Film-forming composition containing a group 4 metal element-containing precursor compound, and method for forming a film using the same

Abstract

The present invention relates to a film-forming composition containing a Group 4 metal element-containing precursor compound, and a method for forming a Group 4 metal element-containing film using the same. The use of the film-forming composition containing the Group 4 metal element-containing precursor compound of the present invention achieves self-limiting film growth by atomic layer deposition (ALD) in a wide temperature range from low to high, enabling the formation of Group 4 metal element-containing films for various purposes at various process temperatures. In particular, according to the method for forming a Group 4 metal element-containing film of the present invention, the ALD film formation rate (GPC) is constant over a wide temperature range, and a Group 4 metal element-containing film of uniform thickness can be formed even on a surface having a groove with a large aspect ratio. Therefore, the above method can be advantageously used in the manufacture of various semiconductor devices such as DRAMs and 3D NAND flash memories.

Description

[Technical field]

[0001] The present invention relates to a film-forming composition containing a Group 4 metal element-containing precursor compound, and a method for forming a film using the same. [Background technology]

[0002] A Group 4 metal element-containing film, particularly a Group 4 metal oxide film having a high dielectric constant, is one of the essential thin films for operating non-memory semiconductor devices such as logic devices, and memory semiconductor devices such as DRAM, flash memory, resistive memory (ReRAM), ferroelectric memory (FeRAM), and phase-change memory (PCRAM).

[0003] In particular, such Group 4 metal element-containing films are used in state-of-the-art technology of organic light-emitting diodes (OLEDs) in the display field, as well as in gate insulating films of memory devices, high-k dielectric films of capacitors, and the like.

[0004] Meanwhile, in the semiconductor and non-semiconductor fields, various products having complex shapes such as high aspect ratios and three-dimensional structures are being developed. As a result, there is a demand for a film-forming composition containing a Group 4 metal element-containing precursor compound for forming a Group 4 metal element-containing film that can be used in atomic layer deposition (ALD), is suitable for process temperatures in various application fields, and can overcome high step ratios. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] J. Niinisto et al., "Novel mixed alkylamido-cyclopentadienyl precursors for ALD of ZrO2 thin films", Journal of Materials Chemistry 2008, 18(43), 5243(https: / / doi.org / 10.1039 / b810922b) DISCLOSURE OF THEINVENTION technical challenges

[0006] The technical problem to be solved by the present invention is to provide a method for forming a Group 4 metal element-containing film, which allows the deposition rate (GPC), which is the film growth per ALD gas supply cycle, to remain constant over a wide temperature range, and allows the formation of a uniform film with excellent step coverage even on surfaces having complex shapes.

[0007] Another technical problem to be solved by the present invention is to provide a film-forming composition containing a Group 4 metal element-containing precursor compound having a specific structure.

[0008] However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems will be clearly understood by those skilled in the art from the following description.

[0009] In order to achieve the above object, the present invention provides a method for forming a Group 4 metal element-containing film, comprising the step of reacting a film-forming composition containing a Group 4 metal element-containing precursor compound represented by the following formula 1 with a reactive gas to form a Group 4 metal element-containing film on a substrate.

[0010] [ka]

[0011] In formula 1, M is Zr or Hf, R 1 is a methyl group, and R 2 is a linear or branched chain C 3 ~C 4 alkyl groups; R 3 ~R 8 each independently represents a linear or branched chain C 1 ~C 4 The alkyl group is selected from the group consisting of:

[0012] Further, there is provided a film-forming composition comprising the Group 4 metal element-containing precursor compound represented by the above formula 1.

[0013] By using the film-forming composition containing the Group 4 metal element-containing precursor compound of the present invention, the self-limiting ALD film growth can be achieved over a wide temperature range, especially at high temperatures, and thus it is possible to form Group 4 metal element-containing films for various applications at various process temperatures.

