Organometallic compounds for depositing high-purity tin oxide, as well as dry etching and deposition reactors for tin oxide films.

Abstract

Provided are an organometallic compound useful for deposition of high purity tin oxide, and a composition containing the compound. 【Solution means】Formula II: Sn(NR 2 (CH2) n A 2 )2 (wherein A 2 is NR 2’ or O; R 2 group is H and an alkyl group and an aryl group having 1 to 10 carbon atoms; R 2’ group is H and an alkyl group or an acyl group and an aryl group having 1 to 10 carbon atoms; n is 2 or 3; optionally, NR 2 (CH2) n NR 2’ forms a cyclic structure) of an organometallic compound is provided.

Description

[Technical Field]

[0001] This disclosure relates to organometallic compounds useful for the deposition of high-purity tin oxide, a dry etching method for dry etching such high-purity tin oxide films, and a deposition reactor used in tin oxide film deposition methods. More specifically, this disclosure describes certain compounds useful in the deposition of high-purity tin oxide, and compositions that provide better stability during storage for compounds useful in the deposition of high-purity tin oxide. This disclosure also describes a method for dry etching tin oxide with a specific etchant gas, and / or a method for dry etching a substrate using a specific etchant gas together with a specific additive. [Background technology]

[0002] The following “Background of the Invention” description refers to certain structures and / or methods. However, these references should not be construed as acknowledging that these structures and / or methods constitute prior art. The applicant expressly reserves the right to demonstrate that such structures and / or methods do not qualify as prior art.

[0003] In the semiconductor industry, tin oxide conformal films are increasingly being used in the fabrication of electronic devices. Such films can be fabricated using chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0004] To obtain the desired film, the reaction compounds used in the deposition process must be thermally stable while exhibiting good reactivity. Such properties allow for the delivery of the compounds to the deposition chamber without decomposition. Decomposition can result in uneven deposition or other defects in the deposited film. The good stability and reactivity profiles exhibited by the compounds of the present invention also mean that less material needs to be delivered to the growth chamber (less material is more economical), shorter cycle times (less material remains in the chamber and needs to be pumped out at the end of the process), and improved throughput because thicker films can be deposited in less time. Thermal stability also means that the material can be purified much more easily after synthesis and is easier to handle.

[0005] While several attempts have been made to discover compounds with the desired thermal stability and good reactivity, there is still a need for compounds with improved thermal stability and / or reactivity that can meet the growing requirements of the industry.

[0006] There is also a need to ensure the stability of reaction compounds during storage. Many reaction compounds used to form tin oxide films are known to undergo disproportionation or polymerization. This can cause problems if the reaction compounds are stored for a certain period before use in the deposition process. Therefore, it is necessary to reduce the effects of disproportionation and improve the storage stability of the reaction gases used in the deposition process to form tin oxide films.

[0007] In atomic layer deposition (ALD) systems, reactive gases are sequentially introduced to achieve the self-controlled growth of conformal thin films of the desired material. In both cases, the reactor is a chamber made of a material that does not react with the chemicals being used. The reactor also needs to withstand high temperatures. This chamber comprises a reactor wall, liner, base, gas injection unit, and temperature control unit. Typically, the reactor wall is made of aluminum, stainless steel, or quartz. Ceramics such as Al2O3, Y2O3, or other novel ceramics may also be used. Special glass, such as quartz, is often used as a liner between the reactor wall and the base in the reactor chamber. To prevent overheating, a coolant, such as water, can be circulated through channels within the reactor wall. The substrate rests on a base that is kept at a controlled temperature. The base is made of a material resistant to the metal-organic compounds used, and graphite may be used.

[0008] When thin film deposition is performed, the film is deposited not only on the desired surface but also on all internal surfaces of the MOCVD or ALD reactor, including the base, walls, and ceiling. The more frequently the reactor is used without cleaning, the thicker the deposit becomes. The deposit eventually begins to peel off, generating particles that can fall onto the substrate wafer, contaminating the wafer and resulting in reduced yield. The reaction gas flowing through the reactor chamber can also be contaminated by the deposit. To avoid this, the reactor must be cleaned regularly. Depending on the reactor configuration and the materials used, complete removal and wet cleaning of reactor components may be necessary for effective cleaning, but this is time-consuming and reduces the reactor's efficiency. Furthermore, reactors are typically composed of a wide range of materials, including 316L and 304 stainless steel, silicon carbide, graphite, tungsten, aluminum, pyrolysis boron nitride, other ceramics, and / or ethylene propylene diene (EPDN) polymers. Removing deposits from all these types of surfaces without using various types of etchants or other cleaning agents can be difficult. Therefore, simpler and more effective means of cleaning the inside of the reactor are desired.

[0009] Furthermore, thin-film manufacturing methods often include an etching step after deposition. At least some of the deposits on the chamber walls are the same material that is etched from the thin film.

[0010] ALD reactors for the fabrication of single wafers containing tin oxide (SnO2) present specific problems in the etching and cleaning of the reaction chamber. For example, such reactors may require the use of highly corrosive Cl or Br-based chemicals, which cause degradation of the chamber material, induce material stress, corrode the substrate material of the ALD chamber, and / or require chamber shields or inserts to protect the chamber walls. When cleaning ALD reactors for tin oxide, using H2, CH4, or other reducing chemicals requires longer etching times and results in byproducts condensing on the reactor surface before exhaust. The use of CH4 may also result in solid tin oxide containing Me-Sn-O, which is known to be more toxic than Sn-O residue. Because the byproducts in the case of tin oxide are prone to low-temperature decomposition, temperature control below -10 to -30°C is required, complicating the tool configuration. Also, the reducing atmosphere may reduce the metal oxide to metal, which can then act as a passivation layer.

[0011] US20040014327A1 “Method for etching high The book "Dielectric Constant Materials and for Cleaning Deposition Chambers for High Dielectric Constant Materials" teaches that metal oxides can be etched using another etchant, COCl2. However, COCl2 is a highly toxic nerve agent. The use of malonyl chloride as an etchant should also be possible, but malonyl chloride is very unstable and decomposes into a liquid at room temperature, making it difficult to obtain in sufficiently high purity, and thus difficult to transport and store for long periods. Therefore, an etchant that solves the above problems is needed. [Overview of the Initiative] [Problems that the invention aims to solve]

[0012] The present disclosure provides compounds useful for the deposition of high purity tin oxide.

Means for Solving the Problems

[0013] The organometallic compound has the following formula I: Q x -Sn-(A 1 R 1 ’ z ) 4-x Formula I (wherein, Q is OR 1 or Cp, each R 1 group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms, each R 1 ’ group is independently selected from the group consisting of alkyl, acyl or aryl groups having 1 to 10 carbon atoms, x is an integer from 0 to 3, when x is 0, A is O, and when x is an integer from 1 to 3, A is N, when A is O, z is 1, and when A is N, z is 2) and includes compounds of.

[0014] The deposition of tin oxide using such compounds is also disclosed. By using the compounds of formula I in the methods disclosed herein, chemical vapor deposition (CVD) and atomic layer deposition (ALD) of tin oxide are made possible.

[0015] In embodiments, Q is Cp, a cyclopentadienyl ligand. In some embodiments, x is 1, and the compound of formula I has the following formula: Cp-Sn-(NR 1 ’2)3 (wherein each R 1 ’ group is independently selected from the group consisting of alkyl, acyl or aryl groups having 1 to 10 carbon atoms).

[0016] In embodiments, x is an integer from 1 to 3. In such embodiments, the compound of formula I has the following formula: (OR 1 )x -Sn-(NR 1 '2) 4-x (In the formula, each R 1 The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having 1 to 10 carbon atoms, and x is an integer from 1 to 3.

[0017] In other embodiments, each R 1 Base and each R 1 The group is an alkyl group having 1 to 10 carbon atoms, independently selected. 1 Base and each R 1 The group is intended to be an independently selected alkyl group having 1 to 6 carbon atoms. In embodiments, each R 1 Base and each R 1 The group is an alkyl group having 1 to 4 carbon atoms, independently selected. In embodiments, each R 1 Base and each R 1 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In embodiments, each R 1 Base and each R 1 The group represents a different alkyl, acyl, or aryl group, especially a different alkyl group.

[0018] In this embodiment, x is 4. In such an embodiment, the compound of formula I is the following: Sn(OR 1 )4(in the formula, each R 1 The group is represented by an alkyl, acyl, or aryl group having 1 to 10 carbon atoms, which is independently selected from the group.

