Heteroreptic triazenate 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 Art

[0001] Homoleptic and heteroleptic metal complexes having at least one nitrogen-containing ligand, methods for producing these metal complexes, and the use of these metal complexes as precursors in chemical vapor deposition processes are known in the prior 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 that comprise or consist of, for example, lanthanide(III) oxides, lanthanide(III)-containing mixed oxides, or lanthanide (Ln)-containing III-V compound semiconductors. Deposition of such metal layers or metal-containing layers on the surface of a substrate can be performed by, for example, metal organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), or metal organic chemical vapor phase epitaxy (MOVPE).

[0003] At this point and hereinafter, the indication of the exact stoichiometry of metal layers, metal films, metal-containing layers or metal-containing films is abandoned. The terms layer and film are used synonymously, and none of these terms includes an indication relating to layer thickness or film thickness.

[0004] Patent Document 1 discloses a lanthanide-containing precursor represented by the general formula Ln(R 1 Cp) m (R 2 -N-C(R 4 )=N-R 2 ) n and a method for depositing a lanthanide-containing film on a semiconductor substrate using such a precursor. The following applies thereby: Ln=Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; R 1 and R 2 are each independently selected from the group consisting of H and C1~C5 alkyl chains; R 4=H or Me; m and n are in the range of 1 to 2. Also, each precursor has a melting point of less than approximately 105°C. Examples of embodiments are shown only for m=2 and n=1, and therefore only for Ln(III) complexes, and these complexes are respectively R 1 It contains two monosubstituted cyclopentadienyl ligands, which are =Me, Et or iPr, and one amidinate ligand. The synthetic procedure shown is mainly for precursors, each of which has an N,N'-dialkyl-substituted acetamidinate ligand and R 1 =R 2 =iPr or tBu and R 4 =Me is R 1 =R 2 =iPr and R 4 Further procedures are described for the preparation of complexes having one N,N'-dialkyl-substituted formamidinate ligand each in the form of =H.

[0005] In these Ln(III) complexes having one or two amidinate ligands, particularly at least one acetamidinate ligand, the ligand NC(R 4 The carbon contained in the )=N skeleton is undesirable. This is particularly true in the case of using these heteroreptic Ln(III) complexes as precursors in chemical vapor deposition processes, because the fabricated Ln layer or Ln-containing layer may be contaminated with carbon and therefore, by no means insignificant, render it unsuitable for its intended application, particularly in the semiconductor sector.

[0006] Patent Document 2 is R 1 and R 2 Formula R is a hydrocarbon radical 1 -N3-R 2This relates to metal complexes having at least one ligand L, and to the use of metal complexes for precipitating metals or metal compounds from a gas phase. For the lanthanide group, two examples are shown: [La(tBu-N3-tBu)3] (see Example 10 on page 37) and [Ce(tBu-N3-tBu)3] (see Example 28 on page 52). These homoreptic lanthanide(III) complexes have relatively high molecular weights of over 600 g / mol (approximately 608 g / mol), respectively.

[0007] The homoreptic cerium(III) complex was prepared by reacting CeCl3 with Li(tBu-N3-tBu), and the homoreptic lanthanum(III) complex was prepared starting from [La(hmds)3](hmds = hexamethyldisilazide) and tBu-HN3-tBu. Thermogravimetric analysis revealed that the product still contained residual traces of hexamethyldisilazide, and the melting process was initiated at a temperature of 103°C (see page 38).

[0008] The melting temperature of approximately 100°C and the relatively high molecular weight, particularly above 600 g / mol, suggest that this lanthanum(III) triazenide complex has a relatively low vapor pressure. Substances with the aforementioned properties, and the low volatility usually associated with these properties, are rather unsuitable for use as precursors in chemical vapor deposition processes (see also claim 21 of Patent Document 2). The reasons for this are numerous: on the one hand, using low-volatility substances generally requires process conditions that result in the quality of the resulting metal layer or metal-containing layer being insufficient for many end uses. In particular, high temperatures are required, and generating these high temperatures unfortunately necessitates complex and costly heating systems. The additional equipment effort and increased energy consumption negatively impact the economic and ecological balance of the process. In the case of thermal decomposition of homoreptic precursors such as [La(tBu-N3-tBu)3], there may be an increased incorporation of parasitic impurities into the semiconductor layer, for example, in the form of carbon, thereby further degrading the layer quality.

[0009] From the aforementioned perspective, known precursor materials for chemical vapor deposition processes are classified as inadequate from ecological and (atomic)economic standpoints.

[0010] Therefore, the object on which the present invention is based is to overcome these and further drawbacks of the prior art and to provide a metal complex that contains metals relevant to the electrical industry, particularly the semiconductor industry, namely scandium, yttrium, lanthanide, or titanium, and that satisfies the requirements imposed on precursor materials for chemical vapor deposition processes. In particular, the metal complex should be characterized by high purity and relatively high vapor pressure and should be suitable as a precursor for the production of high-quality metal layers or metal-containing layers. Furthermore, the metal complex should be able to be produced easily, efficiently, reproducibly, and as cost-effectively as possible, with high purity and good yield, even on an industrial scale. Moreover, the present invention relates to a method for producing a layer on the surface of a substrate consisting of or containing at least one metal, wherein the metal is scandium, yttrium, lanthanide, or titanium, using at least one of the metal complexes presented herein. Furthermore, the subject of the present invention is a substrate having a surface comprising or containing at least one layer made of at least one metal, wherein the metal is as defined herein, and each layer is manufactured using at least one of the metal complexes presented herein. Furthermore, a method for manufacturing an electronic component using at least one of the metal complexes presented herein should be provided. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] U.S. Patent Application Publication No. 2014 / 0335702 [Patent Document 2] International Publication No. 2019 / 115646 [Overview of the Initiative]

[0012] This 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), lanthanides, and titanium (Ti). ii.L C teeth, - Unsubstituted cyclopentadienide anion (C5H5 - ), - General formula R A Cp - Monoalkyl-substituted cyclopentadienide anions represented by the formula (wherein R A (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, provided that R B , R C , R D , R E , and R F (At least two of the elements are not hydrogen (H)) A monoanionic piedner ligand selected from the group consisting of the following: iii. L T The general formula is (R 1 -N3-R 2 ) - The triazenide anion represented by (wherein R 1 and R2 The 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 piedner ligand L C Independently of that, - Unsubstituted cyclopentadienide anion (C5H5 - ), - General formula R A Cp - Monoalkyl-substituted cyclopentadienide anions represented by the formula (wherein R A (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, provided that R B , R C , R D , R E , and R F (At least two of the elements are not hydrogen (H)) A monoanionic piedner ligand selected from the group consisting of, or b) General formula (R 1 -N3-R 2 ) - The triazenide anion represented by (wherein R 1 and R 2 The bases are independent of each other and triazena anion L Tindependently of, 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) which is The problem is solved by the metal complex represented by

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

[0014] In the context of the present invention, the term "lanthanide" means the group consisting of lanthanum and the 14 elements with atomic numbers 58 to 71 following lanthanum: 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 lanthanide homologs, namely scandium (Sc) and yttrium (Y), the lanthanoids are referred to as "rare earth metals".

[0015] General formula [M(L C )(L T )(L Z )](I) [wherein L Z is a monoanionic pi-donor ligand] In the metal complex represented by the above formula, it should be pointed out that the monoanionic pi-donor ligand L C and the monoanionic pi-donor ligand L Z can be envisaged to be different or identical. Furthermore, in the metal complex represented by general formula [M(L C )(L T )(L Z )](I) [wherein L Z is a triazenide anion represented by general formula (R 1 -N3-R 2 )] In the metal complex represented by the above formula, the triazenide anion L T and the triazenide anion L Zmay be different or the same.

