Novel half-sandwich complexes of ruthenium

Abstract

The present invention relates to a half-sandwich complex of the formula η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3 and η 5 -C9H 7-p R1 p Ru(CO)2C m H 2m NR2R3, wherein in the formula, n = 0, 1, 2, 3, 4 or 5, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, the functional group R1 is independently selected from methyl group, ethyl group, propyl group, isopropyl group, and isomers of the butyl functional group, the functional groups R2 and R3 are independently selected from methyl group, ethyl group, propyl group, isopropyl group, and isomers of the butyl functional group.

Description

[Technical Field]

[0001] This invention relates to a novel ruthenium semi-sandwich complex that enables the deposition of a ruthenium thin layer or a ruthenium oxide layer as a ruthenium precursor on a substrate by CVD or ALD (CVD = chemical vapor deposition, ALD = atomic layer deposition). The novel semi-sandwich complex can also be used as a homogeneous catalyst.

[0002] According to the current definition, and in the context of this patent application, CVD is a method in which a vapor of a precursor is continuously supplied from a heated reservoir into a reactor space under negative pressure conditions (0.1 to 10 mbar), and a layer is formed on a heated contact surface of a substrate, such as the contact surface of a semiconductor substrate, by thermal decomposition at a temperature range of, for example, 200 to 800°C. This continuous layer growth process can be assisted by mixing co-reactants and / or by the inflow of an inert carrier gas such as nitrogen or argon.

[0003] According to the current definition, and in the context of this patent application, the ALD method is a method in which precursor vapor is sequentially pulsed from a heated reservoir under negative pressure conditions (0.01 to 10 mbar) to exchange with co-reactants in the reactor space. There, the contact surface of a substrate, such as a semiconductor substrate, heated to a temperature in the range of over 50°C to 300°C, then forms a layer by a self-controlled chemical reaction. Therefore, layer growth is not carried out continuously but periodically during the ALD process. This process can be assisted during each pulse by the inflow of an inert carrier gas such as nitrogen or argon.

[0004] Ruchi Gaur, Lallan Mishra, M. Aslam Siddiqi, and Burak Atakan (RSC Adv., 2014, 4, 33785-33805) provide an overview of ruthenium compounds that can be used for ruthenium layer deposition.

[0005] International Publication No. 2009 / 015270(A1) is for formula Cp(R) n We disclose a semi-sandwich complex of Ru(CO)2(X) (wherein R=C1-C10-alkyl, X=C1-C10-alkyl, and n=1, 2, 3, 4, or 5). International Publication No. 2009 / 015271(A1) discloses the use of such a semi-sandwich complex for depositing ruthenium films by ALD.

[0006] The object of the present invention was to provide ruthenium compounds having improved properties for use in producing ruthenium oxide layers or ruthenium layers by CVD or ALD methods, particularly for use in producing ruthenium layers by CVD or ALD methods in the field of semiconductor manufacturing. The ruthenium compounds found should have high volatility and thermal stability. In other words, they should be evaporable without decomposition at the lowest possible temperature, especially in the range of 50 to 150°C. In the case of CVD, these compounds are intended to be decomposed by heat treatment at temperatures above their boiling point, using co-reactants where applicable, or in the case of ALD, they are intended to form metallic ruthenium or a ruthenium oxide layer, usually by reaction with co-reactants under process pressure. During decomposition to form metallic ruthenium, they should be able to be rapidly deposited in the form of layers that are as pure as possible, containing no foreign atom contamination or only acceptablely small amounts of contamination (e.g., less than 3 atomic percent of carbon, oxygen, or nitrogen in each case). In the field of semiconductor manufacturing, this means that the purest possible ruthenium metal layer from the discovered ruthenium compounds is deposited on the semiconductor contact surface by CVD or ALD. Furthermore, the discovered ruthenium compounds should be liquid at room temperature, sufficiently stable in air and water, non-autoignitable, and as easily synthesized and purified as possible.