[0019] In other embodiments, each R 1 The group is an alkyl group having 1 to 10 carbon atoms, independently selected. 1 The group is intended to be an independently selected alkyl group having 1 to 6 carbon atoms. In embodiments, each R 1The group is an alkyl group having 1 to 4 carbon atoms, independently selected. In embodiments, each R 1 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In embodiments, each R 1 The group represents a different alkyl, acyl, or aryl group, especially a different alkyl group.

[0020] In the embodiment, the organometallic compound is selected from the group consisting of (MeO)2Sn(NMe2)2, (MeO)2Sn(NEtMe)2, (MeO)3Sn(NMe2), (MeO)3Sn(NEtMe), Sn(OMe)4, CpSn(NMe2)3, and CpSn(NMeEt)3.

[0021] Other organometallic compounds are given by the following formula II: Sn(NR 2 (CH2) n A 2 )2 type II (In the formula, Each A 2 , NR 2 'or selected independently of O, Each R 2 The group is independently selected from the group consisting of hydrogen and alkyl or aryl groups having 1 to 10 carbon atoms. Each R 2 The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having hydrogen and 1 to 10 carbon atoms. n is either 2 or 3. Depending on the circumstances, NR 2 (CH2) n NR 2 ' forms a ring structure, In some cases, at least one of the (CH2) groups has one or more substitutions with an alkyl group having 1 to 10 carbon atoms. It contains the compound.

[0022] The deposition of tin oxide using such compounds is also disclosed. The use of the compound of formula II in the methods disclosed herein enables chemical vapor deposition (CVD) and atomic layer deposition (ALD) of tin oxide.

[0023] In an embodiment, A 2 is O, and equation II is equation IIa: Sn(NR 2 (CH2) n O)2(in the formula, each R 2 The group is independently selected from alkyl or aryl groups having 1 to 10 carbon atoms, or selected from alkyl groups having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms). In embodiments, each R 2 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl.

[0024] In the embodiment, each R 2 The group is independently selected from alkyl groups having 1 to 10 carbon atoms. 2 The group is intended to be an independently selected alkyl group having 1 to 6 carbon atoms. In embodiments, each R 2 The group is an alkyl group having 1 to 4 carbon atoms, independently selected. In embodiments, each R 2 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In embodiments, each R 2 The group represents a different alkyl, acyl, or aryl group, particularly a different alkyl group.

[0025] In the embodiment, each R 2 The group is independently selected from hydrogen or alkyl groups having 1 to 10 carbon atoms. 2 The group is intended to be independently selected from hydrogen or alkyl groups having 1 to 6 carbon atoms. In embodiments, each R 2The group is independently selected from hydrogen or alkyl groups having 1 to 4 carbon atoms. In embodiments, each R 2 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In embodiments, each R 2 The group represents hydrogen or a different alkyl, acyl, or aryl group, especially a different alkyl group.

[0026] In one embodiment, n is 2. In another embodiment, n is 3. In the embodiment, at least one of the (CH2) is an alkyl group having 1 to 10 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms. It has multiple substitutions, or one or more substitutions are methyl or ethyl. In certain embodiments, only one of the (CH2) groups has one or more substitutions with alkyl groups such as methyl or ethyl. In more detailed embodiments, one of the (CH2) groups is substituted with two methyl groups.

[0027] In this embodiment, Formula II is, Equation IIb:

[0028] [ka]

[0029] (In the formula, Each R 2 The group is independently selected from the group consisting of hydrogen and alkyl or aryl groups having 1 to 10 carbon atoms. Each R 2 The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having hydrogen and 1 to 10 carbon atoms. Each R 2 '' group and each R 2 The group is an alkyl group having 1 to 10 carbon atoms, selected independently. It is represented as follows.

[0030] In this embodiment, each R in formula IIb 2 , R 2 ', R 2 '', or R 2 The group is independently selected from hydrogen or alkyl groups having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. In a particular embodiment of formula IIb, each R 2 and R 2 ' is hydrogen, and each R 2 '' and R 2 The ''' group is an alkyl group having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, independently selected. In a more detailed embodiment of formula IIb, each R 2 and R 2 ' is hydrogen, and each R 2 '' and R 2 The group is independently selected from ethyl or methyl.

[0031] A 2 NR 2 In some embodiments, NR(CH2) n NR 2 ' forms a ring structure. In a particular embodiment of the ring structure, R 2 and R 2 The group is an alkyl group selected from methyl or ethyl. In embodiments, formula II is formula IIc:

[0032] [ka]

[0033] #1 Formula IIc: It is represented as follows.

[0034] In the mechanism, each (NR 2 (CH2) n A 2) is selected from the group consisting of N,N'-dimethylethylenediamine (NMe(CH2)2NMe), piperazine (N2C4H8), N,N'-diethylethylenediamine (NEt(CH2)2NEt), N,N'-diisopropylethylenediamine (NiPr(CH2)2NiPr), N,N'-di-tert-butylethylenediamine (NtBu(CH2)2NtBu), N,N'-dimethyl-1,3-propanediamine (NMe(CH2)3NMe), 2,2-dimethyl-1,3-propanediamine (NH(CH2)(C(CH3))(CH2)NH), 2-(methylamino)ethanol (NMe(CH2)2O), and 2-(ethylamino)ethanol (NEt(CH2)2O).

[0035] The present disclosure provides a composition that combines a second organometallic compound with a first organometallic compound to reduce the disproportionation of the first organometallic compound and enhance storage stability.

[0036] The composition comprises Formula III: R 3 2Sn(NR 3 ’2)2 Formula III (wherein each R 3 group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms, each R 3 ’ group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms) a first organometallic compound represented by, and Formula IV: Sn(NR 4 2)4 Formula IV (wherein each R 4 group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms) a second organometallic compound represented by.

[0037] In other embodiments, each R 3 , R 3 ’, and R 4The radical is an alkyl group having from 1 to 10 carbon atoms, independently selected. Each R 3 and R 3 ’, and R 4 groups are contemplated to be independently selected alkyl groups having from 1 to 6 carbon atoms. In embodiments, each R 3 and R 3 ’ and R 4 groups are independently selected alkyl groups having from 1 to 4 carbon atoms. In embodiments, each R 3 and R 3 ’ and R 4 groups are independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, tert-butyl, iso-butyl, and n-butyl. In embodiments, each R 3 and R 3 ’ and R 4 groups represent different alkyl, acyl, or aryl groups, particularly different alkyl groups.

[0038] In embodiments, the second organometallic compound is selected from the group consisting of Sn(NMe2)4, Sn(NEt2)4, and Sn(NMeEt)4.

[0039] The present disclosure provides a novel etching method that solves the above problems in conventional methods of etching and cleaning an ALD reactor, particularly an ALD reactor in tin oxide production.

[0040] One way to solve the above problems is a method for removing tin oxide deposits from the inner surface of the reactor chamber or from a substrate within the reactor chamber, comprising introducing an etchant gas into the reactor chamber, the etchant gas having the general formula A 3 O m X n (where A 3 is selected from the group consisting of C, N, and S, O is oxygen, each X is independently selected from the group consisting of halogens, and the subscripts m and nThe compound is greater than zero, process, A step of activating the etchant gas, either before or after the introduction. The process of carrying out an etching reaction between the activated etchant gas and the tin oxide deposit, and The process of exhausting the etchant gas along with the gaseous products of the etching reaction. Includes methods.

[0041] Another method for solving the above-mentioned problem is a method for removing deposits from the inner surface of a reactor chamber or from a substrate inside the reactor chamber, The process involves introducing an etchant gas and an additive into the reactor chamber, wherein the etchant gas is of general formula A 3 O m X n (In the formula, A 3 X is selected from the group consisting of C, N, and S, O is oxygen, and each X is independently selected from the group consisting of halogens, and is a subscript. m and n The additive is a compound (where is greater than zero), and the additive is of the general formula C x H y O z (In formulas, subscripts) x and z The process is one in which (is greater than zero) A step of activating the etchant gas, either before or after the introduction. A step of carrying out an etching reaction between the activated etchant gas and the deposit, and The process of exhausting the etchant gas along with the gaseous products of the etching reaction. Includes methods.

[0042] In one embodiment according to any of the above methods, X represents a combination of two different halogens.

[0043] In one embodiment according to any of the above methods, the generation of the etchant gas is performed before its introduction into the chamber.

[0044] In one embodiment of any of the above methods, blowing a carrier gas into the liquid chemical component to volatilize the liquid chemical component into the etchant is performed before introducing the etchant gas into the chamber.

