Selective deposition agent, method for forming selective thin film including same, semiconductor substrate, and semiconductor device

Abstract

The present invention relates to a selective deposition agent, a method for forming a selective thin film including same, a semiconductor substrate, and a semiconductor device. According to the present invention, by including a predetermined compound that is selectively deposited only on a surface of a SiO2 substrate, a selective thin film may be formed during subsequent deposition of SiN or SiCN. As a result, a high-purity and high-quality selective thin film can be formed, thereby providing effects such as high performance and high reliability in a semiconductor device including a semiconductor substrate including the selective thin film.

Description

Selective deposition agent, selective thin film formation method including the same, semiconductor substrate and semiconductor device

[0001] The present invention relates to a selective deposition agent, a method for forming a selective thin film including the same, and a semiconductor substrate and a semiconductor device. More specifically, the invention relates to a selective deposition agent comprising a predetermined compound that selectively deposits only on the surface of a SiO2 substrate, capable of realizing a selective thin film form when SiN or SiCN is post-deposited, a method for forming a selective thin film of high purity and high quality including the same, and a semiconductor substrate and a semiconductor device manufactured therefrom.

[0002] Due to the advancement of electronic technology, the downscaling of semiconductor devices is progressing rapidly, and consequently, the patterns constituting electronic devices are becoming miniaturized.

[0003] Accordingly, in the semiconductor device manufacturing process, a technology is required to selectively form a new thin film only on a portion of the thin films made of a specific material on a surface where multiple thin films made of different materials are exposed.

[0004] Selective deposition techniques for materials can possess unique selectivity based on surface chemistry. However, such processes are quite rare and generally require surfaces with extremely different surface energies, such as metals and dielectrics. Selective blocking can be achieved by utilizing surface treatment techniques that selectively react with one surface and not with another when the surfaces are similar (e.g., SiO2 versus SiN), thereby effectively blocking any surface reactions during the subsequent deposition process.

[0005] Considering this, chemical blockers or surface treatment technologies have been attempted in selective region atomic layer deposition technology, but there is a problem in that they do not exhibit an effective blocking effect.

[0006] Therefore, continued research in the relevant technical field is required regarding methods and materials for selective deposition on similar surfaces (SiO2 surfaces and SiN or SiCN surfaces).

[0007] [Prior Art Literature]

[0008] [Patent Literature]

[0009] Korean Patent Publication No. 2014-0066220

[0010] In order to solve the problems of the prior art as described above, the present invention aims to provide a selective deposition agent capable of realizing a selective thin film form when SiN or SiCN is post-deposited, comprising a predetermined compound that is selectively deposited only on the surface of a SiO2 substrate.

[0011] In addition, the present invention aims to provide high performance and high reliability to a semiconductor device including a semiconductor substrate by forming a selective thin film of high purity and high quality including the above-mentioned selective deposition agent.

[0012] The above and other objectives of the present invention can all be achieved by the present invention described below.

[0013] To achieve the above objective, the present invention provides a selective deposition agent characterized by comprising a structure including a fluoro group directly connected to a silicon atom.

[0014] The above selective deposition agent may have the structure of XnAa(NR1R2)mSi-SiXnAaBb[Equation 1].

[0015] The above X may be a fluorine, chlorine, or bromine atom, and preferably a fluorine atom.

[0016] The above A, R1, and R2 may each independently be H, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an allyl group, a silylamino group, or a heterocyclic group.

[0017] The above B may be a silylalkyl group or NR1R2.

[0018] Here, the alkyl group constituting the silylalkyl group may have 1 to 6 carbon atoms.

[0019] The above n may be an integer from 1 to 3.

[0020] The above a, m, or b may each be an integer from 0 to 3.

[0021] The above n+m+a+b can be 3.

[0022] The above selective deposition agent may have the structure of Xn(NR1R2)mAaSi-NR3-SiAaXn(NR1R2)m [Equation 2].

[0023] The above X may be a fluorine, chlorine, or bromine atom, and preferably a fluorine atom.

[0024] The above A, R1, and R2 may each independently be an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an allyl group, a silylamino group, or a heterocyclic group.

[0025] The above R3 may be H, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an allyl group, a silylamino group, or a heterocyclic group.

[0026] The above n may be an integer from 1 to 3.

[0027] The above a or m may each be an integer from 0 to 3.

[0028] The above n+m+a can be 3.

[0029]

[0030] The above selective deposition agent may be one or more selected from compounds represented by the following chemical formulas 1 to 4.

[0031] [Chemical Formulas 1 to 4]

[0032]

[0033] The above selective deposition agent may have a To (temperature at the point where Residue=0%) of 200 ℃ or higher during TGA analysis.

[0034] The above selective deposition agent may have a To (temperature at the point where Residue=0%) in the range of 200 to 300 ℃ during TGA analysis.

[0035] The above selective deposition agent may show a heat flow peak within 100 to 300°C during DSC analysis.

[0036]

[0037] In addition, according to the present invention, a method for synthesizing a selective deposition agent comprises a synthesis step of a chloroamine disilane compound or a chloroamine silane compound; and a fluoride substitution step.

[0038] The above chloroamine disilane compound synthesis step can be performed using a chlorodisilane compound and an alkylamine compound in an organic solvent.

[0039] The above chloroaminesilane compound synthesis step can be performed using a chlorosilane compound and a compound having a Si-OH structure under alkyllithium and an organic solvent.

[0040]

[0041] In addition, the present invention comprises the step of depositing and adsorbing the aforementioned selective deposition agent onto a substrate; and the step of forming a SiCN or SiN thin film by injecting a Si precursor compound and a nitriding agent onto the substrate.

[0042] The present invention provides a method for manufacturing a selective thin film, characterized in that the above SiCN or SiN thin film is formed in a portion of the substrate where the selective deposition agent is not adsorbed.