[0007] The present invention Equation η 5 -C5H 5-n R1n Ru(CO)2C m H 2m NR2R3 and η 5 -C9H 7-p R1 p Ru(CO)2C m H 2m A half-sandwich complex selected from the group consisting of compounds of NR2R3 is provided to achieve the object (wherein, n = 0, 1, 2, 3, 4 or 5, preferably 0 or 1, particularly 0, m = 1, 2, 3, 4 or 5, p = 0, 1, 2, 3, 4, 5, 6 or 7, preferably 0 or 1, particularly 0, The functional group R1 is independently selected from methyl group, ethyl group, propyl group, isopropyl group, and isomers of butyl functional group, The functional groups R2 and R3 are independently selected from methyl group, ethyl group, propyl group, isopropyl group, and isomers of butyl functional group).

[0008] As used herein, the term "isomers of butyl functional group" does not include any isomers of butyl functional group having an alicyclic structural unit.

[0009] The half-sandwich complex is preferably of the formula η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m Selected from the group consisting of compounds of NR2R3 (wherein n = 0, 1, 2, 3, 4 or 5, preferably 0 or 1, particularly 0, m = 1, 2, 3, 4 or 5, The functional group R1 is independently selected from methyl group, ethyl group, propyl group, isopropyl group, and isomers of butyl functional group, The functional groups R2 and R3 are independently selected from methyl group, ethyl group, propyl group, isopropyl group, and isomers of butyl functional group). A particularly preferred half-sandwich complex is of the formula η 5 -C5H5Ru(CO)2C m H2m It is of the form NR2R3 (wherein m = 1, 2, 3, 4, or 5, and the functional groups R2 and R3 are independently selected from methyl and ethyl). η 5 -C5H5Ru(CO)2C3H6N(CH3)2 and η 5 -C5H5Ru(CO)2C3H6N(CH2CH3)2, more precisely, η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2, that is, dicarbonyl (η 5 Cyclopentadienyl)(3-dimethylaminopropyl)ruthenium and η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2, that is, dicarbonyl (η 5 (-cyclopentadienyl)(3-diethylaminopropyl)ruthenium is particularly preferred.

[0010] The semi-sandwich complex according to the present invention can form dimers or oligomers. This process may be reversible.

[0011] The present invention also relates to a method for producing a semi-sandwich complex according to the present invention.

[0012] Equation η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3 and η 5 -C9H 7-p R1 p Ru(CO)2C m H 2m A first method for producing a semi-sandwich complex according to the present invention, selected from the group consisting of NR2R3 compounds, is: η 5 C5H 5-n R1 n Ru(CO)2Hal or η 5 -C9H 7-p R1 p Ru(CO)2Hal MC m H 2m NR2R3 type or Zn(C mH 2m NR2R3)2 type organometallic compounds, or Mg(C m H 2m This involves or is related to conversion with a Grignard compound of type NR2R3)X (wherein the formula, n = 0, 1, 2, 3, 4, or 5, preferably 0 or 1, particularly 0. m = 1, 2, 3, 4, or 5. p = 0, 1, 2, 3, 4, 5, 6, or 7, preferably 0 or 1, particularly 0. The functional group R1 is independently selected from isomers of the methyl, ethyl, propyl, isopropyl, and butyl functional groups. Functional groups R2 and R3 are independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Hal = Cl, Br, or I, preferably Cl. M = Li, Na, or K. X = Cl or Br)

[0013] Therefore, this method involves the following steps: (A1)η 5 -C5H 5-n R1 n Ru(CO)2Hal or η 5 -C9H 7-p R1 p Ru(CO)2Hal and MC m H 2m NR2R3 type or Zn(C m H 2m NR2R3)2 type organometallic compounds or Mg(C m H 2m The steps include providing a Grignard compound of type NR2R3)X, (A2) The η provided in step (A1) 5 -C5H 5-n R1 n A step to convert Ru(CO)2Hal, or η 5 -C9H 7-p R1 p MC provided with Ru(CO)2Hal in step (A1)m H 2m NR2R3 or Zn(C m H 2m NR2R3)2 or Mg(C m H 2m NR2R3)X is converted to η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3 or η 5 -C9H 7-p R1 p Ru(CO)2C m H 2m NR2R3 is formed, including.

[0014] The reaction occurring in step (A2) is η 5 -C5H 5-n [ R1 n Ru(CO)2C m H 2m An example of NR2R3 can be represented as follows: η 5 -C5H 5-n R1 n Ru(CO)2Hal + MC m H 2m NR2R3 → η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3 + MHal or 2η 5 -C5H 5-n R1 n Ru(CO)2Hal + Zn(C m H 2m NR2R3)2 → 2η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR-2R3 + ZnHal2 or η 5 -C5H 5-n R1 n Ru(CO)2Hal + Mg(Cm H 2m NR2R3)X→η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3+Mg(Hal)X.