[0045] In one embodiment of any of the above methods, the etchant gas is obtained by blowing a carrier gas into a plurality of liquid chemical components and then combining the resulting gases. It is generated.

[0046] In one embodiment of any of the above methods, the etchant gas is produced by mixing two or more chemical component gases.

[0047] In one embodiment according to any of the above methods, the etchant gas is activated by exposure to an activation mechanism in a gas activation chamber before being introduced into the chamber, the gas activation mechanism being selected from the group consisting of heat, ultraviolet light, and plasma discharge.

[0048] In one embodiment according to any of the above methods, the etchant gas is activated by exposure to a thermal activation mechanism after being introduced into the chamber, the thermal activation mechanism being selected from the group consisting of the overall temperature in the chamber and a local heat source in the chamber.

[0049] In one embodiment of any of the above methods, the etchant gas is selected from the group consisting of COCl2, COBr2, COI2, SOI2, SOCl2, SOBr2, SO2Cl2, SO2Br2, NOCl, NOBr, NOI, SOClBr, SOClF, and SOFBr. In a particular embodiment, thionyl chloride (SOCl2) is used.

[0050] In one embodiment according to any of the above methods, the additive is CO or CO2.

[0051] In one embodiment according to any of the above methods, a halogen-containing additive is added to the gaseous mixture containing the etchant gas.

[0052] In one embodiment according to any of the above methods, the halogen-containing additive is an active halogen or a general formula R 5 X 1 (In the formula, R 5 X is selected from the group consisting of H and Me, 1 It is a compound of a halogen selected from the group consisting of F, Cl, Br, and I.

[0053] In one embodiment according to any of the above methods, the active halogen includes Cl or Br.

[0054] In one embodiment according to any of the above methods, a dilution additive is added to the gaseous mixture containing the etchant gas.

[0055] In one embodiment of any of the above methods, the dilution additive comprises N, Ar, He, or Ne.

[0056] In one embodiment of any of the above methods, the reactor chamber is heated to a temperature of at least 100°C, between 100°C and 900°C, or between 100°C and 400°C.

[0057] In one embodiment according to any of the above methods, the reactor chamber is provided with a pressure between 0.1 mBar and 1,500 mBar, preferably between 0.1 mBar and 1,000 mBar.

[0058] The above-mentioned and other features of the present invention, as well as the advantages of the present invention, will become more apparent in light of the following detailed description of preferred embodiments, as shown in the accompanying figures. As will be understood, the present invention can be modified in various ways without departing from the present invention. Therefore, drawings and descriptions should be considered illustrative in nature and not restrictive.

[0059] Next, embodiments of the present invention will be described as examples with reference to the accompanying drawings. [Brief explanation of the drawing]

[0060] [Figure 1] This is a comparative graph of the vapor pressures of several compounds that can be used to form tin oxide films. [Figure 2] This graph shows the mass percentage of Me2Sn(NMe2)2 as a percentage of the number of days at a storage temperature of 70°C. [Figure 3] This is a photograph of the test specimen obtained after the test according to Example 21. [Figure 4] This is a graph showing the etching rate (A / min) against power (W) in the implementation according to Example 22. [Figure 5] This graph shows the etching rate (A / min) against power (W) in the implementation according to Example 22, where the temperature was 26°C. [Figure 6] This figure shows the 1H NMR spectrum of Sn(NMeEt)4. [Figure 7] This figure shows the 1H NMR spectrum of Sn(OtBu)4. [Figure 8] This figure shows the 1H NMR spectra of Sn(NMeEt)4 before and after the addition of MeOH. [Figure 9] This graph compares the mass percentage of Sn(NMeEt)4 relative to the number of weeks at a storage temperature of 60°C with that of HNMeEt. [Figure 10]This figure shows the 1H NMR spectra of Sn(NMeEt)4 samples at 60°C at weeks 0, 4, and 9. [Figure 11] This graph compares the mass percentage of Sn(NMeEt)4 relative to the number of weeks at a storage temperature of 100°C with that of HNMeEt. [Figure 12] This figure shows the 1H NMR spectra of Sn(NMeEt)4 samples at 100°C during weeks 0, 4, and 9. [Figure 13] This figure shows the 1H NMR spectra of Sn(NMeEt)4 samples at 125°C during weeks 0, 1, and 2. [Figure 14] This figure shows a schematic diagram of a multi-stage vacuum distillation apparatus. [Modes for carrying out the invention]

[0061] The following detailed explanation can be read in conjunction with the attached diagrams, where similar figures represent similar elements.

[0062] The following equation I: Q x -Sn-(A 1 R 1 ' z ) 4-x Equation I (In the formula, Q is OR 1 or Cp, Each R 1 The group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms. Each R 1 The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having 1 to 10 carbon atoms. x is an integer from 1 to 4. If x is 0, A 1 The expression is O, and when x is an integer from 1 to 3, A 1 is N, A 1 If O, then z is 1, and A 1 If z is N, then z is 2. The organometallic compounds are disclosed.

[0063] In some embodiments, Q is a cyclopentadienyl ligand Cp. In some embodiments, x is 1, and the compound of formula I is the following: Cp-Sn-(NR 1 ' 2)3 (in the formula, each R 1 The group is represented as an alkyl, acyl, or aryl group having 1 to 10 carbon atoms, independently selected from that group.

[0064] The compounds of formula I include compounds where x is an integer from 1 to 3. In such embodiments, the compounds of formula I are defined as follows: (OR 1 ) x -Sn-(NR 1 '2) 4-x (In the formula, each R 1 The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having 1 to 10 carbon atoms, and x is an integer from 1 to 3.

[0065] Expression: (OR 1 ) x -Sn-(NR 1 '2) 4-x The compound represented by formula I is each R 1 Base and each R 1 The compound comprises a group in which the group is an alkyl group having 1 to 10 carbon atoms, independently selected. 1 Base and each R 1 The group is intended to be an independently selected alkyl group having 1 to 6 carbon atoms. In particular, each R 1 Base and each R 1 The group is an alkyl group having 1 to 4 carbon atoms, selected independently. More specifically, each R 1 Base and each R 1 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In addition, in some compounds, each R 1 Base and each R 1The group may represent a different alkyl, acyl, or aryl group, particularly a different alkyl group.

[0066] The compounds of formula I include compounds where x is 4. In such embodiments, the compounds of formula I are defined as follows: Sn(OR 1 )4(in the formula, each R 1 The group is represented by an alkyl, acyl, or aryl group having 1 to 10 carbon atoms, which is independently selected from the group.

[0067] Formula: Sn(OR 1 The compound of formula I represented by )4 is each R 1 The compound comprises a group in which the group is an alkyl group having 1 to 10 carbon atoms, independently selected. 1 The group is intended to be an independently selected alkyl group having 1 to 6 carbon atoms. In particular, each R 1 The group is an alkyl group having 1 to 4 carbon atoms, selected independently. More specifically, each R 1 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In addition, in some compounds, each R 1 The group represents a different alkyl, acyl, or aryl group, particularly a different alkyl group.

[0068] The specific organometallic compounds of formula I include: (MeO)2Sn(NMe2)2, (MeO)2Sn(NEtMe)2, (MeO)3Sn(NMe2), (MeO)3Sn(NEtMe), Sn(OMe)4, CpSn(NMe2)3, or CpSn(NMeEt)3.

[0069] Other organometallic compounds are given by the following formula II: Sn(NR 2 (CH2) n A 2 )2 type II (In the formula, Each A 2 , NR 2 'or selected independently of O, Each R2 The group is independently selected from the group consisting of hydrogen and alkyl or aryl groups having 1 to 10 carbon atoms. Each R 2 The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having hydrogen and 1 to 10 carbon atoms. n is either 2 or 3. Depending on the circumstances, NR 2 (CH2) n NR 2 ' forms a ring structure, In some cases, at least one of the (CH2) groups has one or more substitutions with an alkyl group having 1 to 10 carbon atoms. It contains the compound.

[0070] The deposition of tin oxide using such compounds is also disclosed. The use of the compound of formula II in the methods disclosed herein enables chemical vapor deposition (CVD) and atomic layer deposition (ALD) of tin oxide.

[0071] In an embodiment, A 2 is O, and equation II is equation IIa: Sn(NR 2 (CH2) n O)2(in the formula, each R 2 The group is independently selected from alkyl or aryl groups having 1 to 10 carbon atoms, or selected from alkyl groups having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms). In embodiments, each R 2 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl.