[0014] In particular, according to the method for forming a Group 4 metal element-containing film of the present invention, since the GPC does not change over a wide range of temperatures, from low to high, it is possible to form a Group 4 metal element-containing film of uniform thickness even on a surface having a groove with a large aspect ratio, and therefore the method can be advantageously used for manufacturing various semiconductor devices such as DRAMs and 3D NAND flash memories. [Brief description of the drawings]

[0015] [Figure 1] 1 is a graph for comparing 1H-NMR spectra of hafnium (Hf)-containing precursor compounds prepared according to Example 3 of the present invention and Comparative Example 5. [Diagram 2] 1 is a graph showing GPC at temperatures ranging from 250° C. to 400° C. when a zirconium (Zr)-containing film is formed using the film-forming compositions of Example 1 and Comparative Examples 1, 3, and 4 of the present invention. [Diagram 3] 1 is a graph showing GPC at temperatures ranging from 250° C. to 450° C. when a hafnium (Hf)-containing film is formed using the film-forming compositions of Example 3 and Comparative Example 2 of the present invention. [Figure 4] 1 shows transmission electron microscope (TEM) images confirming step coverage of films formed at 300° C. using the film-forming compositions of Example 1 of the present invention and Comparative Examples 1, 3, and 4. [Diagram 5] 1 shows transmission electron microscope (TEM) images confirming the step coverage of films formed at 340° C. and 360° C. using the film-forming compositions of Example 1 and Comparative Examples 3 and 4 of the present invention. [Figure 6]1 shows transmission electron microscope (TEM) images confirming the step coverage of films formed at 350° C. and 400° C. using the film-forming compositions of Example 3 and Comparative Example 2 of the present invention. BEST MODE FOR CARRYING OUT THEINVENTION

[0016] The application is described in more detail hereinafter.

[0017] Advantages and features of the present invention and methods for achieving them will become apparent with reference to the embodiments described herein below. However, the present invention is not limited to the embodiments described below, but may be embodied in various different forms. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. The present invention is defined solely by the claims.

[0018] Furthermore, in this specification, when a component is referred to as being formed "on" another component, it does not only mean that one component is formed directly "on" the other component, but also that the other component(s) are interposed therebetween.

[0019] In this specification, when a part is referred to as "comprising" an element, unless otherwise specified, it should be understood that the part does not exclude other elements, but may also include other elements.

[0020] All numbers and expressions relating to amounts of ingredients, reaction conditions, and the like used in this specification should be understood as being modified by the term "about" unless otherwise specified.

[0021] In this specification, the terms "membrane" and "thin film" refer to both "membrane" and "thin film" unless otherwise specified.

[0022] As used herein, the term "alkyl" or "alkyl group" includes straight-chain or branched-chain alkyl groups and all possible isomers thereof. For example, an alkyl or alkyl group may be a methyl group (Me), an ethyl group (Et), a normal propyl group (Nl), or a propyl group (Pt). n Pr), isopropyl group ( i Pr), normal butyl group ( n Bu), isobutyl group ( i Bu), tert-butyl group (tert-Bu, t Bu), sec-butyl group ( sec Bu) and the like, as well as isomers thereof, but are not limited thereto.

[0023] [Method for forming a Group 4 metal element-containing film] According to an embodiment of the present invention, there is provided a method for forming a Group 4 metal element-containing film, comprising the step of reacting a film-forming composition containing a Group 4 metal element-containing precursor compound represented by the following formula 1 with a reactive gas to form a Group 4 metal element-containing film on a substrate.

[0024] [ka]

[0025] In formula 1, M is Zr or Hf, R 1 is a methyl group, and R 2 is a linear or branched chain C 3 ~C 4 alkyl groups; R 3 ~R 8 each independently represents a linear or branched chain C 1 ~C 4 The alkyl group is selected from the group consisting of:

[0026] In the method for forming a Group 4 metal element-containing film according to an embodiment of the present invention, a film-forming composition containing a Group 4 metal element-containing precursor compound represented by the above formula 1 is used, so that it is possible to form a Group 4 metal element-containing film by chemical vapor deposition (CVD) or ALD at a constant GPC in a wide temperature range, including high and low temperatures.

[0027] In particular, the Group 4 metal element-containing precursor compound represented by formula 1 may be a single-component structure. Here, the term "single-component" refers to a substance that does not contain structural isomers. It does not necessarily mean a 100% pure substance. For example, it may contain 5% or less of impurities. Furthermore, the term "impurities" may refer to all substances other than the Group 4 metal element-containing precursor compound represented by formula 1.

[0028] Specifically, the Group 4 metal element-containing precursor compound represented by formula 1 is 1 When analyzed by H-NMR spectroscopy, the precursor may have a single composition structure (single substance structure) that does not contain structural isomers or mixtures thereof, and the impurity content is, for example, 5% or less, 3% or less, 2% or less, 1% or less, or 0.5% or less. Therefore, the precursor compound containing a Group 4 metal element represented by formula 1 has a high purity of 95% or more, exists in a liquid state at room temperature which is advantageous for the preparation process, and has excellent thermal stability, so that it is possible to easily form various Group 4 metal element-containing films.

