation. Particularly advantageously, heteroleptic tunable complex designs, which form at least one ligand with a nitrogen-based, carbon-free framework (triazenide ligand), allow the formation of a variety of different, particularly customized and application-specifically optimized, metal complexes. The synthesis protocols described herein can thereby advantageously be used in principle to prepare, without significant modifications, metal complexes of the formula [M(L)](I) customized for a particular process, particularly for chemical vapor deposition. C )(L T )(L Z )](I) type compounds.

[0153] [M(L C )(L T )(L ZA further important advantage of the metal complexes of the type (I) described herein is that they meet all the requirements imposed on precursor materials for chemical vapor deposition processes (CVD processes), such as MOCVD, MOVPE, and ALD processes, and are therefore particularly well-suited for use in these types of processes. The complex design of the compounds of formula I not only promotes the incorporation of the desired elements in the desired form, i.e., the respective metals M and nitrogen, into the layers being produced, but also reduces the incorporation of undesired elements such as carbon. The use of these complexes can advantageously be carried out at ideal process temperatures, thereby enabling the production of high-quality metal and metal-containing layers. The produced layers are of high quality in terms of their purity, their composition, and their morphology. Overall, from an (atomic) economic and environmental standpoint, the use of complexes of the type presented herein in chemical vapor deposition processes is particularly advantageous.

[0154] All features and advantages that emerge from the claims, the specification and the drawings, including structural details, spatial arrangements and process steps, may be essential to the invention both alone and in any wide variety of combinations.

Claims

1. general formula [M(L Ｃ )(L Ｔ )(L Ｚ )] (I)、 [In the formula, i. M is a metal central atom selected from the group consisting of scandium (Sc), yttrium (Y), lanthanides, and titanium (Ti); ii. L Ｃ teeth, unsubstituted cyclopentadienide anion, - General formula R Ａ Cp － A monoalkyl-substituted cyclopentadienide anion represented by the formula (wherein R Ａ is selected from the group consisting of straight chain alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms, and - General formula R Ｂ R Ｃ R Ｄ R Ｅ R Ｆ Cp － A polyalkyl-substituted cyclopentadienide anion represented by the formula: Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are independently selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 10 carbon atoms, and branched alkyl groups having 3 to 10 carbon atoms, provided that the R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ At least two of the groups are not hydrogen (H). and a monoanionic pi donor ligand selected from the group consisting of: iii L Ｔ is represented by the general formula (R １ -N ３ -R ２ ) － (In the formula, R １ and R ２ groups are, independently of one another, selected from the group consisting of linear alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms; and iv. L Ｚ teeth, a) monoanionic pi donor ligand L Ｃ Independently of - unsubstituted cyclopentadienide anion (C ５ H ５ － ), - General formula R Ａ Cp － A monoalkyl-substituted cyclopentadienide anion represented by the formula (wherein R Ａ is selected from the group consisting of straight chain alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms, and - General formula R Ｂ R Ｃ R Ｄ R Ｅ R Ｆ Cp － A polyalkyl-substituted cyclopentadienide anion represented by the formula: Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are independently selected from the group consisting of hydrogen (H), linear alkyl groups having 1 to 10 carbon atoms, and branched alkyl groups having 3 to 10 carbon atoms; However, the above R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ At least two of the groups are not hydrogen (H). a monoanionic pi donor ligand selected from the group consisting of: or b) General formula (R １ -N ３ -R ２ ) － A triazenide anion represented by the formula (wherein R １ and R ２ The groups are independently of one another and are the triazenide anion L Ｔ and independently selected from the group consisting of straight chain alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms. is] A metal complex represented by the formula:

2. The lanthanide is i. La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; or ii. La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, and Lu; or iii. La, Ce, Pr, Nd, Eu, Gd, Er, Yb, and Lu; or iv. La, Ce, Nd, Eu, Er, and Lu 2. The metal complex of claim 1, selected from the group consisting of:

3. i. The monoanionic π-donor ligand L Ｃ but, - unsubstituted cyclopentadienide anion (C ５ H ５ － ), - General formula R Ａ Cp － A monoalkyl-substituted cyclopentadienide anion represented by the formula: Ａ groups selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and isomers thereof; - General formula R Ｂ R Ｃ R Ｄ R Ｅ R Ｆ Cp － A polyalkyl-substituted cyclopentadienide anion represented by the formula: Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and isomers thereof, provided that the R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ At least two of the groups are not hydrogen (H). selected from the group consisting of and / or ii. Triazenide anion L Ｔ The R １ and R ２ at least one of the groups is selected from the group consisting of straight chain alkyl groups having 1 to 6 carbon atoms and branched alkyl groups having 3 to 6 carbon atoms; The metal complex according to claim 1 or 2.

4. The ligand L Ｚ but, a) monoanionic pi donor ligand L Ｚ but, - unsubstituted cyclopentadienide anion (C ５ H ５ － ), - General formula R Ａ Cp － A monoalkyl-substituted cyclopentadienide anion represented by the formula: Ａ groups selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and isomers thereof; - General formula R Ｂ R Ｃ R Ｄ R Ｅ R Ｆ Cp － A polyalkyl-substituted cyclopentadienide anion represented by the formula: Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and isomers thereof, provided that the R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ At least two of the groups are not hydrogen (H). a monoanionic pi donor ligand selected from the group consisting of: or b) General formula (R １ -N ３ -R ２ ) － wherein the triazenide anion L Ｚ The R １ and R ２ At least one of the groups is selected from the group consisting of straight chain alkyl groups having 1 to 6 carbon atoms and branched alkyl groups having 3 to 6 carbon atoms.