[0072] In the embodiment, each R 2 The group is independently selected from alkyl groups having 1 to 10 carbon atoms. 2 The group is intended to be an independently selected alkyl group having 1 to 6 carbon atoms. In embodiments, each R 2The group is an alkyl group having 1 to 4 carbon atoms, independently selected. In embodiments, each R 2 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In embodiments, each R 2 The group represents a different alkyl, acyl, or aryl group, particularly a different alkyl group.

[0073] In the embodiment, each R 2 The group is independently selected from hydrogen or alkyl groups having 1 to 10 carbon atoms. 2 The group is intended to be independently selected from hydrogen or alkyl groups having 1 to 6 carbon atoms. In embodiments, each R 2 The group is independently selected from hydrogen or alkyl groups having 1 to 4 carbon atoms. In embodiments, each R 2 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In embodiments, each R 2 The group represents hydrogen or a different alkyl, acyl, or aryl group, especially a different alkyl group.

[0074] In one embodiment, n is 2. In another embodiment, n is 3. In embodiments, at least one of the (CH2) groups has one or more substitutions with alkyl groups having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Alternatively, one or more substitutions are methyl or ethyl. In certain embodiments, only one of the (CH2) groups has one or more substitutions with alkyl groups such as methyl or ethyl. In more detailed embodiments, one of the (CH2) groups is substituted with two methyl groups.

[0075] In this embodiment, Formula II is, Equation IIb:

[0076] [ka]

[0077] (In the formula, Each R 2 The group is independently selected from the group consisting of hydrogen and alkyl or aryl groups having 1 to 10 carbon atoms. Each R 2 The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having hydrogen and 1 to 10 carbon atoms. Each R 2 '' group and each R 2 The group is an alkyl group having 1 to 10 carbon atoms, selected independently. It is represented as follows.

[0078] In this embodiment, each R in formula IIb 2 , R 2 ', R 2 '', or R 2 The group is independently selected from hydrogen or alkyl groups having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. In a particular embodiment of formula IIb, each R 2 and R 2 ' is hydrogen, and each R 2 '' and R 2 The ''' group is an alkyl group having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, independently selected. In a more detailed embodiment of formula IIb, each R 2 and R 2 ' is hydrogen, and each R 2 '' and R 2 The group is independently selected from ethyl or methyl.

[0079] A 2 In some embodiments where N is NR(CH2) n NR' forms a cyclic structure. In certain embodiments of the cyclic structure, the R and R' groups are alkyl groups selected from methyl or ethyl. In embodiments, formula II is formula IIc: Formula IIc:

[0080] [ka]

[0081] It is represented as follows. In the mechanism, each (NR 2 (CH2) n A 2 The substance is selected from the group consisting of N,N'-dimethylethylenediamine (NMe(CH2)2NMe), piperazine (N2C4H8), N,N'-diethylethylenediamine (NEt(CH2)2NEt), N,N'-diisopropylethylenediamine (NiPr(CH2)2NiPr), N,N'-di-tert-butylethylenediamine (NtBu(CH2)2NtBu), N,N'-dimethyl-1,3-propanediamine (NMe(CH2)3NMe), 2,2-dimethyl-1,3-propanediamine (NH(CH2)(C(CH3))(CH2)NH), 2-(methylamino)ethanol (NMe(CH2)2O), and 2-(ethylamino)ethanol (NEt(CH2)2O).

[0082] The compounds of formulas I and II exhibit good reactivity while being thermally stable; therefore, The compounds should be delivered to the deposition chamber without decomposition (decomposition would result in an unevenly deposited film or defects in the deposited film). The good stability and reactivity profiles exhibited by the compounds of the present invention are also expected to reduce the amount of material that needs to be delivered to the growth chamber (less material is more economical), shorten cycle times (because less material remains in the chamber and needs to be pumped out at the end of the process), and improve throughput as thicker films can be deposited in less time. Furthermore, ALD is expected to be possible to carry out at much lower temperatures (or using a wider temperature range) using compounds of formula I or II. Thermal stability also means that the purification of the material after synthesis will be much easier and easier to handle.

[0083] Compounds of formulas I and II have an additional advantage over conventional compounds: the absence of a C-Sn bond. The presence of a C-Sn bond leads to the formation of a Me-Sn-O solid residue, which is known to be more toxic than the residue formed from compounds of formulas I and II. Furthermore, although compounds of formulas I and II have smaller molecular weights than conventional compounds, they are still expected to exhibit higher thermal stability than those conventional compounds.

[0084] Compounds of formula I or II can be prepared by methods known in the art. The following examples illustrate, but are not intended to limit, such methods. [Examples]

[0085] Example 1: Synthesis of Sn(NMeEt)4 Under an inert atmosphere, 67 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L round-bottom flask. The contents of the flask were cooled in an ice / water bath, and then 16 mL of HNMeEt was added dropwise to the reaction flask with vigorous stirring. The reaction mixture was stirred at room temperature for 1 hour, and then cooled again in an ice / water bath. 44.90 mL of SnCl was added dropwise to the reaction flask using a dropper. The reaction flask was covered with aluminum foil, and its contents were left to stir overnight at room temperature. The next day, the LiCl salt was separated from the reaction mixture by filtration. 48.42 g of Sn(NMeEt) (57% yield) was isolated by distillation at 0.05 Torr at 70°C. As shown in Figure 6, 1 ¹H NMR spectroscopy confirmed that the product was Sn(NMeEt)4. [Examples]

[0086] Example 2: Synthesis of Sn(OtBu)4 Under an inert atmosphere, 100 g of SnCl4 and approximately 400 mL of anhydrous hexane were placed in a 1 L round-bottom flask. The contents of the flask were cooled in an ice / water bath, and then 16.6 mL of HNEt2 in 100 mL of anhydrous hexane was slowly added to the reaction flask. The reaction mixture was then stirred at room temperature for 2 hours, and then cooled again in an ice / water bath. Next, a solution of 15.4 mL of tBuOH in approximately 50 mL of anhydrous hexane was added to the flask, and the reaction mixture was left to stir at room temperature overnight. The following day, H2NEt2 was extracted by filtration. + Cl - The salt was separated from the reaction mixture. The solvent was removed from the filtrate by vacuum distillation. As shown in Figure 7, 1 ¹H NMR spectroscopy confirmed that the remaining yellow residue (8g, 38% yield) was Sn(OtBu)4. [Examples]

[0087] Example 3: Synthesis of Sn(OiPr)4 Under an inert atmosphere, 49 g of iPrOH and approximately 400 mL of anhydrous benzene were placed in a 1 L reactor. The contents of the reactor were cooled to 0°C, and 450 g of SnCl was slowly added to the reactor using a dropper. Then, while vigorously stirring, HNMe2 gas was added to the reaction mixture. The reaction mixture was refluxed for 1 hour during the addition of HNMe2. The reaction mixture was left agitated overnight at room temperature. The next day, H2NMe2 was extracted by filtration. + Cl - The salt was separated from the reaction mixture. The solvent was removed from the filtrate by vacuum distillation, leaving the final product. [Examples]

[0088] Example 4: Synthesis of Sn(OEt)4 Under an inert atmosphere, 100 g of SnCl and approximately 400 mL of anhydrous hexane may be placed in a 1 L round-bottom flask. The contents of the flask may be cooled in an ice / water bath, and then 16.6 mL of HNEt2 in 100 mL of anhydrous hexane may be slowly added to the reaction flask. The reaction mixture may then be stirred at room temperature for 2 hours, and then cooled again in an ice / water bath. Next, a solution of 15.4 mL of EtOH in approximately 50 mL of anhydrous hexane may be added to the flask, and the reaction mixture may be stirred overnight at room temperature. The following day, H2NEt2 may be obtained by filtration. + Cl - The salt may be separated from the reaction mixture. The solvent may be removed from the filtrate by vacuum distillation. [Examples]

[0089] Example 5: Synthesis of Sn(OMe)4 Under an inert atmosphere, 100 g of SnCl and approximately 400 mL of anhydrous hexane may be placed in a 1 L round-bottom flask. The contents of the flask may be cooled in an ice / water bath, and then 16.6 mL of HNEt2 in 100 mL of anhydrous hexane may be slowly added to the reaction flask. The reaction mixture may then be stirred at room temperature for 2 hours, and then cooled again in an ice / water bath. Next, a solution of 15.4 mL of MeOH in approximately 50 mL of anhydrous hexane may be added to the flask, and the reaction mixture may be stirred overnight at room temperature. The following day, H2NEt2 may be obtained by filtration. + Cl - The salt may be separated from the reaction mixture. The solvent may be removed from the filtrate by vacuum distillation. [Examples]