[0016] R A The group is also more advantageously selected from the group consisting of linear alkyl groups having 1 to 9 carbon atoms and branched alkyl groups having 3 to 9 carbon atoms, even more advantageously from the group consisting of linear alkyl groups having 1 to 8 carbon atoms and branched alkyl groups having 3 to 8 carbon atoms, particularly advantageously from the group consisting of linear alkyl groups having 1 to 7 carbon atoms and branched alkyl groups having 3 to 7 carbon atoms, especially from the group consisting of linear alkyl groups having 1 to 6 carbon atoms and branched alkyl groups 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 is at least a doubly alkyl-substituted cyclopentadienide anion. It may also be a trialkyl-substituted, tetraalkyl-substituted, or pentaalkyl-substituted cyclopentadienide anion. Particularly in the latter case, R B , R C , R D , R E , and R F It is advantageous for the groups to be the same. In this case, in the simplest case, the monoanionic π-donor ligand is 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 independently selected 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 preferably 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 preferably 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, provided 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 base and R 2 The groups may also be independently selected from the group consisting of linear alkyl groups having 1 to 9 carbon atoms and branched alkyl groups having 3 to 9 carbon atoms, preferably from the group consisting of linear alkyl groups having 1 to 8 carbon atoms and branched alkyl groups having 3 to 8 carbon atoms, more preferably from linear alkyl groups having 1 to 7 carbon atoms and branched alkyl groups having 3 to 7 carbon atoms, and even more preferably from the group consisting of linear alkyl groups having 1 to 6 carbon atoms and branched alkyl groups having 3 to 6 carbon atoms.

[0020] The metal complex represented by Formula I, presented herein, can be advantageously and reproducibly produced by a simple, (atomic) efficient, and relatively inexpensive synthesis. That is, it can be produced with high purity that meets the requirements imposed on precursor materials for chemical vapor deposition processes, in yields ranging from good to very good, and with good space-time yields, i.e., on a commercial scale. The compounds represented by Formula I can be applied to virtually all chemical vapor deposition (CVD) processes, particularly the MOCVD, MOVPE, and ALD processes.

[0021] [M(L C )(L T )(L Z The preparation of type (I) metal complexes is carried out in a non-protic polar solvent, particularly ethers, such as THF or Et2O, starting from anhydrous metal(III) halides and alkali metal cyclopentadienides. Metal(III) halides, especially metal(III) chlorides, are advantageously formed in situ where applicable and exist as THF adducts.

[0022] The terms "in-situ preparation" and "in-situ production" mean, respectively, that the starting materials required for the synthesis of the compounds and intermediates thus produced are reacted in a solvent or solvent mixture in appropriate stoichiometric terms, and the products formed are not isolated thereby. Rather, the solution or suspension containing the intermediate produced in situ is 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 a lithium triazenide to a desired product represented by formula I, e.g., [(EtCp)2Y(tBu-N3-tBu)]. In this step, it is particularly advantageous to select an aprotic, nonpolar solvent, e.g., toluene. The lithium halide, particularly LiCl, produced as the sole by-product, can then be quantitatively or nearly quantitatively separated by an easily and rapidly performable filtration and / or decantation and / or centrifugation step. Following the removal of the solvent, the crude product is similarly easily and rapidly purified by distillation and / or sublimation.

[0024] The compound represented by formula I is 1 ¹H NMR spectroscopy typically yields a purity of at least 97%, favorably over 97%, and especially over 98% or 99%. This is based on the fact that, even after isolation and purification of each metal complex represented by Formula I, impurities may still be present due to volatile organic compounds, particularly due to organic solvents used as part of the synthesis. Empirically, this type of impurity is not decisive with respect to 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 relation to this invention, the terms “high purity” and “extremely pure” refer to a total content of impurities based on undesirable metals, undesirable metalloids, atmospheric oxygen, and water that is less than 1 ppm, ideally less than 100 ppb. In the semiconductor industry, this level of purity is called electronic grade. Potential impurities of the above types, namely based on volatile organic compounds, and especially based on organic solvents used as part of the synthesis, are not considered in this purity specification.

[0026] The yield of the metal complex represented by Formula I, as presented here, is generally 70% or higher. When this process is carried out on an industrial scale, the target compound can be obtained advantageously with comparable yield and purity.

[0027] It is remarkable that the metal complexes represented by formula I, as described herein, exist without solvent after a simple purification step, i.e., distillation or sublimation. In other words, the metal complexes represented by formula I, e.g., [(EtCp)Sc(tBu-N3-tBu)2] and [(EtCp)2Y(tBu-N3-tBu)], cannot be obtained in the form of solvent adducts and solvent adducts of these metal complexes, respectively. This is particularly advantageous in terms of the use of these metal complexes as precursors for producing high-purity metal layers or metal-containing layers by chemical vapor deposition processes. The fact that the metal complexes represented by formula I exist without solvent is remarkable, especially in the case of lanthanide cations, because the small ratio between charge and radius usually results in a high coordination number. General formula (R X -NC(R Y )=NR Z ) - The combination of two cyclopentadienide anions and one amidinate anion can adequately shield the coordination sphere of the Ln(III) cation (see Patent Document 1), but this cannot be expected, for example, for a ligand regime consisting of two cyclopentadienide anions and one triazenaide anion. This is because the triazenaide anion exhibits a relatively sharp bite angle, particularly compared to the amidinate anion.

[0028] The following is presented here [M(L C )(L T )(L Z )](I) type metal complexes are characterized by heteroreptic complex designs and have the general formula (R 1 -N3-R 2 ) -At least one triazenide ligand represented by is formed. The triazenide ligand skeleton is advantageously nitrogen-only, and the anionic N donor ligand skeleton has two alkyl R 1 and R 2 It is stabilized by the group. The nitrogen-containing skeleton clearly reduces the risk present as part of the chemical vapor deposition process, which is that a contaminated (especially carbon) and therefore substandard layer may be produced. Furthermore, the incorporation of desired elements into the produced layer, particularly nitrogen, is promoted, i.e., the incorporation rate of desired elements is improved. It has been found that this risk can be further reduced by the selection of two terminal alkyl groups. Therefore, when using the complex [(EtCp)2Sc(tBu-N3-tBu)] as a precursor material in the MOVPE process, [(MeCp)2Sc(R 1 -N3-R 2 )][where R 1 =R 2 Even lower carbon incorporation rates were observed compared to when using complexes with triazenide ligands that have lower steric requirements and fewer carbon atoms, such as [=Me, Et, or iPr].

[0029] The general formula presented here is [M(L C )(L T )(L Z A further important advantage of the complex type represented by (I) is that a variety of different, especially customized, precursors can be formed by very simple methods. This is because, on the one hand, the ligand regime is variable, i.e., a) cyclopentadienide ligand L C , triazenide ligand L T , and cyclopentadienide ligand L Z a) can form a cyclopentadienide ligand L C , triazenide ligand L T , and triazenide ligand L Z This is because it can form 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 It can be modified in various ways by changing the ligand regime. This is particularly advantageous in terms of the different process conditions to which the precursor material may be exposed, depending on the choice of deposition process, for example. Thus, each customized and application-specific optimized precursor can be modified with relatively little effort, i.e., simply by changing the ligand regime, as well as by changing the ligand regime L C , L T , and L Z This can be formed by changing the substitution pattern. Therefore, optimization can be performed for application in MOCVD processes, ALD processes, or MOVPE processes, for example. In this context, it should be noted that the synthetic routes outlined earlier can be advantageously followed essentially independently of the desired metal center atom and ligand regime. In other words, both the metal center atom and the ligand sphere of the metal center atom can be varied extensively, particularly by modifying the substitution patterns of cyclopentadienide ligands and triazenide ligands, without requiring any essential changes to the synthetic protocol. Rather, only minor changes to the synthetic protocol, if any, may be required, such as changes in solvent and / or temperature adjustments.