[0043] The above-mentioned surface may be SiO2, SiOH, etc.

[0044] The above selective thin film formation method can be carried out at a deposition temperature of 100 to 1,000°C.

[0045] The above selective deposition agent can be thermally decomposed in a temperature range of 100 to 300°C.

[0046] The above deposition can be carried out by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0047]

[0048] In addition, the present invention provides a semiconductor substrate comprising: a substrate; and a selective thin film formed on the substrate; wherein the selective thin film is manufactured by the method described above.

[0049] The above selective thin film may have a deposition-free form of SiCN or SiN.

[0050] The above-mentioned surface may be SiO2, SiOH, etc.

[0051] The above thin film may include a SiO2 thin film region and a SiCN and / or SiN thin film region.

[0052] The height occupied by the above SiO2 thin film region may be lower within a range of 30 Å or less than the height occupied by the above SiCN and / or SiN thin film region.

[0053] The surface of the above SiO2 thin film region can block the deposition of SiCN and / or SiN.

[0054]

[0055] In addition, the present invention provides a semiconductor device characterized by including the aforementioned semiconductor substrate.

[0056] According to the present invention, a selective deposition agent can be provided that includes a structure comprising a fluoro group directly connected to a silicon atom of a precursor compound, which not only increases storage stability by reducing self-reactivity but also reduces the amount of residue on the substrate by increasing the volatility of the functional group desorbed after deposition, while simultaneously enabling high decomposition temperature and film deposition temperature characteristics, and enables atomic layer deposition under high temperature conditions and has excellent storage stability and handling properties.

[0057] In addition, including this, it has the effect of providing a method for forming thin films with thermal stability, improved deposition uniformity, high thin film quality, and precise compositional control, even in high-temperature deposition processes.

[0058] In addition, a semiconductor substrate and a semiconductor device including a thin film formed using the above-mentioned selective deposition agent can provide high performance and high reliability.

[0059] Accordingly, semiconductor substrates and semiconductor devices including the same are suitable for forming gate dielectrics, hard masks, diffusion barriers, and interlayer dielectrics (ILD) in the semiconductor field, and can be applied to manufacturing processes for next-generation devices such as FinFET, GAA (Gate-All-Around), 3D NAND, DRAM, and Logic SoC. In the display manufacturing field, they are advantageous for forming gate dielectrics, passivation films, and interlayer dielectrics within the TFT (Thin Film Transistor) device structure, and can be utilized in the manufacturing of LTPS, oxide TFT, and AMOLED. Furthermore, in the secondary battery industry, they can be applied for the deposition of ceramic coating layers, electrode protection films, or dielectric films, and can be used to form silicon thin films when manufacturing silicon anodes (Si-anodes).

[0060] Figure 1 is a figure showing the hydrogen nuclear magnetic resonance (1H-NMR) spectrum of a compound synthesized according to Example 1 of the present invention.

[0061] Figure 2 is a diagram showing the TGA and DSC analysis results for the compound of Figure 1.

[0062] Figure 3 is a diagram showing the vapor pressure measurement results for the compound of Figure 1.

[0063] Figures 4 and 5 show the hydrogen nuclear magnetic resonance (1H-NMR) spectrum of a compound synthesized according to Example 2 of the present invention.

[0064] Figure 6 is a diagram showing the TGA and DSC analysis results for the compound of Figure 4.

[0065] Figure 7 is a diagram showing the results of measuring the thickness of a silicon-containing thin film obtained by applying a compound synthesized according to Example 2 of the present invention to a SiO2 substrate and a SiCN substrate using an Ellipsometry analysis device.

[0066] The selective deposition agent of the present invention, a selective thin film formation method including the same, and a semiconductor substrate and a semiconductor device are described in detail below.

[0067] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0068] In this specification, when a member is described as being located 'on' another member, this includes not only cases where a member is in contact with another member, but also cases where another member exists between the two members.

[0069] In this specification, when a part is described as 'comprising' a certain component, it means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0070]

[0071] The inventors confirmed that when a specific structure containing a fluoro group directly connected to a silicon element included in a selective deposition agent is included, not only is storage stability increased by reducing self-reactivity, but the amount of residue on the substrate is reduced due to the high volatility of the functional group desorbed after deposition, while simultaneously achieving high decomposition temperature and film formation temperature characteristics. Based on this, they further devoted themselves to research and completed the present invention.

[0072] The above selective deposition agent may have the structure XnAa(NR1R2)mSi-SiXnAaBb [Equation 1]. In this case, it has excellent volatility and thermal stability, exists in a liquid state even at room temperature and pressure, making storage and handling easy, and has the advantage of being suitable as an SiO2 deposition inhibitor based on high reactivity.

[0073] For example, due to the breakdown of weak Si-Si bonds in disilane compounds, two oxygen atoms and Si bond on a SiO2 substrate to form O-SiF2-O bonds, which can block the formation of SiN or SiCN thin films. Since the O-SiF2-O bond is stronger than the O-SiF3 bond, it may also be advantageous for process temperature conditions.

[0074] The above X may be fluorine, chlorine, or bromine, and preferably may be a fluorine atom. In this case, by forming SiF3 bonds with oxygen, it can have the effect of blocking the formation of SiN or SiCN thin films on the SiO2 substrate during a subsequent SiN or SiCN process.

[0075] The above A, R1, and R2 may each independently be an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an allyl group, a silylamino group, or a heterocyclic group.

[0076] When using a tert tert alkyl structure as the above R2, specifically iso-propyl, sec-butyl, iso-butyl, sec-pentyl, iso-pentyl, neo-pentyl, iso-hexyl, or sec-hexyl, it is desirable to exclude its use because the reduction in the stabilization effect between p-orbitals forming hyperconjugation compared to normal alkyl groups and the reduction in the hyperconjugation effect due to the difference in alkyl groups result in poor thermal stability.