[0090] Example 6: Synthesis of (MeO)3Sn(NMeEt) Under an inert atmosphere, 25 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L reactor. The contents of the reactor were cooled to 0°C, and 3.8 g of HNMeEt was added to the solution in approximately 100 mL of anhydrous hexane while vigorously stirring. The reaction mixture was then stirred at room temperature for 1 hour, and then cooled again to 0°C. 415.3 g of Sn(OMe) in approximately 200 mL of anhydrous benzene was added dropwise to the reaction mixture. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiOMe salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0091] Example 7: Synthesis of (EtO)2Sn(NMe2)2 Under an inert atmosphere, 50 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L reactor. The contents of the reactor were cooled to 0°C, and HNMe2 gas was passed through the solution for 30 minutes while vigorously stirring. The reaction mixture was then stirred at room temperature for 1 hour, and then cooled again to 0°C. Sn(OEt)4 in approximately 200 mL of anhydrous benzene 18.8 g was added dropwise to the reaction mixture. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiOEt salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0092] Example 8: Synthesis of (EtO)3Sn(NMe2) Under an inert atmosphere, 25 mL of 2.5 M nBuLi solution in hexane is placed in a 1 L reactor. Approximately 500 mL of anhydrous hexane was loaded. The contents of the reactor were cooled to 0°C, and HNMe2 gas was passed through the solution for 30 minutes while vigorously stirring. The reaction mixture was then stirred at room temperature for 1 hour, and then cooled again to 0°C. Approximately 200 mL of anhydrous benzene contained Sn(OEt)4 18.8 g was added dropwise to the reaction mixture. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiOEt salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0093] Example 9: Synthesis of (EtO)2Sn(NMeEt)2 Under an inert atmosphere, 50 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L reactor. The contents of the reactor were cooled to 0°C, and 7.5 g of HNMeEt was added to the solution in approximately 100 mL of anhydrous hexane while vigorously stirring. The reaction mixture was then stirred at room temperature for 1 hour, and then cooled again to 0°C. 418.8 g of Sn(OEt) in approximately 200 mL of anhydrous benzene was added dropwise to the reaction mixture. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiOEt salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0094] Example 10: Synthesis of (EtO)3Sn(NMeEt) Under an inert atmosphere, 25 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L reactor. The contents of the reactor were cooled to 0°C, and 3.8 g of HNMeEt was added to the solution in approximately 100 mL of anhydrous hexane while vigorously stirring. The reaction mixture was then stirred at room temperature for 1 hour, and then cooled again to 0°C. 418.8 g of Sn(OEt) in approximately 200 mL of anhydrous benzene was added dropwise to the reaction mixture. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiOEt salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0095] Example 11: Synthesis of CpSn(NMe2)3 The dicyclopentadiene dimer was decomposed using fractional distillation, and the prepared Cp-H was used on the same day. In a glove box, 450.0 g of Sn(NMe2) and approximately 400 mL of anhydrous hexane were loaded into a 1 L round-bottom flask. Using a double manifold, 11.0 g of Cp-H was added to the reaction flask, and the reaction mixture was refluxed with stirring for 3 hours. The solvent was removed under vacuum, and the final material was isolated by vacuum distillation. [Examples]

[0096] Example 12: Synthesis of CpSn(NMeEt)3 The dicyclopentadiene dimer was decomposed using fractional distillation, and the prepared Cp-H was used on the same day. In a glove box, Sn(NMeEt)4 was added to a 1 L round-bottom flask. 50.0 g of the compound and approximately 400 mL of anhydrous hexane were loaded. Using a double manifold, 9.3 g of Cp-H was added to the reaction flask, and the reaction mixture was refluxed for 3 hours with stirring. The solvent was removed under vacuum, and the final material was isolated by vacuum distillation. [Examples]

[0097] Example 13: Synthesis of Sn(NMeCH2CH2NMe)2 Under an inert atmosphere, 62 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L reactor. The contents of the reactor were cooled to 0°C, and 7.11 g of NHMeCH2CH2NHMe was added to the solution while vigorously stirring. Subsequently, The reaction mixture was stirred at room temperature for 1 hour, then cooled again to 0°C. 10.0 g of SnCl4 was added dropwise to the reaction mixture in approximately 200 mL of anhydrous hexane. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiCl salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0098] Example 14: Synthesis of Sn(N2C4H8)2 Under an inert atmosphere, 62 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L reactor. The contents of the reactor were cooled to 0°C, and 6.94 g of piperazine was added to the solution while vigorously stirring. The reaction mixture was then stirred at room temperature for 1 hour, and then cooled again to 0°C. 10.0 g of SnCl4 in approximately 200 mL of anhydrous hexane was added dropwise to the reaction mixture. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiCl salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0099] Example 15: Synthesis of Sn(MeNCH2CH2CH2NMe)2 Under an inert atmosphere, 62 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L reactor. The contents of the reactor were cooled to 0°C, and 8.24 g of NHMeCH2CH2CH2NHMe was added to the solution while vigorously stirring. The reaction mixture was then stirred at room temperature for 1 hour, and then cooled again to 0°C. 10.0 g of SnCl4 in approximately 200 mL of anhydrous hexane was added dropwise to the reaction mixture. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiCl salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0100] Example 16: Synthesis of Sn(MeNCH2CH2O)2 Under an inert atmosphere, 62 mL of 2.5 M nBuLi solution in hexane and approximately 500 mL of anhydrous hexane were loaded into a 1 L reactor. The contents of the reactor were cooled to 0°C, and 6.05 g of NHMeCH2CH2OH was added to the solution while vigorously stirring. The reaction mixture was then stirred at room temperature for 1 hour, and then cooled again to 0°C. 10.0 g of SnCl4 in approximately 200 mL of anhydrous hexane was added dropwise to the reaction mixture. The contents of the reaction flask were warmed to room temperature and stirred overnight. The next day, the LiCl salt was separated from the reaction mixture by filtration. The solvent was removed from the filtrate by vacuum distillation. The product was purified by distillation under reduced pressure. [Examples]

[0101] Example 17: Reactivity Test Water was added to Sn(NMeEt)4. An exothermic reaction occurred immediately, forming a white SnO2 solid.

[0102] In further tests, methanol was added to Sn(NMeEt)4. This also immediately triggered an exothermic reaction. Figure 8 shows the reaction of Sn(NMeEt)4 before and after the addition of MeOH. 1 The 1H NMR spectrum is shown. As shown in Figure 8, the final product shows the release of HNMeEt and the complete consumption of the starting material. [Examples]

[0103] Example 18: Thermal Stability Test Thermal stability tests of Sn(NMeEt)4 were conducted at constant temperatures of 60°C, 100°C, and 125°C. The experiment was conducted using stainless steel ampoules stored at [temperature] degrees Celsius for several weeks. NMR was performed to check for any thermal decomposition. Visual inspection was also used to look for solid formation after storage.

[0104] Sn(NMeEt)4 remained stable at 60°C. Specifically, Figure 9 shows the stability of Sn(NMeEt)4 at a storage temperature of 60°C, comparing the mass% of Sn(NMeEt)4 with that of HNMeEt. Figure 10 shows the results of Sn(NMeEt)4 samples at 60°C at weeks 0, 4, and 9. 1 The 1H NMR spectrum is shown.

[0105] Sn(NMeEt)4 showed almost no decomposition at 100°C. In detail, Figure 11 shows the mass% of Sn(NMeEt)4 compared to the mass% of HNMeEt, illustrating the stability of Sn(NMeEt)4 at a storage temperature of 100°C. Figure 12 shows the stability of Sn(NMeEt)4 samples at 100°C at weeks 0, 4, and 9. 1 The 1H NMR spectrum is shown.

[0106] Sn(NMeEt)4 completely decomposed after 2 weeks at 100°C. In detail, Figure 13 shows the results of Sn(NMeEt)4 samples at 125°C at 0, 1, and 2 weeks. 1 The 1H NMR spectrum is shown.

[0107] Furthermore, higher vapor pressures allow for minimizing the heating of chemicals for vapor delivery to the CVD / ALD chamber. For less volatile materials, higher temperatures are required to reach the desired vapor pressure for physical delivery to the chamber. As temperatures rise, the likelihood of thermal decomposition increases. The goal for any precursor is to deliver it at a sufficiently high vapor pressure without inducing thermal decomposition of the material. Figure 1 shows the various vapor pressures of several compounds that can be used to form tin oxide films.