[0030] Furthermore, it is particularly advantageous that the metal complexes represented by formula I presented herein typically have relatively low melting temperatures, generally below 100°C, or below 95°C, or below 90°C, for example, about 80°C for [(MeCp)2Sc(tBu-N3-tBu)] or about 40°C for [(EtCp)2Y(tBu-N3-tBu)]. Additionally, metal complexes with molecular weights of less than 600 g / mol, preferably up to 595 g / mol, and especially less than 595 g / mol, can also be formed. Complexes represented by formula I [wherein M=Sc, Y, or Ti] may also 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. This, advantageously, combined with the low melting temperature, 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)2Sc(tBu-N3-tBu)] and [(EtCp)Sc(tBu-N3-tBu)2] (see Figures 1 and 2), revealed that the transition of these precursor compounds to the gas phase occurs at relatively low temperatures. The fact that this transition occurs without decomposition is particularly advantageous. Consequently, when the types of complexes presented here are used as precursors in the chemical vapor deposition process, the target decomposition of each precursor can be favorably achieved at relatively low process temperatures. Therefore, overall, better availability of the precursors in the gas phase is achieved, ultimately leading to an increase in the incorporation rate of the desired elements. Furthermore, the target decomposition at relatively low process temperatures favorably impacts layer growth. As a result, the fabricated layers are of high quality in terms of purity, composition, and morphology.

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

[0033] For example, an AlScN layer was fabricated using the complex [(EtCp)2Sc(tBu-N3-tBu)] as a precursor material in the MOVPE process. The AlScN layer was 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 100°C. Surprisingly, a sufficiently high precursor vapor pressure was observed even at the relatively low internal temperature of the bubbler within the aforementioned range. The molar flow rate within the generally selected range was achieved by setting the hydrogen flow rate (carrier gas) to be equivalent to the flow rate determined for the precursor. Layer growth rates within the expected range were achieved. Depending on the selected growth conditions in each case, particularly the selected substrate, bubbler internal temperature, and process temperature, the fabricated AlScN layer contained at least approximately 10 atoms of scandium; that is, the scandium incorporation rate was at least approximately 10 atoms. Consequently, the scandium content for the AlScN layer was at least equivalent to the value of approximately 10% recently reported by Streicher et al. (Phys.Status Solidi RRL 2023,17,2200387). This layer was actually obtained at a growth temperature of 900°C by an MOCVD process using bis(methylcyclopentadienyl)scandium chloride ([(MeCp)2ScCl]2).

[0034] Surprisingly, when using the complex [(EtCp)2Sc(tBu-N3-tBu)] presented here, it was found that the scandium incorporation rate was independent of the growth temperature, unlike in the case of the known precursor [(MeCp)2ScCl]2, which was also used by the inventors under the same process conditions.

[0035] The atomic composition of the proportion of AlScN layers manufactured in connection with 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 presented here is [M(L C )(L T )(L Z The metal complex represented by (I) can be described as being able to be produced in high purity, from good to very good yields, using simple methods, even on an industrial scale. Heteroreptic variable complex design, which forms at least one ligand having a nitrogen-based carbon-free skeleton (triazenide ligand), enables the formation of a variety of different metal complexes, each of which is advantageously customized and application-specific. [M(L C )(L T )(L Z The metal complexes of type (I) described herein satisfy all the requirements imposed on precursor materials for chemical vapor deposition processes, and are therefore particularly advantageous as their use in this type of process is predetermined. The complex design of the compounds represented by formula I is particularly advantageous as it brings about both the promotion of the incorporation of desired elements into the layer being produced and the reduction of the incorporation of undesirable elements such as carbon. Advantageously, the use of these complexes can be carried out at ideal process temperatures, thus enabling the production of high-quality metal layers and metal-containing layers. For example, the layers may contain or consist of lanthanide-containing III-V compound semiconductors or Ln oxides. Overall, from an (atomic) economic and environmental standpoint, the use of the types of complexes presented herein in chemical vapor deposition processes is particularly advantageous.

[0037] In the advantageous embodiments of the metal complex 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 It is selected from the group consisting of the following.

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

[0039] According to another embodiment of the metal complex presented herein, i. Monoanionic piedner 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, particularly from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, a monoalkyl-substituted cyclopentadienide anion. - 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, and 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 Polyalkyl-substituted cyclopentadienide anions represented by [at least two of the groups are not hydrogen (H)] To be selected from a group consisting of, and / or ii. Triazena 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. This is expected.

[0040] Also, monoanionic piedner ligand L C However, 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, particularly from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, except for R which is not hydrogen (H). B , R C , R D , R E , and R F It can be assumed that the polyalkyl-substituted cyclopentadienide anion is represented as [at least two of the groups are identical].

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

[0042] Furthermore, monoanionic piedner ligand L C However, 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, particularly from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, provided that R B , R C , R D , R E , and R F If exactly 2, 3, 4, or 5 of the group are not hydrogen (H), then favorably, R B , R C , R D , R E , and R F It can be assumed that the polyalkyl-substituted cyclopentadienide anion is represented by [exactly two or exactly five of the groups not being hydrogen (H)].

[0043] In this case, the piedner 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 - It is an anion selected from the group consisting of the following. Alternatively, the piedner ligand L C For example, Me4Cp - , or Me(Et)2Cp - , or Et2(iBu)Cp -, or Me5Cp - (Cp * ) is also acceptable.

[0044] According to further advantageous embodiments of the metal complex presented herein, ligand L Z However, it is a monoanionic piedner ligand, i. Monoanionic piedner ligand L C Alternatively, monoanionic piedner ligand L Z Selected or ii. Monoanionic piedner ligand L C and monoanionic piedner ligand L Z However, they are independent 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, particularly from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, a monoalkyl-substituted cyclopentadienide anion. - 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, and 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 Polyalkyl-substituted cyclopentadienide anions represented by [at least two of the groups are not hydrogen (H)] Being selected from a group consisting of This is expected.

[0045] In alternative or complementary embodiments, triazena 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.

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

[0047] Ligand L Z If it is a monoanionic piedner ligand, i. Monoanionic piedner ligand L C Alternatively, monoanionic piedner ligand L Z Selected or ii. Monoanionic piedner ligand L C and monoanionic piedner ligand L Z However, they are independent 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 each independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and isomers thereof, in particular from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, provided that at least two of the R B , R C , R D , R E and R F groups that are not hydrogen (H) are the same] polyalkyl-substituted cyclopentadienide anions represented by being selected from the group consisting of can also be envisaged.

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

[0049] Furthermore, i. a monoanionic pi-donor ligand L C or a monoanionic pi-donor ligand L Z is selected, or ii. the monoanionic pi-donor ligand L C and the monoanionic pi-donor ligand L Z are each independently of one another of the general formula R B R C R D R E R F Cp - wherein 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, particularly from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, provided that R B , R C , R D , R E , and R F If exactly 2, 3, 4, or 5 of the group are not hydrogen (H), then favorably, R B , R C , R D , R E , and R F Polyalkyl-substituted cyclopentadienide anions represented by [where exactly 2 or exactly 5 of the groups are not hydrogen (H)] Being selected from a group consisting of This is a possibility.

[0050] In this case, the piedner ligand L C and / or piedner 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 - Selected from the group consisting of the following: Alternatively, the piedner ligand L C and / or piedner ligand L Z For example, Me4Cp - , or Me(Et)2Cp - , or Et2(iBu)Cp - , or Me5Cp - (Cp * ) is also acceptable.

[0051] In yet another variant of the metal complex described here, L Z This is a monoanionic piedner ligand, and monoanionic piedner ligand L C and monoanionic piedner ligand L Z It is assumed that they are the same.

[0052] According to further advantageous embodiments of the metal complex presented herein, ligand L Z The general formula is (R 1 -N3-R 2 ) - [In the formula, triazena anion L Z R 1 and R 2 The triazenide anion is represented by [at least one of the groups being 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].

[0053] In another advantageous embodiment, ligand L Z However, the general formula (R 1 -N3-R 2 ) - [In the formula, triazena anion L Z R 1 base and R 2 The bases are independent of each other and triazena anion L T It is assumed that the triazenaide anion is represented independently of the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers, and is particularly selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

[0054] In further variants of the metal complex presented here, L Z The general formula is (R 1 -N3-R 2 ) - [In the formula, triazena anion L T and triazena anion L ZThis is a triazenoid anion represented as [identical].