[0077] The above B may be a silylalkyl group or NR1R2.

[0078] Here, the alkyl group constituting the silylalkyl group may have 1 to 6 carbon atoms.

[0079] The above n may be an integer from 1 to 3.

[0080] The above a, m, or b may each be an integer from 0 to 3.

[0081] The above n+m+a+b can be 3. In this case, by forming a SiF3 bond with oxygen, it can have the effect of blocking the formation of a SiN or SiCN thin film on a SiO2 substrate in a subsequent SiN or SiCN process.

[0082]

[0083] The above selective deposition agent may have the structure Xn(NR1R2)mAaSi-NR3-SiAaXn(NR1R2)m [Equation 2]. In this case, it has excellent volatility and thermal stability, exists in a liquid state even at room temperature and pressure, making storage and handling easy, and has the advantage of being suitable as a SiO2 deposition inhibitor based on high reactivity.

[0084] For example, due to the breakdown of weak Si-Si bonds in disilane compounds, two oxygen atoms and Si bond on a SiO2 substrate to form O-SiF2-O bonds, which can block the formation of SiN or SiCN thin films. Since the O-SiF2-O bond is stronger than the O-SiF3 bond, it may also be advantageous for process temperature conditions.

[0085] The above X may be fluorine, chlorine, or bromine, and preferably may be a fluorine atom. In this case, by forming SiF3 bonds with oxygen, it can have the effect of blocking the formation of SiN or SiCN thin films on the SiO2 substrate during a subsequent SiN or SiCN process.

[0086] The above A, R1, and R2 may each independently be an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an allyl group, a silylamino group, or a heterocyclic group.

[0087] When using a tert tert alkyl structure as the above R2, specifically iso-propyl, sec-butyl, iso-butyl, sec-pentyl, iso-pentyl, neo-pentyl, iso-hexyl, or sec-hexyl, it is desirable to exclude its use because the reduction in the stabilization effect between p-orbitals forming hyperconjugation compared to normal alkyl groups and the reduction in the hyperconjugation effect due to the difference in alkyl groups result in poor thermal stability.

[0088] The above R3 may be H, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an allyl group, a silylamino group, or a heterocyclic group.

[0089] The above n may be an integer from 1 to 3.

[0090] The above a or m may each be an integer from 0 to 3.

[0091] The above n+m+a can be 3. In this case, by forming a bond with oxygen and SiF3, it can have the effect of blocking the formation of a SiN or SiCN thin film on a SiO2 substrate in a subsequent SiN or SiCN process.

[0092]

[0093] The above selective deposition agent may be, for example, one or more selected from compounds represented by the following chemical formulas 1 to 4. In this case, it not only increases storage stability by reducing self-reactivity but also appropriately provides the effect of reducing the amount of residue on the substrate by increasing the volatility of functional groups desorbed after deposition, while simultaneously realizing high decomposition temperature and film formation temperature characteristics.

[0094] For reference, as shown in Chemical Formulas 1 to 4 above, a coordination bond is formed between silicon and nitrogen due to non-covalent electron pairs included in nitrogen, and the selective deposition agent becomes more stable due to the geometric structural effects of the electron donor and steric hindering group substituted therein, and accordingly, there is an excellent effect of improving thermal stability, storage stability, and the temperature range of the atomic layer deposition process.

[0095] [Chemical Formulas 1 to 4]

[0096]

[0097] As shown in the DSC analysis graphs in Figures 2 and 6 below, the above selective deposition agent exhibits a heat flow peak within 100 to 400°C, 150 to 400°C, or 100 to 300°C, providing a thermal decomposition temperature range with excellent thermal stability and having excellent storage stability and handling properties.

[0098] As shown in the TGA analysis graphs in Figures 2 and 6 below, the above selective deposition agent exhibits a To (temperature at the point where Residue=0%) of 200°C or higher, 180 to 250°C, or 200 to 300°C, and in this case, provides excellent thermal stability and volatility. In this case, as a volatile liquid phase, it has excellent thermal stability even under high temperature conditions, and has the effect of excellent storage stability and handling properties.

[0099] The above selective deposition agent may, for example, have a vapor pressure of 0.5 mmHg or less, or 0.05 to 0.5 mmHg, when measured at 25°C. Within this range, there is an advantage of having a vapor pressure sufficient for deposition during thin film manufacturing and an improved deposition rate.

[0100] As described above, the selective deposition agent of the present invention has excellent volatility and possesses sufficient vapor pressure for thin film deposition processes, thereby having an excellent effect of improving process efficiency when applied to deposition processes such as CVD and ALD.

[0101]

[0102] The selective deposition agent of the present invention can further stabilize the compound through the bond formed between silicon and nitrogen by using nitrogen containing non-covalent electron pairs within the ligand of the selective deposition agent, and as shown in Figure 2, which shows the DSC for the compound of Example 1, the effect of stabilizing the compound can be further enhanced by having fewer thermal decomposition by-products, such as the formation of O-SiF2-O in the thin film through primary Si-Si bond decomposition and secondary Si-N decomposition by two heat flows.

[0103] In particular, the direct bonding between the nitrogen atom and silicon, and furthermore, the direct bonding of silicon atoms on both sides centered around a single nitrogen atom, forms a coordinate covalent bond. When the nitrogen atom is included, it is relatively easy to break compared to other bonds within the compound, so the reaction with the nitriding agent during the thin film formation process can proceed stably, which has the advantage of making the thin film formation process easier. At the same time, due to the chemical stability of the compound itself, it does not decompose thermally at temperatures below 250°C, so it has excellent thermal stability. In addition, it has low reactivity at room temperature, so there is no risk of spontaneous combustion and it has the advantage of being easy to handle.