4. The metal complex according to claim 1, wherein

5. The following characteristics: i. The triazenide anion L Ｔ The R １ group and the R ２ groups are independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and isomers thereof; ii. The triazenide anion L Ｔ The R １ group and the R ２ The groups are identical, iii. L Ｚ is a monoanionic pi donor ligand, and the monoanionic pi donor ligand L Ｃ and the monoanionic pi donor ligand L Ｚ are identical, iv. L Ｚ is represented by the general formula (R １ -N ３ -R ２ ) － wherein the triazenide anion L Ｚ The R １ group and the R ２ groups are independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and isomers thereof; v.L Ｚ is represented by the general formula (R １ -N ３ -R ２ ) － wherein the triazenide anion L Ｚ The R １ group and the R ２ the groups are identical; vi. L Ｚ is represented by the general formula (R １ -N ３ -R ２ ) － wherein the triazenide anion L Ｔ and the triazenide anion L Ｚ are identical.

5. The metal complex of claim 1, wherein the metal complex exhibits one or more of the following:

6. the metal central atom M is selected from the group consisting of Sc, Y, La, Ce, Nd, Eu, Er, Lu, and Ti; A. The ligand L Ｚ is a monoanionic pi donor ligand, i. The monoanionic π-donor ligand L Ｃ Or the monoanionic pi donor ligand L Ｚ is selected, or ii. The monoanionic π-donor ligand L Ｃ and the monoanionic pi donor ligand L Ｚ But independently of each other, - unsubstituted cyclopentadienide anion (C ５ H ５ － ), - General formula R Ａ Cp － A monoalkyl-substituted cyclopentadienide anion represented by the formula: Ａ groups selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; - General formula R Ｂ R Ｃ R Ｄ R Ｅ R Ｆ Cp － A polyalkyl-substituted cyclopentadienide anion represented by the formula: Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, provided that any of the R groups that is not hydrogen (H) is Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ At least two of the groups are identical. is selected from the group consisting of and The triazenide anion L Ｔ The R １ group and the R ２ groups are independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl; or B. The ligand L Ｚ is represented by the general formula (R １ -N ３ -R ２ ) － A triazenide anion represented by the formula: i. two of said triazenide anions L Ｔ and L Ｚ One of the R １ and R ２ The groups are independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. or ii. The triazenide anion L Ｔ The R １ and R ２ group, and the triazenide anion L Ｚ The R １ and R ２ groups are each independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. and and The monoanionic pi donor ligand L Ｃ but, - unsubstituted cyclopentadienide anion (C ５ H ５ － ), - General formula R Ａ Cp － A monoalkyl-substituted cyclopentadienide anion represented by the formula: Ａ groups selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; - General formula R Ｂ R Ｃ R Ｄ R Ｅ R Ｆ Cp － A polyalkyl-substituted cyclopentadienide anion represented by the formula: Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are independently selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, provided that any of the R groups that is not hydrogen (H) is Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ At least two of the groups are identical.

6. The metal complex of claim 1, selected from the group consisting of:

7. i. The metal complex is evaporable without decomposition or sublimable without decomposition; and / or ii. The molecular weight of the metal complex is less than 600 g / mol; 7. The metal complex according to claim 1 .

8. i. consisting of at least one metal M; the at least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium; or ii. Contains at least one metal M; a layer in which the at least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium; On the surface of a substrate, particularly a semiconductor substrate, - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I) at least one metal complex represented by the formula: or - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I)] and an aprotic nonpolar solvent.

1. A method for manufacturing a vehicle using Steps below: A. - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I) the formation of at least one metal complex represented by the formula: or - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I) and an aprotic non-polar solvent; and B. i. consisting of at least one metal M; or ii. Contains at least one metal M depositing a layer onto said surface of said substrate using at least one metal complex formed in step A as a precursor compound. A method comprising:

9. On the surface, i. consisting of at least one metal M; the at least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium; or ii. Contains at least one metal M; The at least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium. A substrate presenting at least one layer, The metal layer made of at least one metal M or the layer containing at least one metal M is - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I) at least one metal complex represented by the formula: or - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I)] and an aprotic nonpolar solvent. A substrate manufactured using the

10. - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I) at least one metal complex represented by the formula: or - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I)] and an aprotic nonpolar solvent.

1. A method for manufacturing electronic components, in particular electronic semiconductor components, using Steps below: A. - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I) the formation of at least one metal complex represented by the formula: or - a compound of the general formula [M(L Ｃ ) (L Ｔ ) (L Ｚ ) (I) and an aprotic non-polar solvent; B. i. consisting of said at least one metal M; or ii. Depositing a layer containing said at least one metal M on the surface of a substrate; and C. Completion of the electronic components, particularly the electronic semiconductor components A method comprising:

Images