[0055] According to yet another embodiment of the metal complex presented herein, i. Triazena anion L T R 1 base and R 2 The base is the same. and / or ii. L Z However, the general formula (R 1 -N3-R 2 ) - [In the formula, triazena anion L Z R 1 base and R 2 The base is a triazenaid anion represented as [identical]. This is expected.

[0056] In yet another advantageous embodiment of the metal complex described herein, the metal central atom M is selected from the group consisting of Sc, Y, La, Ce, Nd, Eu, Er, Lu, and Ti. A. Ligand L Z However, it is a monoanionic piedner ligand, i. Monoanionic piedner ligand L C Alternatively, monoanionic piedner ligand L Z Selected or ii. Monoanionic piedner ligand L C and monoanionic piedner ligand L Z However, they are independent 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, 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 The 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 Polyalkyl-substituted cyclopentadienide anions represented by [at least two of the groups are identical] Selected from the group consisting of, and Triazena anion L T R 1 base and R 2 The groups are independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. or B. Ligand L Z However, the general formula (R 1 -N3-R 2 ) - [In the formula, i. Two triazena 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. Triazena anion L T R 1 and R 2 The base, and triazena anion L Z R 1 and R 2Triazena anions represented by [each group independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl] And, and Monoanionic piedner 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, 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 The 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 Polyalkyl-substituted cyclopentadienide anions represented by [at least two of the groups are identical] Being selected from a group consisting of This is expected.

[0057] According to variant A, for example, piedner ligand L C and / or piedner ligand L Z However, Cp - (C5H5 -), MeCp - (MeC5H4 - ), EtCp - (EtC5H4 - ), iPrCp - (iPrC5H4 - ), iBuCp - (iBuC5H4 - ), sBuCp - (sBuC5H4 - ), tBuCp - (tBuC5H4 - ), Et2Cp - (Et2C5H3 - ), and Me5Cp - (Cp * , C5Me5 - ), it may be assumed that it is selected from the group consisting of the foregoing. Also, triazenido ligand L T is, for example, (Me-N3-Me) - , (iPr-N3-iPr) - , (iPr-N3-tBu) - , (tBu-N3-tBu) - , and (iBu-N3-iBu) - can be selected from the group consisting of the foregoing.

[0058] According to Variant B, triazenido ligand L T and / or triazenido ligand L Z is, for example, (Me-N3-Me) - , (iPr-N3-iPr) - , (iPr-N3-tBu) - , (tBu-N3-tBu) - , and (iBu-N3-iBu) - can be selected from the group consisting of the foregoing. Also, monoanionic pi-donor ligand L C is, for example, Cp - (C5H5 - ), MeCp - (MeC5H4 - ), EtCp - (EtC5H4 - ), iPrCp - (iPrC5H4 - ), iBuCp -(iBuC5H4 - ), sBuCp - (sBuC5H4 - ), tBuCp - (tBuC5H4 - ), Et2Cp - (Et2C5H3 - ), and Me5Cp - (Cp * , C5Me5 - Selected from the group consisting of ).

[0059] According to further embodiments of the metal complex described herein, the metal complex is a compound of 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] JPEG0007917733000002.jpg182130 It holds.

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

[0061] This is particularly advantageous because the uptake rate of each metal M increases, based on the fact that the metal complex transitions to the gas phase without decomposition. The uptake rate of nitrogen also increases. The resulting layers are of high quality in terms of their purity, composition, and morphology. Overall, this property of the metal complex has a particularly favorable impact on the (atomic)economic and ecological balance of the process. For further details on the advantages of the precursor compound transitioning to the gas phase without decomposition, please refer to the information above on this point.

[0062] According to further favorable alternative or complementary variants, the molecular weight of the metal complex is less than 600 g / mol, favorably up to 595 g / mol, and especially less than 595 g / mol.

[0063] In comparison, the two homoreptic Ln(III) triazenide complexes (Ln=La or Ce) described in Patent Document 2 each have a molecular weight of over 600 g / mol (approximately 608 g / mol).

[0064] The generally relatively small molecular weights of the metal complexes described herein, represented by Formula I, up to 595 g / mol and especially less than 595 g / mol, are advantageous in that they facilitate particularly (energy) efficient transfer of the metal complexes into the gas phase.

[0065] Metal complexes represented by formula I [wherein M = Sc, Y, or Ti] may have molecular weights less than 550 g / mol or less than 500 g / mol, for example, in the range of 350 g / mol to 550 g / mol. Therefore, in the case of the Y(III) compound shown earlier, represented by formula I.1, the molecular weight is between 400 g / mol and 450 g / mol, i.e., about 431 g / mol, and in the case of the Sc(III) complex shown earlier, represented by formula I.2, it is between 350 g / mol and 400 g / mol, i.e., about 360 g / mol.

[0066] Furthermore, this challenge is, i. Consists of at least one type of metal M, At least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium. or ii. Containing at least one type of metal M, At least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium. A layer is placed on the surface of a substrate, especially a semiconductor substrate. - General formula [M(L) described in one or more of the above embodiments C )(L T )(LZ )](I) represents at least one metal complex, or - General formula [M(L) described in one or more of the above embodiments C )(L T )(L Z A solution comprising at least one metal complex represented by (I) and an aprotic nonpolar solvent. This is solved by a method for manufacturing using [the specified method].

[0067] Therefore, this method involves the following steps: A. - Formation of at least one metal complex according to one or more of the embodiments described above, or - Formation of a solution comprising at least one metal complex and an aprotic nonpolar solvent as described in one or more of the above embodiments. and B. i. Composed of at least one type of metal M, or ii. Contains at least one type of metal M Deposition of layers onto the substrate surface 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) At least one metal complex of type [M(L C )(L T )(L Z The solution formed, which contains at least one metal complex represented by (I), is ( 1Based on the high purity of these metal complexes (at least 97%, preferably more than 97%, and especially more than 98% or 99%, as determined by 1H NMR spectroscopy), they are particularly well suited as precursor compounds or precursor compound-containing solutions for producing high-quality layers on the surface of a substrate. Thereafter, the layer consists 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. Also suitable for producing high-quality layers containing the aforementioned metal complex represented by general formula I, and solutions containing at least one such metal complex, are suitable.

[0069] In relation to this invention, the terms “high purity” and “extremely pure” refer to a total content of impurities based on undesirable metals, undesirable metalloids, atmospheric oxygen, and water that is less than 1 ppm, ideally less than 100 ppb. In the semiconductor industry, this level of purity is called electronic grade. Potential impurities based on volatile organic compounds, particularly organic solvents used as part of the synthesis, are not considered in this purity specification. With respect to this type of impurity, the purity of the metal complex represented by Formula I is typically at least 97%, favorably greater than 97%, and especially greater than 98% or 99%.

[0070] The deposition of each scandium layer, yttrium layer, lanthanide layer (lanthanide being, 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, such as a MOCVD process, a MOVPE process, or an ALD process.

[0071] For example, corundum foil or a thin metal foil can be used as the substrate. The substrate itself may be part of a component and / or may already have a semiconductor layer, such as 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 contain silicon, silicon carbide, germanium, gallium nitride, gallium arsenide, indium phosphide, glass such as SiO2, and / or synthetic materials such as silicon, or may consist entirely of one or more of these materials. Furthermore, the wafer may exhibit one or more wafer layers, each having a surface. The manufacture of a layer consisting of at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides being, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, or the manufacture of a layer containing at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides being, 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 an Ln2O3 layer, and may also be, for example, a layer containing a mixed oxide of two lanthanides or a layer consisting of a mixed oxide of two lanthanides.

[0073] Furthermore, this problem is apparent on the surface, i. Consists of at least one type of metal M, At least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium. or ii. Containing at least one type of metal M, At least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium. A substrate having at least one layer, A metal layer consisting of at least one metal M, or a layer containing at least one metal M, - General formula [M(L) described in one or more of the above embodiments C )(L T )(L Z )](I) represents at least one metal complex, or - General formula [M(L) described in one or more of the above embodiments C )(L T )(L Z A solution comprising at least one metal complex represented by (I) and an aprotic nonpolar solvent. Manufactured using This is solved by the circuit board.