[0104]

[0105] For example, the above selective deposition agent can be synthesized by including, for example, a chloroamine disilane compound synthesis step; and a fluoride substitution step.

[0106] The above chloroaminedisilane compound synthesis step can be performed using a chlorodisilane compound and an alkylamine compound in an organic solvent.

[0107] The above chlorodisilane compound may be hexachlorodisilane, etc.

[0108] The above alkylamine compound may be methylamine, ethylamine, propylamine, butylamine, diisopropylamine, silylamine, etc.

[0109] The above organic solvent may be a polar solvent or a non-polar solvent.

[0110] The above chlorodisilane compound, alkylamine compound and organic solvent may be used in a molar ratio of 1:2:20 to 1:7:90, preferably 1:4:40 to 1:5:50.

[0111] The fluoride source used in the above fluoride substitution step may be a transition metal fluoride selected from AgF, AgF2, ZnF2, CuF2, CuF2·H2O, NiF2, SnF2, InF3, ScF3, TiF3, MnF3, CoF3, CrF3, AuF3, FeF3, MnF3, BiF3, and SbF3.

[0112] The above fluoride source may be included in a range of 1 to 3 moles or 1.1 to 2 moles based on 1 mole of the above chloroamine disilane.

[0113] The above fluoride source can be introduced using an ether solvent.

[0114] The above ether solvent may be bis(2-methoxyethyl)ether (diglyme), dipropylene glycol dimethyl ether (DMM), tetrahydrofuran (THF), diethyl ether, etc.

[0115] The above ether solvent may be included in a range of 5 to 50 moles or 10 to 40 moles based on 1 mole of the above chloroaminesilane compound.

[0116] The above substitution temperature can be performed at room temperature throughout the entire reaction, for example, at 20 to 30°C.

[0117] The above selective deposition agent can be synthesized according to the following reaction scheme 1 as a specific example.

[0118] [Reaction Equation 1]

[0119]

[0120] As another example, the above selective deposition agent can be synthesized by including, for example, a chloroaminesilane compound synthesis step; and a fluoride substitution step.

[0121] The above chloroaminesilane compound synthesis step can be performed using a chlorosilane compound and a compound having a Si-OH structure in alkyllithium and an organic solvent.

[0122] The above chlorosilane compound may be tetrachlorosilane, etc.

[0123] The compound having the above Si-OH structure may be, for example, hexamethyldisilazane.

[0124] The above organic solvent may be a polar solvent and / or a non-polar solvent.

[0125] The above organic solvent may be one or more of hexane and tetrahydrofuran, for example.

[0126] The above tetrachlorosilane compound, the compound having a Si-OH structure, and the organic solvent can be used, for example, in a molar ratio of 1:0.5:1 to 1:1.5:10, preferably in a molar ratio of 1:0.8:1.6 to 1:1.2:10.

[0127] The above tetrachlorosilane compound, compound having a Si-OH structure, hexane, and trihydrofuran may be used, for example, in a molar ratio of 1:0.5:0.5:0.5 to 1:1.5:4:6, preferably in a molar ratio of 1:0.8:0.8:0.8 to 1:1.2:4:6.

[0128] Here, alkyllithium can be added in a content range that is typically usable as an initiator, for example, in a range of 100 to 300 parts by weight, preferably 100 to 200 parts by weight, relative to 100 parts by weight of a tetrachlorosilane compound.

[0129] The fluoride source used in the above fluoride substitution step may be a transition metal fluoride selected from AgF, AgF2, ZnF2, CuF2, CuF2·H2O, NiF2, SnF2, InF3, ScF3, TiF3, MnF3, CoF3, CrF3, AuF3, FeF3, MnF3, BiF3, and SbF3.

[0130] The above fluoride source may be included in a range of 1 to 3 moles or 1.1 to 2 moles based on 1 mole of the chloroaminesilane compound.

[0131] The above fluoride source can be introduced using an etherification solvent.

[0132] The above ether solvent may be bis(2-methoxyethyl)ether (diglyme), dipropylene glycol dimethyl ether (DMM), tetrahydrofuran (THF), diethyl ether, etc.

[0133] The above ether solvent may be included in a range of 5 to 50 moles or 10 to 40 moles based on 1 mole of the above chloroaminesilane compound.

[0134] The above substitution temperature can be performed at room temperature throughout the entire reaction, for example, at 20 to 30°C.

[0135] The above selective deposition agent can be synthesized according to the following reaction scheme 2 as a specific example.

[0136] [Reaction Equation 2]

[0137]

[0138] Furthermore, the present invention comprises the steps of: depositing and adsorbing the selective deposition agent onto a substrate (wafer); and injecting a Si precursor compound and a reducing agent onto the substrate to form a SiCN or SiN thin film; wherein the SiCN or SiN thin film is formed in a portion where the selective deposition agent is not adsorbed, thereby enabling the effective formation of a selective thin film.

[0139] The selective thin film formation method of the present invention allows the SiCN or SiN thin film to be deposited to a height of at least 30 Å by using the selective deposition agent. Specifically, compared to Comparative Example 1 described later which used monoaminosilane, the use of disilane or disilazane unique to the present invention allows the surface of the SiO2 thin film to form O-SiF2-O bonds, which not only effectively block the deposition of SiCN and / or SiN but also ensures excellent thermal stability and maintains a constant vapor pressure, thereby enabling the stable and uniform formation of the thin film and improving the deposition rate, which can increase productivity.

[0140] The above selective thin film formation method can be carried out, for example, at a deposition temperature of 100 to 1,000°C. In this case, relatively high-temperature deposition is possible, which can improve process efficiency and reduce the thermal decomposition of compounds used in the deposition process, thereby providing excellent effects that greatly improve the stability and productivity of the deposition process.