[0015] The starting compounds mentioned in the three reaction equations above are: η 5 -C5H 5-n R1 n Ru(CO)2Hal can be prepared according to or similar to RJ Kulawiec, JW Faller, and RHCrabtree, Organometallics 1990, 9, 745, or S. Dev, JPSelegue, J. Organomet. Chem. 1994, 469, 107. η 5 -C5H 5-n R1 n The method for preparing Ru(CO)2Hal involves using commercially available tricarbonyldichlororuthenium(II) and η 5 -C5H 5-n R1 n Tl or η 5 -C5H 5-n R1 n This includes reactions with Si(CH3)3.

[0016] MC m H 2m NR2R3, Mg(C m H 2m NR2R3)X or Zn(C m H 2m The preparation of NR2R3)2 type organometallic starting materials requires no further explanation and is part of the standard knowledge of those skilled in the art, i.e., chemists. In this regard, HalC m H 2m NR2R3 is the corresponding commercially available hydrochloride HalC m H 2m N + HR2R3Cl -Therefore, it can be produced by reaction with a base such as KOH (see Example 2 described below).

[0017] It goes without saying that it is advantageous to carry out the work in steps (A1) and especially (A2) while excluding water and oxygen as much as possible. Step (A2) is conveniently carried out in an aprotic solvent. A suitable reaction temperature is, for example, in the range of 10°C to 70°C.

[0018] A preferred embodiment of the first method described above consists of a corresponding method for producing a half-sandwich complex according to the present invention, wherein these half-sandwich complexes are of formula: η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3, especially when n=0, In particular, η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 or η 5 Selected from the group consisting of compounds of the form -C5H5Ru(CO)2(CH2)3N(CH2CH3)2.

[0019] Equation η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3 and η 5 -C9H 7-p R1 p Ru(CO)2C m H 2m A second, and preferred, method for producing a semi-sandwich complex according to the present invention, selected from the group consisting of NR2R3 compounds, is: dimer [η 5 -C5H 5-n R1 n Ru(CO)2]2 or dimer [η 5 -C9H 7-p R1 p Ru(CO)2]2 is converted to HalC in the presence of reducing agent Y. m H 2mThis includes or involves the conversion using NR2R3 (in the formula, n = 0, 1, 2, 3, 4, or 5, preferably 0 or 1, particularly 0. m = 1, 2, 3, 4, or 5. p = 0, 1, 2, 3, 4, 5, 6, or 7, preferably 0 or 1, particularly 0. The functional group R1 is independently selected from isomers of the methyl, ethyl, propyl, isopropyl, and butyl functional groups. Functional groups R2 and R3 are independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Hal = Cl, Br, or I, preferably Cl. Y is selected from Li, Na, K, Mg, Ca, Zn, H2, hydrazine, NaK alloy, NaH, lithium naphthalide, sodium naphthalide, potassium naphthalide, NaBH4, and LiAlH4.

[0020] Therefore, this method is (B1)[η 5 -C5H 5-n R1 n Ru(CO)2]2 or [η 5 -C9H 7-p R1 p Ru(CO)2]2,HalC m H 2m Steps to provide NR2R3 and Y, (B2) Step (B1) provided [η 5 -C5H 5-n R1 n Ru(CO)2]2 or [η 5 -C9H 7-p R1 p Ru(CO)2]2 is converted to HalC provided in step (B1) in the presence of Y provided in step (B1). m H 2m React with NR2R3, η 5 -C5H 5-n R1 n Ru(CO)2C m H 2mNR2R3 or η 5 -C9H 7-p R1 p Ru(CO)2C m H 2m The process includes the step of forming NR2R3.

[0021] As a result, reducing agent Y reduces the carbon atom directly bonded to Hal.

[0022] This reaction used sodium as the reducing agent Y. η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m An example of formation can be shown below.

[0023] [η 5 -C5H 5-n R1 n Ru(CO)2]2 + 2HalC m H 2m NR2R3+2Na→ 2NaHa+2η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3.