[0108] Furthermore, it has been found that it is difficult to keep a single reaction compound stable during storage. Specifically, the reaction compounds used to deposit tin oxide films have been found to become disproportionate over time. Additives have been found to prevent dimerization in such compounds. Specifically, formula IV:Sn(NR 42) A second organometallic compound selected from the compounds represented by 4 has been found to have the ability to inhibit the dimerization of tin compounds used to deposit tin oxide films. In certain compounds contained in formula IV, each R 4 The group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms.

[0109] The compound of formula IV is, each R 4 The compound comprises a group in which the group is an alkyl group having 1 to 10 carbon atoms, independently selected. 4 The group is intended to be an independently selected alkyl group having 1 to 6 carbon atoms. In particular, each R 4 The group is an alkyl group having 1 to 4 carbon atoms, selected independently. More specifically, each R 4 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In addition, in some compounds, each R 4 The group may represent a different alkyl, acyl, or aryl group, particularly a different alkyl group.

[0110] The specific organometallic compounds of formula IV include: Sn(NMe2)4, Sn(NEt2)4, and Sn(NMeEt)4.

[0111] Organometallic compounds that may be beneficial upon addition of the second organometallic compound of formula IV include formula III:R 3 2Sn(NR 3 '2)2 (In the formula, Each R 3 The group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms. Each R 3 (The group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms.) It contains compounds represented by [the formula shown].

[0112] The compound of formula I is each R3 Base and each R 3 The compound comprises a group in which the group is an alkyl group having 1 to 10 carbon atoms, independently selected. 3 Base and each R 3 The group is intended to be an independently selected alkyl group having 1 to 6 carbon atoms. In particular, each R 3 Base and each R 3 The group is an alkyl group having 1 to 4 carbon atoms, selected independently. More specifically, each R 3 Base and each R 3 The group is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and n-butyl. In addition, in some compounds, each R 3 Base and each R 3 The group may represent a different alkyl, acyl, or aryl group, particularly a different alkyl group. [Examples]

[0113] Example 19: Disproportionation Test Disproportionation stability tests were conducted on Me2Sn(NEtMe)2 with and without Sn(NMe2)4 in stainless steel containers stored at a constant temperature of 70°C for several days. NMR was performed to determine the mass % of Me2Sn(NEtMe)2 at various points during storage to confirm whether any disproportionation occurred. For comparison, Me2Sn(NEtMe)2 was stored alone in one container, and Me2Sn(NEtMe)2 with 10 mol% Sn(NMe2)4 added was stored in another container. Figure 2 is a graph showing the disproportionation rates of Me2Sn(NMe2)2 alone and in a mixture with Sn(NMe2)4.

[0114] The test results, as shown in Figure 6, indicate that the addition of Sn(NMe2)4 virtually prevented disproportionation and substantially improved storage stability.

[0115] In some cases, etching of the deposited tin oxide film is desired. Furthermore, as described above, the deposition chamber used to form the tin oxide film needs to be cleaned, which includes removing the tin oxide film formed on the inner surface of the reactor chamber. It is desirable to use a dry etching method for both etching the tin oxide film formed on the substrate and for removing unwanted tin oxide film from the inner surface of the reactor chamber. However, dry etching of tin oxide has proven difficult for the reasons listed above. However, the dry etching method disclosed herein solves these problems. An exemplary embodiment of the dry etching method is shown below.

[0116] In use, the dry etching method involves heating the entire reactor chamber to a high temperature exceeding 100°C, for example, between 100°C and 900°C, and supplying etchant gas from a gas source connected to the reactor chamber. More specifically, in embodiments of thermal etching in a quartz CVD / ALD furnace, the high temperature is between 400°C and 900°C, while in embodiments of plasma etching in an aluminum, stainless steel, or ceramic ALD chamber, the high temperature is between 100°C and 400°C. The etchant gas flows through the reactor chamber before being exhausted along with any reaction products generated and pumped out through a gas exhaust line. The gas pressure in the reactor chamber is typically maintained between 0.1 mBar and 1,000 mBar (atmospheric pressure), but can rise to 1,500 mBar during the dry etching cycle.

[0117] In embodiments, the etchant gas is activated to enhance the generation of free radicals and thereby enhance the etching method. Activation can be achieved by thermal activation, ultraviolet (UV) excitation, or plasma discharge. The gas enters the activation chamber. Inside the activation chamber, a large volume of gas is exposed to an activation energy source such as a heater (thermal activation), a UV lamp (UV activation), or an ionizing RF field (plasma activation). Thermal activation can be performed by heating the MOVPE (metal-organic vapor deposition) reactor. Alternatively, the etchant gas can be preheated in a heating chamber before being injected into the reactor. In the case of UV or plasma discharge activation, the etchant gas is activated in the activation chamber by exposure to UV light or high-frequency plasma discharge before being injected into the reactor. The activated gas exits the activation chamber through an outlet and enters the MOCVD (metal-organic chemical deposition) reactor chamber.

[0118] Etchant gas is general formula A 3 OX2 (in the formula, A 3X is C, N, or S, where O is oxygen, and each X is independently selected from halogens. For example, the etchant gas may contain a carbonyl, thionyl, or nitrosyl group (CO, SO, or NO) combined with a halogen (i.e., chlorine, bromine, or iodine (Cl, Br, or I)). COCl2, COBr2, COI2, SOI2, SOCl2, SOBr2, SO2Cl2, SO2Br2, NOCl, NOBr, NOI, SOClBr, SOClF, and SOFBr are examples of suitable etchant gases. The etchant gas may originate from neat material or, alternatively, be produced by combinations of distinct components such as CO, SO, SO2, or NO mixed with Cl2, Br2, or I2. The etchant gas may be mixed with a carrier gas such as argon, nitrogen, or hydrogen. For etchant components available in gaseous form, the etchant gas or its components may be supplied directly from one or more gas cylinders. For etchant gas components that are normally in liquid form, the required gaseous state can be achieved by blowing a carrier gas into a container containing the liquid etchant components to volatilize the liquid components into etchant, thereby producing a mixture of carrier gas and etchant vapor. Alternatively, the liquid chemical components may be heated until vaporized, at which point the vapor may be combined with the carrier gas as needed and introduced into the reactor chamber. The etchant gas may contain additional amounts of halogens to enhance etching. The etchant gas may contain additional amounts of methyl halide, hydrogen halide, or other halogen compounds to enhance etching.

[0119] In the reaction chamber, etchant gas reacts with metal-containing deposits to form volatile metal halides, which are removed by purging the etchant gas. Typical reactions involve the reaction of metal oxides with a purging gas, forming metal halides with residual oxygen that binds to carbonyl / thionyl / nitrosyl groups. For example: Ga2O3 + 3SOBr2 → 2GaBr3 + 3SO2 2Ga2O3+6SOBrCl→GaClBr2+GaBrCl2+GaCl3+GaBr3+6SO2 Ga2O3 + 3NOBr → GaBr3 + 3NO2 SnO2 + 2SOCl2 → SnCl4 + 2SO2 Other metal-containing deposits also react to form metal halides. Oxides are cited as an example of the most difficult deposits to remove due to the strong affinity of metals for oxygen.

[0120] Once metal halides are formed, they need to be removed from the reaction chamber. One method of removal is to reduce the pressure inside the chamber to move the halides away from the reactor chamber. Another option, which can be used alone or in combination with reduced pressure inside the chamber, is to heat the chamber to a temperature sufficient to evaporate or sublimate the halides.

[0121] It has been discovered that COCl2 can be particularly useful as an etchant gas for removing tin oxide and other metal oxides that are difficult to remove. However, phosgene gas (COCl 2) is an extraordinarily dangerous nerve agent. Therefore, it was determined that by adding a gas mixture of SOCl2 or NOCl with CO or CO2, it is possible to achieve etching functionality similar to that of COCl2 without the chemical hazards associated with COCl2.

[0122] In further embodiments, the etchant gas includes additives to improve etching rate, etching selectivity, or the survival time of by-products. Such additives may be carbon or hydrogen-containing gases, for example, those of the general formula C x H y O z The formula may contain gases (where x, y, and z are numbers between 0 and 10).

[0123] In further embodiments, the etchant gas may also contain diluent additives or supports to improve the etching rate, etching selectivity, or the survival time of by-products. Such additives may include relatively inert gases such as N2, Ar, He, and Ne.