[0141] The above selective thin film formation method may, for example, be deposited by mixing the selective deposition agent with a solvent as needed. The solvent may, for example, be an organic solvent, and specifically, may be one selected from the group consisting of hexane, octane, tetrahydrofuran (THF), dimethoxyethane (DME), benzene, toluene, dichloromethane (DCM), dichloroethane (DCE), or mesitylene. In this case, there is an advantage in that the viscosity or vapor pressure of the precursor compound can be easily controlled during thin film deposition.

[0142] The above selective thin film formation method may further include, for example, a step of depositing using plasma on a thin film formed on the substrate, in which case a high-quality thin film can be obtained even under deposition conditions of a relatively low temperature. The plasma may be, for example, oxygen plasma, but is not limited thereto.

[0143]

[0144] The selective thin film formation method of the present invention may be implemented by including one or more of the following steps:

[0145] - A step of adsorbing a selective deposition agent to a portion of a target substrate (substrate, etc.);

[0146] - A step of purging the unadsorbed selective deposition agent with an inert gas;

[0147] - A step of forming a thin film region of SiCN or SiN with a height of at least 30 Å in the region excluding the SiO2 thin film region blocked by the selective deposition agent by injecting a precursor compound and a nitriding agent;

[0148] - A step of purging by-products and unreacted substances with an inert gas during the above reaction.

[0149] The above selective thin film formation method may, for example, have the above steps as one cycle and repeat the cycle tens of times or more until a thin film of a desired height is formed. Specifically, the number of cycle repetitions may be 50 to 1000 times, preferably 100 to 300 times, in which case the height of the thin film is appropriately achieved and process efficiency can be increased.

[0150]

[0151] As a specific example, the above selective thin film formation method may be implemented by including the following steps:

[0152] a) a step of introducing a target substrate (substrate, etc.) into a reaction chamber and maintaining it at a firing temperature;

[0153] b) a first purging step of injecting an inert gas into the reaction chamber;

[0154] c) a step of injecting the selective deposition agent of the present invention into the reaction chamber above and adsorbing it to a portion of the substrate;

[0155] d) a secondary purging step of injecting an inert gas into the reaction chamber to leave the selective deposition agent chemically adsorbed on the substrate and remove the selective deposition agent physically adsorbed;

[0156] e) sequentially injecting a precursor compound and a nitrating agent into the reaction chamber to form a SiCN or SiC thin film in an area other than the region occupied by the chemically adsorbed selective deposition agent; and

[0157] f) A third purging step for discharging the reaction by-products and unreacted materials, etc., to the outside of the reaction chamber.

[0158] The height occupied by the above SiO2 thin film region may be lower within a range of 30 Å or less than the height occupied by the above SiCN and / or SiN thin film region.

[0159] The above selective thin film formation method may perform steps a) to f) as one cycle, and the cycle may be repeated. Specifically, the number of cycle repetitions may be 50 to 1000 times, preferably 100 to 300 times, in which case the height of the thin film is appropriately realized and process efficiency can be increased.

[0160] The above selective thin film formation method may be carried out, for example, by chemical vapor deposition (CVD), organometallic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma enhanced vapor deposition (PECVD), atomic layer deposition (ALD), or plasma enhanced atomic layer deposition (PEALD), and preferably by chemical vapor deposition or atomic layer deposition, but is not limited thereto. The above chemical vapor deposition or atomic layer deposition method has the advantage of being able to form a film of uniform height even on a surface with a structure having a large aspect ratio by supplying the raw material to the substrate in a gaseous state, for example, and to form a uniform selective thin film by supplying the selective deposition agent of the present invention at a uniform concentration to large-area or roll-shaped substrates.

[0161] The above deposition temperature may be, for example, 100 to 1,000 ℃, specifically 150 to 500 ℃, preferably 150 to 400 ℃, and more preferably 150 to 350 ℃. In this case, high-temperature deposition is possible, which improves process efficiency and reduces the thermal decomposition of compounds used in the deposition process, thereby providing excellent effects in significantly improving the stability and productivity of the deposition process. In addition, the content of impurities such as carbon in the manufactured thin film can be reduced and crystallinity improved, thereby improving the physical properties of the thin film.

[0162] For example, the above deposition may use a time-division deposition apparatus that supplies deposition materials sequentially.

[0163] As another example, a spatial division deposition apparatus can be used in which a substrate rotates and reciprocates between a space filled with one type of raw material gas and a space filled with another type of raw material gas.

[0164] As another example, if the above substrate is a polymer substrate in the form of a roll, a roll-to-roll deposition apparatus that winds it into a roll shape can be used.

[0165]

[0166] The above Si precursor compound is not limited to conventionally used Si precursor compounds, and examples include TDMAS (trisdimethylaminosilane).

[0167] The above nitrating agent may be one or more selected from nitrogen (N2), hydrazine (N2H4) and ammonia (NH3), for example, but is not limited thereto.

[0168] Specifically, when a nitrating agent such as ammonia or hydrazine is used, a metal nitride thin film such as SiCN or SiN can be formed in the region other than the thin film region occupied by SiO2, where O-SiF2-O is formed on the surface by the selective deposition agent.

[0169] In the above selective thin film formation method, the injection time of the selective deposition agent may be, for example, 1 to 30 seconds, preferably 1 to 20 seconds, and more preferably 2 to 10 seconds, and within this range, the height uniformity of the thin film is improved so that a uniform thin film can be easily manufactured even on a substrate of a complex shape.

[0170] In the above selective thin film forming method, the injection time of the nitriding agent may be, for example, 1 to 40 seconds, preferably 1 to 30 seconds, and more preferably 2 to 10 seconds, and within this range, the physical properties of the thin film are improved due to excellent coverage and uniform coating properties.