[0024] Sodium naphthalide is used as the reducing agent Y. 5 -C5H 5-n R1 n Ru(CO)2C m H 2m In the example of NR2R3 formation, the reaction can be described as follows: [η 5 -C5H 5-n R1 n Ru(CO)2]2 + 2HalC m H 2m NR2R3+2C 10 H8Na→ 2NaHal+2C 10 H8+2η 5 -C5H 5-n R1 n Ru(CO)2Cm H 2m NR2R3.

[0025] The starting compound [η] mentioned in the two reaction equations above 5 -C5H 5-n R1 n Ru(CO)2]2 can be prepared according to or similar to Kai F. Kalz, Nicole Kindermann, Sheng-Qi Xiang, Andreas Kronz, Adam Lange, and Franc Meyer, Organometallics, 2014, 33, 1475-1479.

[0026] HalC m H 2m The above points apply to the preparation of NR2R3.

[0027] It goes without saying that it is advantageous for those skilled in the art to carry out the work in steps (B1) and especially (B2) while excluding water and oxygen as much as possible. Step (B2) is conveniently carried out in an aprotic solvent. Depending on the reducing agent Y selected, a suitable reaction temperature is, for example, in the range of -78 to 70°C.

[0028] A preferred embodiment of the second method described above is: Equation η 5 -C5H 5-n R1 n Ru(CO)2C m H 2m NR2R3, especially when n=0, η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 or η 5 The present invention comprises a corresponding method for producing a semi-sandwich complex selected from the group consisting of compounds of -C5H5Ru(CO)2(CH2)3N(CH2CH3)2.

[0029] The semi-sandwich complex according to the present invention achieves the objective described at the beginning. These can be used as homogeneous catalysts. In particular, they are outstandingly useful as precursors for producing ruthenium layers or ruthenium oxide layers on a substrate by CVD or ALD methods, especially as precursors for producing ruthenium layers in semiconductor manufacturing, i.e., ruthenium layers on the contact surface of a semiconductor substrate. These can be evaporated at atmospheric pressure in a temperature range of 50-150°C, or more precisely, without decomposition. Semi-sandwich complex η according to the present invention 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 and η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2 is particularly suitable for depositing high-purity ruthenium layers on the contact surface of semiconductor substrates by CVD or ALD methods.

[0030] The semi-sandwich complex according to the present invention is superior to the aforementioned compound known from International Publication No. 2009 / 015270(A1) that does not contain dialkylamino substituents with respect to the objective described at the beginning, and this is the semi-sandwich complex η according to the present invention 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 and η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2 is compound η described in International Publication No. 2009 / 015270(A1). 5 -As shown by comparison with C5H5Ru(CO)2(CH2CH3). From the thermogravimetric analysis of the compound (see Figure 5), the semi-sandwich complex and η according to the present invention 5 -C5H5Ru(CO)2(CH2CH3) can be evaporated in a particularly preferred temperature range of 50-150°C (start of downward curve). The mathematical derivatives of the functions obtained from thermogravimetric analysis of the analyzed compounds (see Figure 6) clearly show a single minimum value in each case of the semi-sandwich complex according to the present invention, thus indicating only thermal events attributable solely to the evaporation process. In contrast, η 5For -C5H5Ru(CO)2(CH2CH3), it is possible to observe two minimum values ​​located close to each other on the curve, and therefore two thermal events. These represent, on the one hand, the evaporation process, and on the other hand, an additional decomposition event. Thus, the semi-sandwich complex according to the present invention achieves the objective described at the beginning, by completely and undecomposed evaporable compounds η 5 -This is achieved in a superior manner than C5H5Ru(CO)2(CH2CH3). Such a decomposition process of the ruthenium precursor during evaporation can typically result in a low-quality layer when producing a ruthenium layer or ruthenium oxide layer by vapor deposition. As a result of the decomposition, not only the vaporized precursor molecules but also the decomposition products of the precursor are located in the gas space, which no longer follow the same deposition mechanism as the actual precursor molecules and can therefore increase the proportion of foreign atoms in the structured layer. Furthermore, the semi-sandwich complex according to the present invention ensures a more stable production process for ruthenium layers or ruthenium oxide layers by vapor deposition. Compound η 5 -C5H5Ru(CO)2(CH2CH3) decomposes during heating above its boiling point, and therefore its composition changes over time, but the composition of the semi-sandwich complex according to the present invention remains constant over time. Therefore, the process parameters selected at the start of the deposition process are effective over a long period of time without adaptation, but compound η 5 The process parameters of -C5H5Ru(CO)2(CH2CH3) require adaptation during the deposition process. [Examples]