[0074] The above [M(L C )(L T )(L Z )](I) At least one metal complex of type [M(L C )(L T )(L Z The solution used, comprising at least one metal complex represented by (I), is particularly well suited as a precursor compound or precursor compound-containing solution for producing a high-quality layer on the surface of a substrate, based on the high purity of these metal complexes.

[0075] The definition of the term "high purity" is given in relation to a method for manufacturing a layer consisting of at least one type of metal M or a layer containing at least one type of metal M on the surface of a substrate.

[0076] The deposition of each scandium layer, yttrium layer, lanthanide layer (lanthanide being, 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, such as a MOCVD process, a MOVPE process, or an ALD process.

[0077] The substrate may be, for example, corundum foil or a thin metal foil. The substrate itself may be part of a component and / or may already have 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 contain silicon, silicon carbide, germanium, gallium nitride, gallium arsenide, indium phosphide, glass such as SiO2, and / or synthetic materials such as silicon, or may consist entirely of one or more of these materials. Furthermore, the wafer may exhibit one or more wafer layers, each having a surface. The manufacture of a layer consisting of at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides being, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, or the manufacture of a layer containing at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides being, 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 an Ln2O3 layer, and may also be, for example, a layer containing a mixed oxide of two lanthanides or a layer consisting of a mixed oxide of two lanthanides.

[0079] Furthermore, this challenge is, - General formula [M(L) described in one or more of the above embodiments C )(L T )(L Z )](I) represents at least one metal complex, or - General formula [M(L) described in one or more of the above embodiments C )(L T )(L Z A solution comprising at least one metal complex represented by (I) and an aprotic nonpolar solvent. This is solved by methods for manufacturing electronic components, particularly electronic semiconductor components, using [the specified method].

[0080] Therefore, this method involves the following steps: A. - The general formula [M(L) C )(L T )(L Z Formation of at least one metal complex represented by (I), or - General formula [M(L) described in one or more of the above embodiments C )(L T )(L Z Formation of a solution comprising at least one metal complex represented by (I) and an aprotic nonpolar solvent, B. i. Composed of at least one type of metal M, or ii. Contains at least one type of metal M Deposition of layers onto the surface of the substrate, and C. Completion of electronic components, especially electronic semiconductor components. Includes.

[0081] Electronic components, particularly electronic semiconductor components, include, for example, detectors, optical elements, semiconductor diodes, lasers, electronic switching elements, and especially field-effect transistors or high-electron-mobility transistors or fiber optic emitters or fiber optic sensors.

[0082] The above [M(L C )(L T )(L Z )](I) At least one metal complex of type [M(L C )(L T )(L Z The solution used, comprising at least one metal complex represented by (I), is particularly well suited as a precursor compound or precursor compound-containing solution for producing a high-quality layer on the surface of a substrate, based on the high purity of these metal complexes.

[0083] The definition of the term "high purity" is given in relation to a method for manufacturing a layer consisting of at least one type of metal M or a layer containing at least one type of metal M on the surface of a substrate.

[0084] The deposition of each scandium layer, yttrium layer, lanthanide layer (lanthanide being, 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, such as a MOCVD process, a MOVPE process, or an ALD process.

[0085] The substrate may be, for example, corundum foil or a thin metal foil. The substrate itself may be part of a component and / or may already have 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 contain silicon, silicon carbide, germanium, gallium nitride, gallium arsenide, indium phosphide, glass such as SiO2, and / or synthetic materials such as silicon, or may consist entirely of one or more of these materials. Furthermore, the wafer may exhibit one or more wafer layers, each having a surface. The manufacture of a layer consisting of at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides being, for example, La, Ce, Nd, Eu, Er, or Lu), and titanium, or the manufacture of a layer containing at least one metal selected from the group consisting of scandium, yttrium, lanthanides (lanthanides being, 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 an Ln2O3 layer, and may also be, for example, a layer containing a mixed oxide of two lanthanides or a layer consisting of a mixed oxide of two lanthanides.

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

[0088] [Figure 1] This graph shows the TGA curve and SDTA curve (a curve from differential thermal analysis performed simultaneously with the TGA measurement; synchronous differential thermal analysis) of the metal complex [(EtCp)2Sc(dbt)], which is dbt = di-tert-butyltriazenide anion, prepared according to Example 3.1. [Figure 2] This graph shows the TGA and SDTA curves for the metal complex [(EtCp)Sc(dbt)2], which is a dbt = di-tert-butyltriazenide anion, prepared according to Example 4. [Figure 3] This graph shows the TGA and SDTA curves for the known complex [(MeCp)2ScCl]2. [Modes for carrying out the invention]

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

[0090] Figure 3 shows the TGA curve of the known precursor material [(MeCp)2ScCl]2 for comparison. This Sc(III) complex was prepared according to the procedure described in International Publication No. 2018 / 086730.

[0091] The x-axis plots the temperature in °C for both TGA and SDTA measurements in each case, with the relevant values ​​displayed above the x-axis.

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

[0093] From the TGA curves presented in Figures 1 and 2, it can be seen that both the Sc(III) complex [(EtCp)2Sc(dbt)] and the Sc(III) complex [(EtCp)Sc(dbt)2] are evaporable at low temperatures, i.e., around 200°C, without favorable decomposition. The low melting temperatures of these compounds can be read from their respective related SDTA curves: approximately 10°C for the complex [(EtCp)2Sc(dbt)] and approximately 45°C for the compound [(EtCp)Sc(dbt)2].

[0094] In contrast, the TGA curve shown in Figure 3 reveals that the known Sc(III) precursor [(MeCp)2ScCl]2 unfortunately does not evaporate without decomposing. The melting temperature of this known complex is approximately 160°C.

[0095] Based on the fact that the Sc(III) complexes [(EtCp)2Sc(dbt)] and [(EtCp)Sc(dbt)2] can be manufactured in high purity 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 designated as precursor materials for the production of high-quality scandium layers or scandium-containing layers, such as AlScN layers, on semiconductor substrates in the chemical vapor deposition (CVD) process. This has been confirmed, for example, by using the complex [(EtCp)2Sc(dbt)] in the MOVPE process. Information on this point has been previously described.

[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) and (iPrCp)(MeCp)Nd(dibt).

[0097] Therefore, 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 = dimethyltriazena anion, (Me-N3-Me) - dpt = diisopropyltriazena anion, (iPr-N3-iPr) - ;pbt=isopropyl-tert-butyltriazena anion, (iPr-N3-tBu) - dbt = di-tert-butyltriazena anion, (tBu-N3-tBu) - ;dibt=diisobutyltriazena anion (iBu-N3-iBu) - .

[0098] Substances and methods All reactions were carried out under a protective gas atmosphere using the standard Schlenk technique. The starting materials and solvents used had a purity of Pa.

[0099] All nuclear magnetic resonance spectroscopy measurements were performed using a Bruker AV II 300 type instrument. 1 1H NMR and 13 The 13C NMR spectrum was calibrated to the relevant residual proton signal of the solvent (C6D6) as an internal standard: 1 H: 7.16 ppm (s); 13 C: 128.0 ppm (tr). Chemical shifts are shown in ppm and refer to the delta scale. All signals are denoted by the following abbreviations depending on the splitting pattern of these signals: s (singlet), t (triplet), q (quartet), or m (multiplet). The bond between two atomic nuclei A and B via an n bond is in Hertz (Hz). n J AB It is expressed as a formal coupling constant.

[0100] Infrared spectrum measurements are typically performed using a Bruker Alpha ATR-IR spectrometer. Absorption bands are measured at wavenumber (cm²). -1 The spectrum is shown as follows, and the intensity is represented by the following abbreviations: w (weak), m (medium), s (strong). The spectrum is always normalized to the band with the strongest intensity.