[0171]

[0172] The above substrate (wafer) may include, for example, one or more substrates selected from the group consisting of glass, silicon, metal polyester (PE), polyethyleneterephthalate (PET), polyethylenenapthalate (PEN), polycarbonate (PC), polyetherimide (PEI), polyethersulfone (PES), polyetheretherketone (PEEK), and polyimide (PI), but is not limited thereto.

[0173]

[0174] The present invention provides a semiconductor substrate comprising: a substrate; and a selective thin film formed on the substrate; wherein the selective thin film is manufactured by the method described above.

[0175] The above-mentioned surface may have a form such as SiO2, SiOH, etc., for example.

[0176] The above selective thin film can have a deposition-free form of SiCN or SiN by blocking the deposition of SiCN and / or SiN.

[0177] The above thin film may include a SiO2 thin film region and a SiCN and / or SiN thin film region.

[0178] The height occupied by the above SiO2 thin film region may be lower within a range of 30 Å or less than the height occupied by the above SiCN and / or SiN thin film region.

[0179] The surface of the above SiO2 thin film can form O-SiF2-O bonds to block the deposition of SiCN and / or SiN.

[0180] The thin film containing the above-mentioned selective deposition agent may, for example, have a single-layer structure or a multi-layer structure.

[0181] The thin film of the above single-layer structure may be formed, for example, by depositing the above selective deposition agent.

[0182] The above-described multilayer thin film may be a stacked structure formed, for example, by sequentially depositing the above-described selective deposition agent and other precursors.

[0183]

[0184] A semiconductor substrate or semiconductor device including the above thin film can be provided.

[0185] First, in the semiconductor field, examples include gate dielectrics, hard masks, diffusion barriers, and interlayer dielectrics (ILD), but are not limited to these, and can also be applied to manufacturing processes for next-generation devices such as FinFET, GAA (Gate-All-Around), 3D NAND, DRAM, and Logic SoC.

[0186] In addition, in the field of display manufacturing, it is advantageous for forming gate insulating layers, passivation films, and interlayer insulating layers within the structure of TFT (thin-film transistor) devices, and can be utilized in the manufacturing of LTPS, oxide TFT, and AMOLED.

[0187] Furthermore, in the secondary battery industry, it can be applied for the deposition of ceramic coating layers, electrode protective films, or insulating films, and can also be used to form silicon thin films when manufacturing silicon anodes (Si-anodes).

[0188]

[0189] Hereinafter, preferred embodiments are presented to aid in understanding the present invention; however, the following embodiments are merely illustrative of the invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the invention, and that such variations and modifications fall within the scope of the appended claims.

[0190]

[0191] [Example 1]

[0192] Synthesis of fluoroaminodisilane compounds

[0193] [Reaction Equation 1]

[0194]

[0195] According to the above reaction scheme 1, 50 g (0.19 mol) of HCDS (hexachlorodisilane) and 801.24 g (9.30 mol) of hexane (n-hexane) were added to a flame-dried 2 L flask under an anhydrous and inactive atmosphere, and then cooled to -20°C or lower while stirring.

[0196] 93.14 g (0.92 mol) of DIPA (diisopropylamine) was slowly added while maintaining the temperature at -10℃ to 0℃.

[0197] After the addition of DIPA was finished, the temperature was gradually raised to room temperature and stirred for 3 hours. After removing the filtered solvent, 65.18 g of (DIPA)Cl2Si-SiCl2(DIPA) (yield 88%, 0.16 mol) was obtained.

[0198] 65.18 g (0.16 mol) of the obtained (DIPA)Cl2Si-SiCl2(DIPA) was added to a flame-dried 1 L flask in an anhydrous and inactive atmosphere along with 526.94 g (3.93 mol) of Diglyme, and while stirring, 35.30 g (0.20 mol) of antimony trifluoride (SbF3) was slowly added while maintaining the temperature at 20°C to 30°C.

[0199] After the addition was finished, the reaction was completed by stirring at room temperature for 5 hours.

[0200] After the reaction was completed, the filtrate was filtered and vacuum distilled under conditions of 30℃~50℃ / 50torr to obtain 35.37g of (DIPA)F2Si-SiF2(DIPA), a compound of Chemical Formula 3, as the target compound (yield 65%, 0.11mol, GC purity 96.8%).

[0201] 1H-NMR (CDCl3): 1.24ppm (d, 12H, N-(CH-(CH3)2)2), 3.35ppm (m, 2H, N-(CH-(CH3)2)2)

[0202] 29Si-NMR (C6D6): -85ppm (t, Si)

[0203]

[0204] The hydrogen nuclear magnetic resonance (1H-NMR) spectrum for the compound of Chemical Formula 3 above is shown in Fig. 1 below, the TGA and DSC analysis results are shown in Fig. 2 below, and the vapor pressure measurement results are shown in Fig. 3 below.

[0205] As shown in Figure 1 below, it was confirmed that the compound synthesized through Example 1 is Trifluorodiisopropylaminosilane (TFDIPAS).

[0206] As shown in Figures 2 and 3 below, the DSC analysis results of the compound synthesized through Example 1 confirmed decomposition peaks at 145°C (Si-Si) and 175°C (Si-N), and confirmed that the vapor pressure at 50°C was 0.14 torr.

[0207]

[0208] [Example 2]

[0209] Synthesis of fluorosilylaminosilane compounds

[0210] [Reaction Equation 2]

[0211]

[0212] According to reaction scheme 2 above, 230.9 g of n-BuLi (2.5 M in hexane) and 400.46 g of hexane (4.65 mol) were added to a flame-dried 2 L flask under an anhydrous and inactive atmosphere, and the mixture was cooled to below -20°C while stirring. While maintaining the internal temperature between -10°C and 0°C, 150 g of HMDS (hexamethyldisilazane) (0.93 mol) was slowly added. After the addition of HMDS was finished, the temperature was slowly raised to room temperature and stirred for 8 hours.