[0124] The methods disclosed herein enable low-temperature etching of SnO2, as well as other metal oxides that are selective for quartz, oxides, ceramics, aluminum, and other materials.

[0125] Furthermore, the method disclosed herein, using the disclosed etchant gas, forms reaction byproducts that are more volatile than those produced by hydrogen-containing molecules, and thus the reaction byproducts can be more easily removed from the chamber before they redeposit on the chamber walls.

[0126] As shown in the following examples, the method disclosed herein is also less corrosive and does not corrode the aluminum surface compared to the method using Cl2 as the etchant. [Examples]

[0127] Example 20 Aluminum, anodized, and Viton specimens were immersed in 21.5 g of SOCl at 60°C. After two weeks, no signs of change were observed. A small amount of brownish solid was loosely adhering to the aluminum specimen, but the aluminum surface itself was unaffected, and no further solid was observed after the first few days. Separately, the same three specimens were sealed in stainless steel ampoules containing 3 g of liquid chlorine and kept at 60°C for two days. Almost no change was observed in the anodized material. However, only a small amount remained in the aluminum. The aluminum was virtually converted into a yellowish-beige solid. The Viton exhibited a significant decrease in tensile strength and easily broke into two pieces when pulled from the mass of yellowish-beige solid. Photographs of the above results are shown in Figure 3. [Examples]

[0128] Example 21: Effect of power on SnO2 etching rate at 26°C and 75°C Etching was performed on a substrate having an exposed SnO2 layer on Si. The substrate was prepared at 50°C and 330 Å. Each run at 26°C had an etching time of 60 seconds, while each run at 75°C had an etching time of 30 seconds. Each run included a flow rate of 2 sccm (vapor draw) and a pressure set to 350 mTorr (0.467 mBar). Figure 4 shows a graph of etching rate (Å / min) against power (W) during the runs. Figure 5 shows a graph of etching rate (Å / min) against power (W) only for runs at 26°C.

[0129] As the results show, the etching rate of SnO2 increases exponentially with power. The effect of power on the increase in etching rate at ambient temperature is similar for both SnO2 and SiO2. However, etching of SiO2 was not observed at 75°C and 100W. Furthermore, the selectivity for SnO2 etching at a low pressure of 350 mTorr (0.467 mBar) at 26°C is approximately 13:1, while at 1 Torr (1.333 mBar) it is 3:1. [Examples]

[0130] Example 22: Etching rate of SnO2 film at 300W and 26℃ Etching was performed on a substrate having an exposed layer of SnO2 on a Si base. The substrate was prepared at 50°C and 330 Å. Each run was performed at a temperature of 26°C, a flow rate of 2 sccm (vapor extraction), a pressure set to 350 mTorr (0.467 mBar), and a power of 300 W. Only the run time differed between runs, and the resulting various etching rates are shown in Table 1 below.

[0131] [Table 1] [Examples]

[0132] Example 23: Influence of Power on the Etching Rate of SnO₂ at 26°C Etching of a substrate having an exposed layer of SnO₂ on Si was carried out. The substrate was prepared at 50°C and 330 Å. Each run included a temperature of 26°C, a flow rate of 2 sccm (vapor extraction), a pressure set at 350 mTorr (0.467 mBar), and an etching time of 60 seconds. Only the run time differed between runs, and the following Table 2 shows the various etching rates obtained as a result.

[0133] [Table 2] [Examples]

[0134] Example 24: Influence of Power on the Etching Rate of SnO₂ at 75°C Etching of a substrate having an exposed layer of SnO₂ on Si was carried out. The substrate was prepared at 50°C and 330 Å. Each run included a temperature of 75°C, a flow rate of 2 sccm (vapor extraction), a pressure set at 350 mTorr (0.467 mBar), and an etching time of 30 seconds. Only the run time differed between runs, and the following Table 3 shows the various etching rates obtained as a result.

[0135] [Table 3] [Examples]

[0136] Example 25: Influence of Temperature on the Etching Rate of SnO₂ Etching of a substrate having an exposed layer of SnO₂ on Si was performed. The substrate was prepared at 50 °C and 330 Å. Each of the implementations included a flow rate of 2 sccm (vapor extraction), a pressure set at 350 mTorr (0.467 mBar), an etching time of 30 seconds, and a power of 200 W. Only the implementation time differed between the implementations, and Table 4 below shows the various etching rates obtained as a result.

[0137]

Table 4

[0138] Fractional distillation From the theoretical modeling of the activation energy required to remove ligands from molecules via hydrolysis reactions, a wide range of activation energies are observed between molecules. Therefore, differences in reactivity are observed. This indicates that when the activation energy is low, the molecule is likely to be a highly reactive molecule towards the formation of SnO₂, but this value also indicates that the molecule may be prone to decomposition and reaction during the synthesis and purification processes. Therefore, it is difficult to obtain pure compounds within the ranges of Formulas I and II, and in particular, it will be difficult to obtain assay purities exceeding 95%, and even more so exceeding 99%.

[0139] However, when fractional vacuum distillation is used, assay purities exceeding 95%, and even more so exceeding 99%, can be obtained for compounds within the range of Formula I or II. Although various forms of fractional distillation are known in the chemical manufacturing industry, they have not been used for the purification of organometallic materials containing compounds of Formula I or II.

[0140] As shown in the schematic diagram in Figure 14, multiple-effect or multi-stage distillation (MED) is a distillation process commonly used for seawater desalination. The process consists of multiple stages or "effects." (In the schematic diagram in Figure 14, the first stage is at the top. The upper region of each stage is vapor, and the lower region of each stage is the liquid feed material. The material flowing through the pipe at the bottom of the VC along the left side of the diagram is the condensate. It is not shown how the feed material enters the stages other than the first stage, but the method should be easily understood. F - feed. S - introduction of heated vapor. C - discharge of heated vapor. W - discharge of purified material (condensate). R - discharge of waste material. O - introduction of refrigerant. P - discharge of refrigerant. The VC is the condenser for the final stage.) In each stage, the feed material is heated by the vapor in the tubes. Some of the feed material evaporates, and this vapor flows into the tubes of the next stage, heating and evaporating more distillate. Each stage essentially reuses energy from the previous stage.

[0141] The apparatus can be viewed as a series of closed spaces separated by tube walls, with a heat source at one end and a heat sink at the other. Each space is under a pressure lower than atmospheric pressure due to the vacuum. Each space consists of two interconnected subspaces: the outside of the tube at stage n and the inside of the tube at stage n+1. Each space has a lower temperature and pressure than the previous space, and the tube walls are at an intermediate temperature between the temperatures of the fluids on both sides. The pressure within the space cannot be in equilibrium with the temperature of the walls of the subspaces on either side, and is instead at an intermediate pressure. As a result, the feed material evaporates because the pressure in the first subspace is too low or the temperature is too high. In the second subspace, the vapor condenses because the pressure is too high or the temperature is too low. This allows evaporation energy to be transferred from the warmer first subspace to the colder second subspace. In the second subspace, energy flows through the tube wall to the next, even colder space by conduction.

[0142] Those skilled in the art will understand that, as described in relation to preferred embodiments, additions, deletions, modifications, and substitutions not described in detail can be made without departing from the scope of the invention as defined in the appended claims.

Claims

1. Formula I: Q ｘ -Sn-(A １ R １ ’ ｚ ) ４－ｘ Formula I (In the formula, Q is OR １ or Cp, Each R １ The group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms. Each R １ The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having 1 to 10 carbon atoms. x is an integer from 1 to 4, When x is 0, A １ is O, and when x is an integer from 1 to 3, A １ is N A １ If is O, then z is 1, and A １ If z is N, then z is 2. Organometallic compounds.

2. The organometallic compound according to claim 1, wherein x is an integer from 1 to 3.

3. Q is OR １ The organometallic compound according to claim 1 or 2.

4. The organometallic compound according to claim 1 or 2, wherein Q is Cp.

5. The organometallic compound according to claim 4, wherein x is 1.

6. Each R １ The organometallic compound according to any one of claims 1 to 5, wherein the group is independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.

7. Each R １ An organometallic compound according to any one of claims 1 to 6, wherein the group is Me.

8. When z is 2, each R １ The organometallic compound according to any one of claims 1 to 7, wherein ' represents a combination of two different alkyl, acyl, or aryl groups.

9. The organometallic compound according to claim 1, wherein x is 4.

10. Each R １ The organometallic compound according to any one of claims 1 to 3 and 6 to 9, wherein the group is independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.