[0101] Thermogravimetric analysis was performed using the Mettler Toledo TGA / DSC3+STAR system. Combined SDTA measurements were performed alongside each TGA measurement. Samples were measured in aluminum oxide, aluminum, or sapphire crucibles, depending on the method and aggregation state. Each sample was heated to its final temperature at a defined heating rate between 5 K / min and 25 K / min. The resulting spectra were evaluated 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 the mixture was stirred for 3 days after warming to room temperature. To the resulting colorless suspension, 50 mL of EtCpLi (56.3 mmol) solution in THF was added dropwise 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 suspension thus obtained 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. Then, 4.2 g of Li(dbt) (25.6 mmol) was added little by little. 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 was removed from the filtrate under vacuum, and the crude product was distilled under vacuum at 180°C. The product was obtained as a colorless oil, which slowly solidified into 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] 90.5 g of (EtCp)2YCl (291 mmol) in 600 mL of n-hexane was gradually added to 47.5 g of Li(dbt) (291 mmol) 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 its boiling point for 3 hours. The resulting suspension was filtered, and the filter cake was washed three times with 50 mL of n-hexane. The solvent was removed from the filtrate under vacuum, and the crude product was distilled under vacuum at 180°C. The product was obtained as a colorless oil that slowly solidified at room temperature. Yield: 78% (98 g; 227 mmol).

[0104] Melting temperature: approximately 40°C;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)2Sc(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. The filtrate was concentrated to a volume of approximately 30 mL and cooled to 0°C. Subsequently, 3.2 g of Li(dbt) (20 mmol) was added gradually. 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 was removed from the filtrate 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: Approximately 80°C (estimated value); 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 on Example 2: The synthesis of [(MeCp)2Sc(dbt)] can be carried out similarly to Example 1.2, starting from [(MeCp)2ScCl].

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

[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 gradually added at 0°C. After melting, the Li(dbt) was stirred at room temperature for 16 hours. The resulting suspension was heated to its boiling point for 3 hours, followed by thermal filtration. The solvent of the filtrate was removed by distillation. The residue was then distilled (under dynamic vacuum, i.e., approximately 1 * 10 -3 [(EtCp)2Sc(dbt)] was obtained in the form of a yellow oily substance by mbar (155°C). Yield: 73% (80g; 201 mmol).

[0110] Example 3.2: Preparation of [(EtCp)2Sc(dbt)] starting from [(EtCp)2ScCl] [ka] 70 g of [(EtCp)2ScCl](262 mmol) in 600 mL of n-hexane was gradually added to 42.8 g of Li(dbt)(262 mmol) 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 its boiling point for 3 hours. The resulting suspension was filtered, and the filter cake was washed three times with 50 mL of n-hexane. The solvent was removed from the filtrate under vacuum. The residue was distilled (under dynamic vacuum, i.e., approximately 1 * 10 -3 [(EtCp)2Sc(dbt)] was obtained in the form of a yellow oily substance by mbar (155°C). Yield: 81% (82g; 212 mmol).

[0111] Melting temperature: approximately 10°C; 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: [ScCl3 * Preparation of [(EtCp)Sc(dbt)2] starting from [3THF] [ka] 7.35g of [ScCl3 * 3THF (20 mmol) was suspended in 50 mL of THF. EtCpK (20 mmol) solution 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. 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 gradually. 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 was removed from the filtrate 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: approximately 45°C; 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 [Cp2Ti(pbt)] starting from [Cp2TiCl] [ka] To 10.68 g of [Cp2TiCl](50 mmol) in 150 mL of n-hexane, 7.46 g of Li(pbt)(50 mmol) is gradually added over 2 hours at 0°C. The reaction mixture is stirred at 0°C for 2 hours, and then stirred at room temperature for 16 hours. Subsequently, the reaction mixture is heated to its 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 is removed from the filtrate under vacuum. [(Cp)2Ti(pbt)] is obtained by distillation of the residue.

[0115] From the successful synthesis in Examples 1.2 and 3.2, it can be concluded that the reaction of [Cp2TiCl] with Li(pbt) yields the desired target compound [(Cp)2Ti(pbt)], similar to that in Examples 1.2 and 3.2.

[0116] According to Example 1.2, the compound [(EtCp)2Y(dbt)] was obtained starting from [(EtCp)2YCl] and Li(dbt). Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt) in comparable yield and purity to the complex [(EtCp)2Y(dbt)].

[0117] If the titanium(III) complex [Cp2TiCl] is reacted with Li(pbt) in a manner similar to Example 1.2 or Example 3.2, instead of [(EtCp)2YCl] or [(EtCp)2ScCl], then [(Cp)2Ti(pbt)] is obtained. This is because Ti 3+ Complex, Y 3+ Complexes, and Sc 3+ This is because complexes behave chemically in a similar manner.

[0118] The yield and purity of [(Cp)2Ti(pbt)] achieved by this example are the same as or identical to those obtained by the synthesis of [(EtCp)2Y(dbt)] (Example 1.2) and [(EtCp)2Sc(dbt)] (Example 3.2) described 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 gradually added over 2 hours at 0°C. The reaction mixture is stirred at 0°C for 2 hours, then stirred at room temperature for 16 hours. The reaction mixture is then heated to its 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 is removed from the filtrate under vacuum. [(iPrCp)(EtCp)Eu(dbt)] is obtained by distillation of the residue.

[0120] From the successful synthesis in Examples 1.2 and 3.2, it can be concluded that the reaction of [(iPrCp)(EtCp)EuCl] with Li(pbt) yields the desired target compound [(iPrCp)(EtCp)Eu(dbt)], similar to the reactions in Examples 1.2 and 3.2.

[0121] According to Example 1.2, the compound [(EtCp)2Y(dbt)] was obtained starting from [(EtCp)2YCl] and Li(dbt). Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt) in comparable yield and purity to the complex [(EtCp)2Y(dbt)].

[0122] If europium(III) complex [(iPrCp)(EtCp)EuCl] is reacted with Li(pbt) in a manner similar to Example 1.2 or Example 3.2, instead of [(EtCp)2YCl] or [(EtCp)2ScCl], then [(iPrCp)(EtCp)Eu(dbt)] is obtained. This is because the Eu intended as the starting material here 3+ Lanthanide(III) complexes such as complexes are Y 3+ Complex and Sc 3+ This is because it behaves chemically similarly to a complex.

[0123] The yield and purity of [(iPrCp)(EtCp)Eu(dbt)] achieved by this example are the same as or identical to the yield and purity obtained by the synthesis of [(EtCp)2Y(dbt)] (Example 1.2) and [(EtCp)2Sc(dbt)] (Example 3.2) described 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 gradually added over 2 hours at 0°C. 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 its 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 is removed from the filtrate under vacuum. [(iPrCp)Lu(dbt)2] is obtained by distillation of the residue.

[0125] From the successful synthesis in Examples 1.2 and 3.2, it can be concluded that the reaction of isopropylcyclopentadienyllutetium dichloride [(iPrCp)LuCl2] with Li(pbt) yields the desired target compound [(iPrCp)Lu(dbt)2], similar to Examples 1.2 and 3.2, but with a molar ratio of [(iPrCp)LuCl2]:Li(pbt) of 1:2.

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

[0127] Instead of [(EtCp)2YCl] or [(EtCp)2ScCl], the lutetium(III) complex [(iPrCp)LuCl2] is reacted with Li(pbt) in a manner similar to Example 1.2 or Example 3.2, but with a molar ratio of [(iPrCp)LuCl2]:Li(pbt) of 1:2 to obtain [(iPrCp)Lu(dbt)2]. This is because the Lu intended as the starting material here 3+ Lanthanide(III) complexes such as complexes are Y 3+ Complex and Sc 3+ This is because it behaves chemically similarly to a complex.

[0128] The yield and purity of [(iPrCp)Lu(dbt)2] achieved by this example are the same as or identical to those obtained by the synthesis of [(EtCp)2Y(dbt)] (Example 1.2) and [(EtCp)2Sc(dbt)] (Example 3.2) described above.

[0129] Example 8: Preparation of [(tBuCp)Er(dmt)(dpt)] starting from [(tBuCp)ErCl2] [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 gradually added over 2 hours at 0°C. Subsequently, 6.76 g of Li(dpt)(50 mmol) is gradually added over 2 hours at 0°C. The reaction mixture is stirred at 0°C for 2 hours, and then stirred at room temperature for 16 hours. The reaction mixture is then heated to its 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 is removed from the filtrate under vacuum. [(tBuCp)Er(dmt)(dpt)] is obtained by distillation of the residue.