[0213] 157.9 g (0.93 mol) of SiCl4 and 536.11 g (7.43 mol) of THF were added to a flame-dried 3 L flask under an anhydrous and inactive atmosphere, and the mixture was cooled to below -20°C while stirring. While maintaining the internal temperature between -10°C and 0°C, the previously reacted Li(btsa) solution was slowly added. After the addition was finished, the temperature was slowly raised to room temperature and stirred for 5 hours. Then, the solvent was removed under reduced pressure, extracted with n-hexane, and filtered.

[0214] After removing the solvent from the filtrate under reduced pressure, 243.8 g of Cl3Si(btsa) Trichloro(bis(trimethyl)silylamine) was obtained (yield 89%, 0.83 mol).

[0215] After obtaining, 243.8 g (0.83 mol) of Cl3Si(btsa) was added to a flame-dried 2 L flask in an anhydrous and inactive atmosphere along with 503.6 g (6.62 mol) of dipropylene glycol dimethyl ether (DMM), and while stirring, 177.5 g (0.99 mol) of antimony trifluoride (SbF3) was slowly added while maintaining the temperature at 20°C to 30°C.

[0216] After the addition was finished, the reaction was completed by stirring at room temperature for 12 hours. After the reaction was completed, the filtrate was filtered and the liquid was subjected to vacuum distillation at room temperature and 600 torr to obtain 132 g of F3SiN(SiMe3)2 (yield 65.0%, 0.83 mol, GC purity 99.5%), which is the compound represented by Chemical Formula 4 as the target compound.

[0217] 1H-NMR (CDCl3): 0.27ppm (s, 18H, N-(Si(CH3)2)2)

[0218] 29Si-NMR (CDCl3): -83ppm (q, SiF3), 8.3ppm (s, N-(Si(CH3)2)2)

[0219]

[0220] Figures 4 and 5 below show the hydrogen nuclear magnetic resonance (1H-NMR) spectrum of the compound synthesized according to Example 2, and Figure 6 below shows the TGA and DSC analysis results for the compound of Figure 4.

[0221] As shown in Figures 4 and 5 below, it was confirmed that F3SiN(SiMe3)2 was synthesized, and as shown in Figure 6 below, a decomposition peak at 230℃ was confirmed as a result of DSC analysis.

[0222]

[0223] [Test Example 1: Evaluation of Adsorption Energy and Contact Angle]

[0224] The results of the preliminary evaluation of the adsorption energy with each substrate using computational simulation for the compounds synthesized in Examples 1 and 2 above, using Software: Gaussian 16, Method: DFT-D3 / B3LYP, Basis Sets: 6-31+G(d,p), are shown in Table 1 below.

[0225] SiO2 Ads (KJ / mol)SiN Ads (KJ / mol)Δ Ads (KJ / mol) Example 1-116.57-82.44-34.13 Example 2-58.29-41.48-16.81

[0226] In addition, the inhibitor prepared in Examples 1 and 2 above was dipped into actual SiO2, and the water contact angle was measured to evaluate the change in hydrophilicity or hydrophobicity of the substrate surface.

[0227] Contact angle measurements were performed using Phoenix MT(T) equipment. After dropping 3 μl of deionized water onto the substrate surface, the contact angle was measured by photographing the shape of the water droplet using a CCD camera.

[0228] The measured contact angle used was the average value of the left and right contact angles calculated by the equipment software, and the average value was shown in Table 2 below after repeating measurements at different locations on the substrate three or more times under the same conditions.

[0229]

[0230] Through the computational simulation results in Table 1 above, the selectivity for SiO2 substrates compared to SiN was confirmed.

[0231]

[0232] Furthermore, from the WCA results of Table 2 above, the contact angles of the SiO2 substrates treated with the compounds prepared in Example 1 or 2 prior to injecting the silane precursor compounds were 56.24° and 113.08°, respectively.

[0233] For reference, the contact angle of an untreated SiO2 substrate with the compound prepared in Example 1 or 2 was 43.83°, and it was confirmed that the contact angle significantly increased when the compound prepared in Example 1 or 2 was used.

[0234] From these results, it can be seen that the compounds prepared in Examples 1 and 2 adsorbed onto the SiO2 surface to form an organic inhibitor layer that increases the hydrophobicity of the surface. Thus, it is expected that the inhibitor layer formed on the surface effectively shields the active OH groups on the substrate surface.

[0235]

[0236] [Test Example 2: Selective Deposition Test Between SiO2 Substrate and SiCn Substrate]

[0237] SiO2 and SiCN substrates were used to confirm the selective deposition of silicon-containing thin films. Atomic Layer Deposition (ALD) was adopted as the deposition method. The overall process proceeded in the following order: starting with surface treatment of the substrates, a step of selectively adsorbing the compound of Example 1 or 2 to prevent nucleation, and a step of selectively manufacturing a silicon-containing thin film. Through this process, thin film formation was excluded on the SiO2 surface, while selective silicon-containing thin film growth was induced only on the SiCN surface.

[0238] Specifically, the surface treatment of the substrates was performed by immersing the surface of each SiO2 and SiCN substrate in a 0.5 wt% HF solution for 1 minute, followed by sequentially washing and drying in isopropyl alcohol and DI water.

[0239] Then, the precursor in the selective adsorption step was the compound prepared in Example 2 above, and the substrate temperature was maintained at 150°C.

[0240] The vaporized precursor was transported into the chamber using nitrogen gas as the carrier gas and selectively adsorbed only onto the SiO2 substrate, after which a purging process was performed using nitrogen gas.

[0241] The above atomic layer deposition process was repeated for a certain period as one cycle, and the detailed process conditions are shown in Table 3 below.