11. at least one R １ The organometallic compound according to any one of claims 1 to 3 and 6 to 10, wherein the group is Me.

12. (MeO) ２ Sn(NMe ２ ) ２ (MeO) ２ Sn (NETMe) ２ (MeO) ３ Sn(NMe ２ ), (MeO) ３ Sn(NEtMe), Sn(OMe) ４ , CpSn(NMeEt) ３ , and CpSn(NMe ２ ) ３ An organometallic compound according to claim 1, selected from the group consisting of the following.

13. Formula II: Sn(NR ２ (CH ２ ) ｎ A ２ ) ２ Formula II (In the formula, Each A ２ NR ２ 'or selected independently of O, Each R ２ The group is independently selected from the group consisting of hydrogen and alkyl or aryl groups having 1 to 10 carbon atoms. Each R ２ The group is independently selected from the group consisting of alkyl, acyl, or aryl groups having hydrogen and 1 to 10 carbon atoms. n is 2 or 3, Depending on the circumstances, NR ２ (CH ２ ) ｎ NR ２ ' forms a ring structure, Depending on the circumstances, (CH ２ (At least one of these has one or more substitutions with an alkyl group having 1 to 10 carbon atoms.) Organometallic compounds.

14. Each A ２ ∇O, and equation II is equation IIa: Sn(NR ２ (CH ２ ) ｎ O) ２ The organometallic compound according to claim 13, as represented by [the specified formula].

15. Each R ２ The organometallic compound according to claim 14, wherein the group is independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.

16. CH ２ The organometallic compound according to claim 13, wherein at least one of the members has one or more substitutions by an alkyl group having 1 to 10 carbon atoms.

17. CH in each amine ２ The organometallic compound according to claim 16, wherein only one of the members has one or more substitutions by an alkyl group having 1 to 10 carbon atoms.

18. The CH in each amine ２ The organometallic compound according to claim 17, wherein one of the above has two substitutions with methyl or ethyl.

19. Each A ２ N is given by equation II, and equation II is equation IIb: 【Chemistry 1】 (In the formula, each R ２ '' group and each R ２ The group is an alkyl group having 1 to 10 carbon atoms, selected independently. The organometallic compound according to any one of claims 13 and 16 to 18, as represented by the following:

20. Each R ２ '' group and each R ２ The organometallic compound according to claim 19, wherein the group is methyl or ethyl.

21. Each R ２ Base and each R ２ The organometallic compound according to any one of claims 16 to 20, wherein the group is independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.

22. Each R ２ Base and each R ２ An organometallic compound according to any one of claims 16 to 20, wherein the group is hydrogen.

23. Each NR ２ (CH ２ ) ｎ NR ２ The organometallic compound according to claim 13, wherein ' forms a cyclic structure.

24. Equation II is Equation IIc: 【Chemistry 2】 The organometallic compound according to claim 23, as represented by the following:

25. Each (NR ２ (CH ２ ) ｎ A ２ ) is selected from the group consisting of N,N'-dimethylethylenediamine (NMe(CH ２ ) ２ NMe), piperazine (N ２ C ４ H ８ ), N,N'-diethylethylenediamine (NEt(CH ２ )) ２ NEt), N,N'-diisopropylethylenediamine (NiPr(CH ２ )) ２ NiPr), N,N'-di-tert-butylethylenediamine (NtBu(CH ２ )) ２ NtBu), N,N'-dimethyl-1,3-propanediamine (NMe(CH ２ )) ３ NMe), 2,2-dimethyl-1,3-propanediamine (NH(CH ２ )(C(CH ３ ))(CH ２ ))NH), 2-(methylamino)ethanol (NMe(CH ２ )) ２ O), and 2-(ethylamino)ethanol (NEt(CH ２ )) ２ O), the organometallic compound according to claim 13.

26. Formula I: R ３ ２ Sn(NR ３ ’ ２ ) ２ Formula I (In the formula, Each R ３ The group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms. Each R ３ ' group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms) A first organometallic compound represented by, and Formula II: Sn(NR ４ ２ ) ４ Formula II (In the formula, each R ４ The group is independently selected from the group consisting of alkyl or aryl groups having 1 to 10 carbon atoms. A composition comprising a second organometallic compound represented by .

27. The aforementioned R ３ 'Base and the R ４ The composition according to claim 26, wherein the base is the same.

28. Each R ３ The composition according to claim 26 or 27, wherein the group is independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.

29. Each R ３ 'Base and each R ４ The composition according to any one of claims 26 to 28, wherein the group is independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.

30. The second organometallic compound is Sn(NMe ２ ) ４ , Sn(NET ２ ) ４ , and Sn(NMeet) ４ A composition according to any one of claims 26 to 29, selected from the group consisting of the following.

31. A method for removing tin oxide deposits from the inner surface of a reactor chamber or from a substrate within the reactor chamber, The process involves introducing an etchant gas into the reactor chamber containing tin oxide deposits, wherein the etchant gas is of general formula A ３ O ｍ X ｎ (In the formula, A ３ It is selected from the group consisting of C, N, and S, O is oxygen, Each X is independently selected from the group consisting of halogens. Subscript ｍ and ｎ (is greater than zero) The compound, process, A step of activating the etchant gas, either before or after the introduction. The process of carrying out an etching reaction between the activated etchant gas and the tin oxide deposit, and A step of exhausting the etchant gas together with the gaseous products of the etching reaction. Methods that include...

32. A method for removing deposits from the inner surface of a reactor chamber or from a substrate within the reactor chamber, The process involves introducing an etchant gas and an additive into the reactor chamber, wherein the etchant gas is of general formula A ３ O ｍ X ｎ (In the formula, A ３ It is selected from the group consisting of N and S, O is oxygen, Each X is independently selected from the group consisting of halogens. Subscript ｍ and ｎ (is greater than zero) The compound is of the general formula C ｘ H ｙ O ｚ (In the formula, subscripts) ｘ and ｚ The process is one in which (is greater than zero) A step of activating the etchant gas, either before or after the introduction. A step of carrying out an etching reaction between the activated etchant gas and the deposit, and A step of exhausting the etchant gas together with the gaseous products of the etching reaction. Methods that include...

33. The method according to claim 31 or 32, wherein X represents a combination of two different halogens.

34. The method according to any one of claims 31 to 33, further comprising the step of generating the etchant gas before introducing it into the chamber.

35. The method according to any one of claims 31 to 34, further comprising the step of blowing a carrier gas into a liquid chemical component to volatilize the liquid chemical component into the etchant before introducing the etchant gas into the chamber.

36. The method according to claim 35, wherein the etchant gas is produced by blowing a carrier gas into a plurality of liquid chemical components and then combining the resulting gases.

37. The method according to claim 35, wherein the etchant gas is produced by mixing two or more chemical component gases.

38. The method according to any one of claims 31 to 37, wherein the etchant gas is activated by exposure to an activation mechanism in a gas activation chamber before being introduced into the chamber, and the gas activation mechanism is selected from the group consisting of heat, ultraviolet light, and plasma discharge.

39. The method according to any one of claims 31 to 38, wherein the etchant gas is activated by exposure to a thermal activation mechanism after being introduced into the chamber, and the thermal activation mechanism is selected from the group consisting of the overall temperature in the chamber and a local heat source in the chamber.

40. The etchant gas is thionyl chloride (SOCl ２ The method according to any one of claims 31 to 39.

41. The aforementioned additive is CO or CO ２ The method according to any one of claims 32 to 40.

42. The method according to any one of claims 31 to 41, wherein a halogen-containing additive is added to the gaseous mixture containing the etchant gas.

43. The method according to claim 42, wherein the halogen-containing additive is an active halogen or a compound of the general formula RY (wherein R is selected from the group consisting of H and Me, and Y is a halogen selected from the group consisting of F, Cl, Br, and I).

44. The method according to claim 43, wherein the active halogen comprises Cl or Br.

45. The method according to any one of claims 31 to 44, wherein a diluent is added to the gaseous mixture containing the etchant gas.

46. The method according to claim 45, wherein the dilution additive comprises N, Ar, He, or Ne.

47. The method according to any one of claims 31 to 46, further comprising the step of heating the reactor chamber to a temperature of at least 100°C, preferably between 100°C and 900°C, more preferably between 100°C and 400°C.

48. The method according to any one of claims 31 to 47, further comprising the step of applying a pressure to the reactor chamber between 0.1 mBar and 1,500 mBar, preferably between 0.1 mBar and 1,000 mBar.

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