[0031] All reactions and handling of compounds sensitive to air and moisture were carried out under a dry argon atmosphere (Air Liquide, 99.995% purity) using the standard Schlenk process. All solvents were dried (MBraun Solvent Purification System) and stored under an argon atmosphere via molecular sieves (4A). All vacuum operations (e.g., solvent removal, sublimation, vacuum distillation) were performed under 10 -1 ~10 -2The analysis was performed at a pressure of mbar. Sample preparation for analytical purposes was carried out in a glove box under an argon atmosphere. All commercially available chemicals were used without further purification.

[0032] Elemental C, H, and N analysis was performed using an Elementar CHNS analyzer, model Vario Mikro Cube. Ru content was measured after microwave decomposition using a Spectro ICP-OES analyzer, model Spectro Acros. Oxygen content was calculated by summing the measurement results for C, H, N, and Ru and taking the difference from 100.

[0033] A Bruker Avance III 400 NMR spectrometer was used for NMR spectral characterization. All spectra were analyzed using the internal solvent signal (C6D5H) and analyzed with MestReNova v.10.0.2-15465 software from Mestrelab Research SL.

[0034] The infrared spectrum was measured using a PerkinElmer FT-IR Spectrometer Two, placed inside an argon-filled glove box, with a PerkinElmer UATR Two ATR unit.

[0035] Thermogravimetric analysis was performed at atmospheric pressure and a heating rate of 5 K / min using a Netzsch STA 409 PC LUXX placed in a glove box filled with argon (sample size approximately 10 mg) (N2, flow rate = 300 mL / min).

[0036] Isothermal thermogravimetric measurements were performed in a Netzsch STA 409 PC LUXX crucible in a glove box filled with argon, at an N2 gas flow rate of 90 sccm. The weight in all three isothermal measurements was approximately 14 mg. After reaching the isothermal temperature (heating rate 10 K / min), the temperature was maintained constant. The evaporation rate was derived from the slope of a linear regression. The crucible surface area was 0.29706 cm² for a crucible diameter of 0.615 cm. 2 That is the case.

[0037] Example 1 (Preparation of the reducing agent sodium naphthalide): 1.6 g of naphthalene was dissolved in 50 mL of tetrahydrofuran (THF), and 288 mg of freshly cut sodium was added to the solution at room temperature. The mixture was stirred at room temperature for 20 hours and then used without further post-treatment.

[0038] Example 2 (Preparation of N,N-dimethylaminopropyl chloride): N,N-dimethylaminopropyl chloride hydrochloride [Cl(CH2)3N + H(CH3)2Cl - The mixture was mixed with 1.9 equivalents of KOH (powder, industrial grade) while being cooled in an ice bath, and stirred overnight. The resulting colorless oily substance was distilled under vacuum to obtain another 1.9 equivalents of KOH (pellets, industrial grade) (the distillation receiver was cooled with liquid nitrogen). The resulting distillate was distilled again under vacuum (the distillation receiver was cooled with liquid N2), and the resulting oily substance was used below without further purification.

[0039] Example 3 (Alternative Examples 3a and 3b): Example 3a of the present invention (Dicarbonyl(η) 5 (-cyclopentadienyl)(3-dimethylaminopropyl)ruthenium[η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 or η 5 - Prepare C5H5Ru(CO)2DMP with sodium naphthalide: Using a Schlenk tube, 1.0 g of [η] in 60 mL of THF 5To a solution of -C5H5Ru(CO)2]2 (prepared according to Kai F. Kalz, Nicole Kindermann, Sheng-Qi Xiang, Andreas Kronz, Adam Lange, and Franc Meyer (Organometallics, 2014, 33, 1475-1479)), 18.9 mL of the sodium naphthalide solution from Example 1 was added dropwise while stirring. The resulting mixture was stirred at room temperature for 4 hours. Then, 548 mg of N,N-dimethylaminopropyl chloride solution was added dropwise to 10 mL of THF. The reaction mixture was stirred at room temperature for 20 hours, the solvent was removed under reduced pressure, and the residue was extracted to diethyl ether (stirring time 5-20 hours). After removing the diethyl ether under vacuum, any naphthalene still present in the crude product was removed by sublimation (55°C) under vacuum. The residue was purified by vacuum distillation, and the product was obtained as an oil (yield approximately 30%).