[0242] Precursor Substrate Temperature Process Pressure Precursor Injection Purge Cycle °C Torr Nitrogen Bubble Time Nitrogen Time Cycle sc cm sec sc cm sec Example 2 1 5 0 4 5 0 6 0 2 0 0 3 0 5

[0243] At this time, immediately after the selective adsorption process of the above compound, the silicon substrates were heated to 600°C for the manufacture of a silicon-containing thin film and then maintained at a constant temperature.

[0244] To form a silicon-containing thin film, a SiCl4 compound was used as the precursor and ammonia was used as the reactant. The chamber pressure was maintained at 1 torr, and the vaporized precursor was transported into the chamber using nitrogen gas as the carrier. The precursor was not adsorbed on the SiO2 substrate where the previously adsorbed selective adsorption compound had been adsorbed, but was selectively adsorbed only on the SiCN substrate. Subsequently, a purging process was performed using nitrogen gas.

[0245] The reaction process was carried out using ammonia as the reaction gas, and a purging process was performed using nitrogen gas to remove reaction byproducts. The above atomic layer deposition process was repeated for a certain period as one cycle, and the detailed process conditions are as shown in Table 4 below.

[0246] Precursor Substrate Temperature Process Pressure Precursor Injection Purge Reaction Gas Purge Cycle °C Torr Nitrogen Bubble Time Nitrogen Time Ammonia Time Nitrogen Time Cycle sccm sec sccm sec sccm sec sccm sec SiCl460011001030005600020300010100SiCl460011001030005600020300010150SiCl460011001030005600020300010200

[0247] Selective silicon-containing thin films were finally formed on each SiO2 and SiCN substrate through the above process steps, and their thickness was measured using an Ellipsometry analysis instrument. The results are shown in Table 5 and Figure 7 below.

[0248] Silicon-containing thin film thickness according to process cycle substrate Difference in silicon-containing thin film thickness between substrates CycleSiO2SiN[Å][Å][Å]1000424215026462200418746

[0249] As shown in the table above, according to the present invention, when a structure including a fluoro group directly connected to a silicon element is included in a selective deposition agent, not only is storage stability increased by reducing self-reactivity, but the volatility of the functional group desorbed after deposition is high, thereby reducing the amount of residue on the substrate and simultaneously realizing high decomposition temperature and film formation temperature characteristics. Including this, it is possible to manufacture a uniform thin film by exhibiting improved thermal stability during a high-temperature deposition process and maintaining a constant composition by exhibiting a constant vapor pressure, and thus improve productivity by increasing the deposition rate. In particular, compared to conventional SiN films, SiCN films have lower dielectric constant and introduce carbon, which provides advantages such as stress dispersion, improved film quality, and inhibition of degradation, making them suitable for various fields such as semiconductor processes, secondary batteries, and display manufacturing processes.

Claims

1. A selective deposition agent characterized by comprising a disilane-based compound having a structure containing a fluoro group directly connected to a silicon atom.

2. In Paragraph 1, The selective deposition agent has a structure of XnAa(NR1R2)mSi-SiXnAaBb [Formula 1], wherein X is a fluorine atom, A, R1, and R2 are each independently an alkyl group, alkenyl group, allyl group, silylamino group, or heterocyclic group having 1 to 6 carbon atoms, B is a silylalkyl group or NR1R2, n is an integer from 1 to 3, and a, m, or b are each integers from 0 to 3.

3. In Paragraph 1, The selective deposition agent has the structure of Xn(NR1R2)mAaSi-NR3-SiAaXn(NR1R2)m [Formula 2], wherein X is a fluorine atom and may be, A, R1, and R2 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an allyl group, a silylamino group, or a heterocyclic group, R3 is H, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an allyl group, a silylamino group, or a heterocyclic group, n is an integer from 1 to 3, and a or m is each an integer from 0 to 3.

4. In Paragraph 2 or 3, A selective deposition agent characterized in that n+m+a+b in Equation 1 above, or n+m+a in Equation 2 above, is each 3.

5. In Paragraph 1, The selective deposition agent is characterized by being one or more selected from compounds represented by the following chemical formulas 1 to 4. [Chemical Formulas 1 to 4] 6. In Paragraph 1, The above selective deposition agent is characterized by having a To (temperature at the point where Residue=0%) of 200 ℃ or higher during TGA analysis, a To (temperature at the point where Residue=0%) of 200 to 300 ℃ during TGA analysis, or a heat flow peak appearing within 100 to 300 ℃ during DSC analysis.

7. A method for synthesizing a selective deposition agent comprising: a synthesis step of a chloroamine disilane compound or a chloroamine silane compound; and a fluoride substitution step.

8. In Paragraph 7, A method for synthesizing a selective deposition agent, characterized in that the chloroamine disilane compound synthesis step is performed using a chlorodisilane compound and an alkylamine compound in an organic solvent.

9. In Paragraph 7, A method for synthesizing a selective deposition agent, characterized in that the chloroaminesilane compound synthesis step above is performed using a chlorosilane compound and a compound having a Si-OH structure under alkyl lithium and an organic solvent.

10. A step of depositing and adsorbing the selective deposition agent of claim 1 onto a substrate; and The method includes the step of forming a SiCN or SiN thin film by injecting a Si precursor compound and a nitriding agent onto the above substrate; A method for manufacturing a selective thin film characterized in that the above SiCN or SiN thin film is formed in a portion where the above selective deposition agent is not adsorbed.

11. In Paragraph 10, A method for manufacturing a selective thin film characterized in that the above deposition is carried out by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

12. A substrate; and an optional thin film formed on the substrate; comprising, A semiconductor substrate characterized by the above-mentioned selective thin film being manufactured by the method according to claim 10.

13. In Paragraph 12, A semiconductor substrate characterized in that the selective thin film is in a deposition-free form of SiCN or SiN.

14. In Paragraph 12, A semiconductor device characterized by including the above-mentioned semiconductor substrate.

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