[0130] From the successful synthesis in Examples 1.2 and 3.2, it can be concluded that the reaction of tert-butylcyclopentadienylerbium dichloride [(tBuCp)ErCl2] with lithium salts Li(dmt) and Li(dpt) yields the desired target compound [(tBuCp)Er(dmt)(dpt)], similar to Examples 1.2 and 3.2, but with a molar ratio of [(tBuCp)ErCl2]:lithium salt of 1:2.

[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 1:1. Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt) in comparable yield and purity to the complex [(EtCp)2Y(dbt)].

[0132] Instead of [(EtCp)2YCl] or [(EtCp)2ScCl], the erbium(III) complex [(tBuCp)ErCl2] is reacted with Li(dmt) and Li(dpt) in a manner similar to Example 1.2 or Example 3.2, provided that the molar ratio of [(tBuCp)ErCl2]:lithium salt is 1:2, to obtain [(tBuCp)Er(dmt)(dpt)]. This is because the Er intended as the starting material here is 3+ Lanthanide(III) complexes such as complexes are Y 3+ Complex and Sc 3+ This is because it behaves chemically similarly to a complex.

[0133] The yield and purity of [(tBuCp)Er(dmt)(dpt)] achieved by this example are the same as or identical to the yield and purity obtained by the synthesis of [(EtCp)2Y(dbt)] (Example 1.2) and [(EtCp)2Sc(dbt)] (Example 3.2) described 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 gradually added over 2 hours at 0°C. 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 its 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 is removed from the filtrate under vacuum. [(Et2Cp)La(dbt)2] is obtained by distillation of the residue.

[0135] From the successful synthesis in Examples 1.2 and 3.2, it can be concluded that the reaction of diethylcyclopentadienyllanthane dichloride [(Et2Cp)LaCl2] with the lithium salt Li(dbt) yields the desired target compound [(Et2Cp)La(dbt)2], similar to Examples 1.2 and 3.2, but with a molar ratio of [(Et2Cp)LaCl2]:lithium salt of 1:2.

[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 1:1. Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt) in comparable yield and purity to the complex [(EtCp)2Y(dbt)].

[0137] Instead of [(EtCp)2YCl] or [(EtCp)2ScCl], if the lanthanum(III) complex [(Et2Cp)LaCl2] is reacted with Li(dbt) in a manner similar to Example 1.2 or Example 3.2, but with a molar ratio of [(Et2Cp)LaCl2]:lithium salt of 1:2, then [(Et2Cp)La(dbt)2] is obtained. This is because the La(dbt) complex intended as the starting material here is 3+ Lanthanide(III) complexes such as complexes are Y 3+ Complex and Sc 3+ This is because it behaves chemically similarly to a complex.

[0138] The yield and purity of [(Et2Cp)La(dbt)2] achieved by this example are the same as or identical to those obtained by the synthesis of [(EtCp)2Y(dbt)] (Example 1.2) and [(EtCp)2Sc(dbt)] (Example 3.2) described above.

[0139] Example 10: [(Cp * Starting from )(MeCp)CeCl] [(Cp * 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 gradually added over a period of 2 hours at 0°C. The reaction mixture is stirred at 0°C for 2 hours, followed by 16 hours at room temperature. Then, the reaction mixture is heated to its 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 in the filtrate is removed under vacuum. By distillation of the residue, [(Cp * )(MeCp)Ce(dmt)] is obtained.

[0140] From the successful synthesis in Examples 1.2 and 3.2, [(Cp * The reaction of [(MeCp)CeCl] with Li(dmt) yields the desired target compound [(Cp * The conclusion is reached that (MeCp)Ce(dmt) is obtained.

[0141] According to Example 1.2, the compound [(EtCp)2Y(dbt)] was obtained starting from [(EtCp)2YCl] and Li(dbt). Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt) in comparable yield and purity to the complex [(EtCp)2Y(dbt)].

[0142] Instead of [(EtCp)2YCl] or [(EtCp)2ScCl], use the cerium(III) complex [(Cp * When reacting [(MeCp)CeCl] with Li(dmt) in a manner similar to Example 1.2 or Example 3.2, [(Cp * (MeCp)Ce(dmt) is obtained. This is because the Ce intended as the starting material here 3+ Lanthanide(III) complexes such as complexes are Y 3+ Complex and Sc 3+ This is because it behaves chemically similarly to a complex.

[0143] This embodiment achieves [(Cp * The yield and purity of [(EtCp)2Y(dbt)] (Example 1.2) and [(EtCp)2Sc(dbt)] (Example 3.2) are the same as or identical to the yield and purity obtained by the synthesis of [(EtCp)2Y(dbt)] (Example 3.2) described 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 gradually added over 2 hours at 0°C. 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 its 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 is removed from the filtrate under vacuum. [(iPrCp)(MeCp)Nd(dibt)] is obtained by distillation of the residue.

[0145] From the successful synthesis in Examples 1.2 and 3.2, it can be concluded that the reaction of [(iPrCp)(MeCp)NdCl] with Li(dibt) yields the desired target compound [(iPrCp)(MeCp)Nd(dibt)], similar to the reactions in Examples 1.2 and 3.2.

[0146] According to Example 1.2, the compound [(EtCp)2Y(dbt)] was obtained starting from [(EtCp)2YCl] and Li(dbt). Similarly, according to Example 3.2, the complex [(EtCp)2Sc(dbt)] was obtained starting from [(EtCp)2ScCl] and Li(dbt) in comparable yield and purity to the complex [(EtCp)2Y(dbt)].

[0147] If the neodymium(III) complex [(iPrCp)(MeCp)NdCl] is reacted with Li(dibt) in a manner similar to Example 1.2 or Example 3.2, instead of [(EtCp)2YCl] or [(EtCp)2ScCl], then [(iPrCp)(MeCp)Nd(dibt)] is obtained. This is because the Nd intended as the starting material here is 3+ Lanthanide(III) complexes such as complexes are Y 3+ Complex and Sc 3+ This is because it behaves chemically similarly to a complex.

[0148] The yield and purity of [(iPrCp)(MeCp)Nd(dibt)] achieved by this example are the same as or identical to the yield and purity obtained by the synthesis of [(EtCp)2Y(dbt)] (Example 1.2) and [(EtCp)2Sc(dbt)] (Example 3.2) described above.

[0149] The present invention is not limited to any one of the embodiments described above and is highly modifiable.

[0150] The present invention relates to the formula [M(L C )(L T )(L Z This indicates that the following applies to metal complexes represented by ): M = scandium, yttrium, lanthanide, or titanium; L C = Unsubstituted cyclopentadienide anions, monoalkyl-substituted or polyalkyl-substituted cyclopentadienide anions; L T = Triazena anion (R 1 -N3-R 2 ) - [In the formula, R 1 and R 2 [These are, independently of each other, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms];L Z a)L C Independent of L C Select from the group described, or b) L T Independent of L T The group is selected from those that describe the subject.

[0151] Furthermore, the subject of the present invention is the use of at least one such metal complex for manufacturing a layer on the surface of a substrate consisting of or containing at least one metal M, and for manufacturing electronic components. Moreover, the present invention relates to a substrate having a layer on its surface consisting of or containing at least one metal M, and manufactured using such a metal complex.

[0152] The general formula presented here is [M(L C )(L T )(L Z The metal complexes represented by (I) can be produced in high purity, from good to very good yields, using simple methods, even on an industrial scale. It is remarkable and advantageous that these compounds exist without solvent after isolation and purification by distillation or sublimation. It is particularly advantageous that heteroreptic variable complex designs, which form at least one ligand having a nitrogen-based carbon-free skeleton (triazenide ligand), allow for the formation of a variety of different metal complexes, each customized and application-specific. Thus, the synthesis protocols described herein can be advantageously customized, in principle, for specific processes of chemical vapor deposition, without significant modification [M(L] C )(L T )(L Z )](I) It can be applied to the production of type (I) compounds.