[0040] Example 3b of the present invention (Dicarbonyl (η) 5 (-cyclopentadienyl)(3-dimethylaminopropyl)ruthenium[η 5 -C5H5Ru(CO)2(CH2)3N(CH3)2 or η 5 -C5H5Ru(CO)2DMP] is prepared using a Na / K alloy): 300 mg of potassium and 100 mg of sodium were weighed into a Schlenk tube and gently shaken to form a liquid Na / K alloy. The alloy was suspended in 20 mL of THF and 1.0 g of [η] was added. 5A solution of -C5H5Ru(CO)2]2 (prepared according to Kai F. Kalz, Nicole Kindermann, Sheng-Qi Xiang, Andreas Kronz, Adam Lange, and Franc Meyer (Organometallics, 2014, 33, 1475-1479)) was mixed with 40 mL of THF and stirred at room temperature for 20 hours. After removing the solvent under vacuum, the crude product was mixed with 60 mL of diethyl ether. The mixture was filtered and then mixed with 548 mg of N,N-dimethylaminopropyl chloride at room temperature and stirred again at room temperature for 20 hours. The reaction mixture was filtered again, and after removing the solvent under vacuum, the remaining dark red oily crude product was vacuum distilled at 65°C. The product was isolated as a yellowish oil in a yield of 710 mg (51%).

[0041] Elemental analysis: [Table 1]

[0042] 1 H-NMR (200MHz, C6D6): δ (ppm) = 4.55 (s, 5H), 2.30 (t, 2H), 2.20 (s, 6H), 1.84 (quint., 2H), 1.76 (t, 2H).

[0043] 13 C-NMR(50MHz,C6D6):δ(ppm)=203.4(2C,η 5 -C5H5Ru(CO)2C3H6N(CH3)2),88.8(5C, η 5 -C5H5Ru(CO)2C3H6N(CH3)2), 64.6(1C, η 5 -C5H5Ru(CO)2CH2CH2CH2N(CH3)2), 46.1(2C,η 5 -C5H5Ru(CO)2C3H6N(CH3)2), 38.2(1C,η 5 -C5H5Ru(CO)2CH2CH2CH2N(CH3)2), -5.7(1C,η 5-C5H5Ru(CO)2CH2CH2CH2N(CH3)2).

[0044] LIFDI-MS m / z):308.044=[M] +

[0045] Example 4 of the present invention (Dicarbonyl (η) 5 -Cyclopentadienyl)(3-diethylaminopropyl)ruthenium[η 5 -C5H5Ru(CO)2(CH2)3N(CH2CH3)2 or η 5 -C5H5Ru(CO)2DEP] is prepared using a Na / K alloy): The synthesis was carried out in the same manner as in Example 3b) using the following substances and their weights. 300 mg potassium 100 mg sodium 1.0g of [η 5 -C5H5Ru(CO)2]2 674 mg of N,N-diethylaminopropyl chloride After vacuum distillation at 75°C, 810 mg (54%) of the product was isolated as a yellow oily substance.

[0046] Elemental analysis: [Table 2]

[0047] 1 H-NMR (200MHz, C6D6): δ(ppm)=4.56(s,5H),2.52(m,4H+2H),1.87(m,2H),1.75(m,2H),1.05(t,6H).

[0048] 13 C-NMR(50MHz,C6D6):δ(ppm)=203.1(2C,η 5 -C5H5Ru(CO)2C3H6N(CH2CH3)2),88.6 (5C,η 5 -C5H5Ru(CO)2C3H6N(CH2CH3)2), 58.1(1C,η 5-C5H5Ru(CO)2CH2CH2CH2N(CH2CH3)2), 47.6(2C,η 5 -C5H5Ru(CO)2C3H6N(CH2CH3)2), 37.9(1C,η 5 -C5H5Ru(CO)2CH2CH2CH2N(CH2CH3)2), 12.6(2C,η 5 -C5H5Ru(CO)2C3H6N(CH2CH3)2), -5.7(1C,η 5 -C5H5Ru(CO)2CH2CH2CH2N(CH2CH3)2).

[0049] LIFDI-MSm / z):337.010=[M] +

[0050] Comparative Example 5 (Dicarbonyl (η) 5 -Cyclopentadienyl(ethyl)ruthenium, η 5 -C5H5Ru(CO)2(CH2CH3), η 5 -C5H5Ru(CO)2Et prepared with Na / K alloy): The synthesis was carried out in the same manner as in Example 3b) using the following substances and their weights. 300 mg potassium 100 mg sodium 1.0g of [η 5 -C5H5Ru(CO)2]2 491 mg of ethyl bromide After vacuum distillation at 65°C, the product was isolated as a yellow oily substance.

[0051] 1 H-NMR(200MHz,C6D6):δ(ppm)=4.53(s,5H),1.87(q,2H),1.52(t,3H)

[0052] 13 C-NMR 50MHz,C6D6:δ(ppm)=203.1(2C,η 5 -C5H5Ru(CO)2(CH2CH3)) 88.6(5C,η 5-C5H5Ru(CO)2(CH2CH3)),30.5(1C,η 5 -C5H5Ru(CO)2(CH2CH3)), -9.8(1C,η 5 -C5H5Ru(CO)2(CH2CH3)). [Brief explanation of the drawing]

[0053] [Figure 1] The ATR-IR spectrum of η5-C5H5Ru(CO)2(CH2)3N(CH3)2 is shown. [Figure 2] The results of the thermogravimetric analysis of η5-C5H5Ru(CO)2(CH2)3N(CH3)2 are shown. [Figure 3] The results of isothermal gravimetric analysis of η5-C5H5Ru(CO)2(CH2)3N(CH3)2 at 80°C, 100°C, and 120°C are shown, with evaporation rates of E80°C = 15.1 μg / min-1 / cm-2; E100°C = 54.5 μg / min-1 / cm-2; and E120°C = 176.1 μg / min-1 / cm-2. [Figure 4] The liquid implantation field desorption ionization (LIFDI) mass spectrum of η5-C5H5Ru(CO)2(CH2)3N(CH3)2 is shown. [Figure 5] The results of a comparative analysis of thermogravimetric analysis of η5-C5H5Ru(CO)2(CH2)3N(CH3)2, η5-C5H5Ru(CO)2(CH2)3N(CH2CH3)2, and η5-C5H5Ru(CO)2(CH2CH3) are shown. [Figure 6] The smoothed derivatives of the functions obtained from thermogravimetric analysis of η5-C5H5Ru(CO)2(CH2)3N(CH3)2, η5-C5H5Ru(CO)2(CH2)3N(CH2CH3)2, and η5-C5H5Ru(CO)2(CH2CH3) are shown.

Claims

1. Formula η ５ -C ５ H ５－ｎ R1 ｎ Ru(CO) ２ C ｍ H ２ｍ NR2R3 and η ５ -C ９ H ７－ｐ R1 ｐ Ru(CO) ２ C ｍ H ２ｍ A half-sandwich complex selected from the group consisting of compounds of NR2R3 and η, wherein in the formula n = 0, 1, 2, 3, 4, or 5, m = 1, 2, 3, 4, or 5. p = 0, 1, 2, 3, 4, 5, 6, or 7, Functional group R1 is independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. A semi-sandwich complex in which functional groups R2 and R3 are independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups.

2. During the ceremony, n = 0 or 1, m = 1, 2, 3, 4, or 5. Functional group R1 is independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Functional groups R2 and R3 are independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups, formula η ５ -C ５ H ５－ｎ R1 ｎ Ru(CO) ２ C ｍ H ２ｍ The semi-sandwich complex according to claim 1, selected from the group consisting of NR2R3 compounds.

3. The semi-sandwich complex according to claim 2, wherein n = 0, m = 1, 2, 3, 4, or 5, and functional groups R2 and R3 are independently selected from methyl and ethyl.

4. η ５ -C ５ H ５ Ru(CO) ２ (CH ２ ) ３ N(CH ３ ) ２ or η ５ -C ５ H ５ Ru(CO) ２ (CH ２ ) ３ N(CH ２ CH ３ ) ２ It is a semi-sandwich complex.