[0153] [M(L C )(L T )(L ZA further important advantage of the metal complexes of type (I) described herein is that these metal complexes meet all the requirements imposed on precursor materials for chemical vapor deposition processes (CVD processes), such as MOCVD processes, MOVPE processes, and ALD processes, and are therefore predetermined for use in this type of process in particular. The complex design of the compounds represented by formula I not only facilitates the incorporation of desired elements in a preferred form, i.e., each metal M and nitrogen into the layer being produced, but also results in a reduction of the incorporation of undesirable elements such as carbon. The use of these complexes can be advantageously carried out at ideal process temperatures, and thus high-quality metal layers and metal-containing layers can be produced. The layers produced are of high quality in terms of the purity of these layers, the composition of these layers, and the morphology of these layers. Overall, from an (atomic) economic and environmental standpoint, the use of the types of complexes presented herein in chemical vapor deposition processes is particularly advantageous.

[0154] All features and advantages derived from the claims, specification, and drawings, including structural details, spatial arrangement, and process steps, may be essential to the present invention, either individually or in a wide range 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 － Monoalkyl-substituted cyclopentadienide anions represented by the formula (wherein R Ａ (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 － polyalkyl-substituted cyclopentadienide anion represented by (in the formula, R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are each 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 piedner ligand selected from the group consisting of the following: iii. L Ｔ The general formula is (R １ -N ３ -R ２ ) － (In the formula, R １ and R ２ The groups are triazena anions (selected independently 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 piedner ligand L Ｃ Independently of that, - Unsubstituted cyclopentadienide anion (C ５ H ５ － ), - General formula R Ａ Cp － Monoalkyl-substituted cyclopentadienide anions represented by the formula (wherein R Ａ (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. However, the R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ (At least two of the groups are not hydrogen (H)) A monoanionic piedner ligand selected from the group consisting of, or b) General formula (R １ -N ３ -R ２ ) － The triazenide anion represented by the formula (where R １ and R ２ The bases are independent of each other and triazena anion L Ｔ (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] A metal complex represented by [the symbol].

2. The aforementioned lanthanide, 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 A metal complex according to claim 1, selected from the group consisting of the following.

3. i. The monoanionic piedner 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 [wherein the R Ａ The group is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers. - General formula R Ｂ R Ｃ R Ｄ R Ｅ R Ｆ Cp － A polyalkyl-substituted cyclopentadienide anion represented by the formula [wherein the 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, provided that 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. Triazena anion L Ｔ of the aforementioned 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. The metal complex according to claim 1 or 2.

4. The ligand L Ｚ but, a) Monoanionic piedner 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 [wherein the R Ａ The group is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers. - General formula R Ｂ R Ｃ R Ｄ R Ｅ R Ｆ Cp － polyalkyl-substituted cyclopentadienide anion represented by [in the formula, said R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are each independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, pentyl, and isomers thereof, with the proviso that at least two of said R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ groups are not hydrogen (H)] A monoanionic piedner 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 the triazenide anion L Ｚ of the aforementioned 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. The metal complex according to claim 1 or 2.

5. The following characteristics: i. The triazena anion L Ｔ of the aforementioned R １ base and the R ２ The groups are independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers. ii. The triazena anion L Ｔ of the aforementioned R １ base and the R ２ The base is the same. iii. L Ｚ The monoanionic piedner ligand L Ｃ and the monoanionic piedner ligand L Ｚ They are identical. iv. L Ｚ However, the general formula (R １ -N ３ -R ２ ) － A triazenide anion represented by the formula [wherein the triazenide anion L Ｚ of the aforementioned R １ base and the R ２ The groups are independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and their isomers. v. L Ｚ However, the general formula (R １ -N ３ -R ２ ) － A triazenide anion represented by the formula [wherein the triazenide anion L Ｚ of the aforementioned R １ base and the R ２ The base is the same. vi. L Ｚ However, the general formula (R １ -N ３ -R ２ ) － A triazenide anion represented by the formula [wherein the triazenide anion L Ｔ and the triazena anion L Ｚ [They are identical] A metal complex according to claim 1 or 2, exhibiting one or more of the following characteristics.

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 However, it is a monoanionic piedner ligand, i. The monoanionic piedner ligand L Ｃ Alternatively, the monoanionic piedner ligand L Ｚ Selected or ii. The monoanionic piedner ligand L Ｃ and the monoanionic piedner ligand L Ｚ However, they are independent of each other. - Unsubstituted cyclopentadienide anion (C ５ H ５ － ), - General formula R Ａ Cp － A monoalkyl-substituted cyclopentadienide anion represented by the formula [wherein the R Ａ 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 － A polyalkyl-substituted cyclopentadienide anion represented by the formula [wherein the R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ The group is independently selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, except that R is not hydrogen (H). Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ At least two of the elements are identical. Selected from the group consisting of, and The aforementioned triazena anion L Ｔ of the aforementioned R １ base and the R ２ The groups are independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. or B. The ligand L Ｚ However, the general formula (R １ -N ３ -R ２ ) － A triazena anion represented by the formula [wherein, i. Two of the triazena 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 triazena anion L Ｔ of the aforementioned R １ and R ２ The base, and the triazena anion L Ｚ of the aforementioned R １ and R ２ Each group is independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. And, and The monoanionic piedner 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 [wherein the R Ａ 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 － A polyalkyl-substituted cyclopentadienide anion represented by the formula [wherein the R Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ The group is independently selected from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, except that R is not hydrogen (H). Ｂ , R Ｃ , R Ｄ , R Ｅ , and R Ｆ At least two of the elements are identical. A metal complex according to claim 1 or 2, selected from the group consisting of the following.

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. The metal complex according to claim 1 or 2.

8. i. Consists of at least one type of metal M, The at least one metal M is selected from the group consisting of scandium, yttrium, lanthanides, and titanium. or ii. Containing at least one type of metal M, The aforementioned at least one metal M comprises a layer selected from the group consisting of scandium, yttrium, lanthanides, and titanium. On the surface of the substrate, - General formula [M(L)] as described in claim 1 or 2 Ｃ ) (L Ｔ ) (L Ｚ At least one metal complex represented by ) ] (I), or - General formula [M(L)] as described in claim 1 or 2 Ｃ ) (L Ｔ ) (L Ｚ A solution comprising at least one metal complex represented by (I) and an aprotic nonpolar solvent. A method for manufacturing using The following steps: A. - General formula [M(L)] as described in claim 1 or 2 Ｃ ) (L Ｔ ) (L Ｚ Formation of at least one metal complex represented by ) ] (I), or - General formula [M(L)] as described in claim 1 or 2 Ｃ ) (L Ｔ ) (L Ｚ Formation of a solution comprising at least one metal complex represented by (I) and an aprotic nonpolar solvent, and B. i. A material consisting of at least one type of metal M, or ii. Contains at least one type of metal M Deposition of the layer onto the surface of the substrate, using at least one metal complex formed in step A as a precursor compound. Methods that include...

9. - General formula [M(L)] as described in claim 1 or 2 Ｃ ) (L Ｔ ) (L Ｚ At least one metal complex represented by ) ] (I), or - General formula [M(L)] as described in claim 1 or 2 Ｃ ) (L Ｔ ) (L Ｚ A solution comprising at least one metal complex represented by (I) and an aprotic nonpolar solvent. A method for manufacturing electronic components using, The following steps: A. - The general formula [M(L)] described in any one of claims 1 to 7 Ｃ ) (L Ｔ ) (L Ｚ Formation of at least one metal complex represented by ) ] (I), or - The general formula [M(L)] described in any one of claims 1 to 7 Ｃ ) (L Ｔ ) (L Ｚ Formation of a solution comprising at least one metal complex represented by (I) and an aprotic nonpolar solvent, B. i. Made of at least one of the metals M, or ii. Deposition of the layer containing at least one metal M onto the surface of the substrate. and C. Completion of the aforementioned electronic components Methods that include...

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