5. A semi-sandwich complex according to any one of claims 1 to 4, which is in the form of a dimer or oligomer.

6. η ５ -C ５ H ５－ｎ R1 ｎ Ru(CO) ２ Hal or η ５ -C ９ H ７－ｐ R1 ｐ Ru(CO) ２ Hal, MC ｍ H ２ｍ NR2R3 type or Zn(C ｍ H ２ｍ NR2R3) ２ Organometallic compounds of the type or Mg(C ｍ H ２ｍ This includes conversion with a Grignard compound of type NR2R3)X, in which, n = 0, 1, 2, 3, 4, or 5, m = 1, 2, 3, 4, or 5. p = 0, 1, 2, 3, 4, 5, 6, or 7, Functional group R1 is independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Functional groups R2 and R3 are independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Ha = Cl, Br, or I, preferably Cl. M = Li, Na, or K, A method for producing the half-sandwich complex according to claim 1, wherein X = Cl or Br.

7. η ５ -C ５ H ５－ｎ R1 ｎ Ru(CO) ２ Hal, MC ｍ H ２ｍ NR2R3 type or Zn(C ｍ H ２ｍ NR2R3) ２ Organometallic compounds of the type, or Mg(C ｍ H ２ｍ This includes conversion with a Grignard compound of type NR2R3)X, in the formula n = 0 or 1, m = 1, 2, 3, 4, or 5. Functional group R1 is independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Functional groups R2 and R3 are independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Ha = Cl, Br, or I, M = Li, Na, or K, A method for producing the half-sandwich complex according to claim 2, wherein X = Cl or Br.

8. The method according to claim 7, wherein n = 0, m = 1, 2, 3, 4, or 5, and functional groups R2 and R3 are independently selected from methyl and ethyl.

9. C ｍ H ２ｍ = (CH ２ ) ３ The method according to claim 8, wherein the functional groups R2 and R3 each represent methyl or ethyl.

10. dimer [η ５ -C ５ H ５－ｎ R1 ｎ Ru(CO) ２ ] ２ or dimer [η ５ -C ９ H ７－ｐ R1 ｐ Ru(CO) ２ ] ２ In the presence of reducing agent Y, HalC ｍ H ２ｍ This includes reacting with NR2R3, in the formula, n = 0, 1, 2, 3, 4, or 5, m = 1, 2, 3, 4, or 5. p = 0, 1, 2, 3, 4, 5, 6, or 7, Functional group R1 is independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Functional groups R2 and R3 are independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Ha = Cl, Br, or I, Y is Li, Na, K, Mg, Ca, Zn, H ２ Hydrazine, NaK alloy, NaH, lithium naphthalide, sodium naphthalide, potassium naphthalide, NaBH ４ and LiAlH ４ A method for producing the semi-sandwich complex according to claim 1, selected from the following.

11. Dimer [η ５ -C ５ H ５－ｎ R1 ｎ Ru(CO) ２ ２ is reacted with HalC ｍ H ２ｍ NR2R3 in the presence of reducing agent Y, wherein​ n = 0 or 1, m = 1, 2, 3, 4, or 5. Functional group R1 is independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups. Functional groups R2 and R3 are independently selected from isomers of methyl, ethyl, propyl, isopropyl, and butyl functional groups; Ha = Cl, Br, or I, Y is Li, Na, K, Mg, Ca, Zn, H ２ , hydrazine, NaK alloy, NaH, lithium naphthalide, sodium naphthalide, potassium naphthalide, NaBH ４ and LiAlH ４ A method for producing the half-sandwich complex according to claim 2, selected from

12. The method according to claim 11, wherein n = 0, m = 1, 2, 3, 4, or 5, and functional groups R2 and R3 are independently selected from methyl and ethyl.

13. C ｍ H ２ｍ = (CH ２ ) ３ The method according to claim 12, wherein the functional groups R2 and R3 each represent methyl or ethyl.

14. Use of a semi-sandwich complex according to any one of claims 1 to 5, or a semi-sandwich complex produced according to the method of any one of claims 6 to 13, as a precursor or homogeneous catalyst in a CVD or ALD process for producing a ruthenium layer or ruthenium oxide layer on a substrate.

15. The use according to claim 14 for manufacturing a ruthenium layer, wherein the substrate is a semiconductor substrate having one or more contact surfaces on which a ruthenium layer should be provided.

Images