[0029] Furthermore, it is possible to form a uniform film with excellent coverage even on a substrate having a pattern (groove) on its surface, a porous substrate, a plastic substrate, or a substrate having a complex shape in a three-dimensional structure, thereby making it possible to provide a high-quality Group 4 metal element-containing film. Therefore, it has technical significance in that it can be advantageously used for various applications in the field of semiconductor devices and can exhibit excellent characteristics.

[0030] Specifically, according to an embodiment of the present invention, a film-forming composition containing a Group 4 metal element-containing precursor compound is used to form a Group 4 metal element-containing film, specifically a zirconium (Zr)-containing film or a hafnium (Hf)-containing film, at a temperature of, for example, 150° C. to 500° C., 200° C. to 500° C., 200° C. to 450° C., 250° C. to 450° C., 250° C. to 400° C., 250° C. to 380° C., 250° C. to 360° C., or 250° C. to 350° C. When formed by ALD at a temperature of 0°C or 250°C to 340°C, the rate of change of GPC (ΔGPC, %) is close to zero or small, for example, 30% or less, less than 30%, 29% or less, 25% or less, 20% or less, 18% or less, 16% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, or 4% or less.

[0031] The Group 4 metal element-containing precursor compound represented by formula 1 is described in detail in the "Film-forming composition" section below.

[0032] A method for forming a Group 4 metal element-containing film according to an embodiment of the present invention includes the steps of providing at least a portion of a substrate in a reaction chamber (first step), supplying a gaseous film-forming composition to the reaction chamber (second step), and supplying a reactive gas to the reaction chamber (third step).

[0033] Furthermore, according to the method for forming a Group 4 metal element-containing film, the gas supply cycle including the second step and the third step can be repeated multiple times, for example, several times, tens of times, hundreds of times, or thousands of times, to form a Group 4 metal element-containing film having a desired thickness.

[0034] In addition, between the second and third steps, argon (Ar) gas, nitrogen (N 2 The method may further include a step of supplying an inert gas such as argon (Ar) gas, nitrogen (N) gas, or the like to the reaction chamber to remove the film forming composition (gas) remaining in the reaction chamber. 2The method may further include supplying an inert gas, such as a .OMEGA.) gas, to the reaction chamber to remove any remaining reaction gas in the reaction chamber.

[0035] Specifically, a method for forming a Group 4 metal element-containing film may include a step (a first step) of providing at least a portion of a substrate in a reaction chamber.

[0036] The substrate may be one selected from, but not limited to, conventional semiconductor wafers, compound semiconductor wafers, and plastic substrates (PI, PET, PES, and PEN).Furthermore, substrates with holes or grooves may be used, and porous substrates with large surface areas may be used.

[0037] In particular, for example, a Group 4 metal element-containing film having a uniform thickness of several nanometers (nm) to several micrometers (μm) can be formed on a substrate having a pattern (groove) on its surface, a porous substrate, or a plastic substrate in various temperature ranges of 150°C to 500°C, and an excellent effect is exhibited in that a Group 4 metal element-containing film can be formed uniformly on the deepest surface and upper surface of a fine pattern (groove) on a substrate, the fine pattern (groove) having at least one fine groove having an aspect ratio of 1 or more, for example, about 1 to 50 or more, and a width of 1 μm or less, for example, about 1 μm to 10 nm or less.

[0038] The method for forming a Group 4 metal element-containing film may include a step (second step) of supplying a film-forming composition including a Group 4 metal element-containing precursor compound in a gaseous state to a reaction chamber.

[0039] The film-forming composition containing the Group 4 metal element precursor compound is delivered in a gaseous state to form a Group 4 metal element-containing oxide film on a substrate. Additionally, film-forming compositions containing other components may be used in conjunction with the film-forming composition to form a Group 4 metal element-containing composite metal oxide film or nanolaminate film, such as Zr-Si-O, Hf-Si-O, Hf-Zr-O, ZrO 2 / Al 2 O 3 / ZrO 2 , or ZrO2 / Al 2 O 3 / TiO 2 A film of the above can be formed.

[0040] Specifically, when a film-forming composition containing a Group 4 metal element-containing precursor compound is supplied to a reaction chamber, the film-forming composition containing a Group 4 metal element-containing precursor compound is supplied onto a substrate using a carrier gas or a dilution gas, and a Group 4 metal element-containing film can be formed at a process temperature of 150°C to 500°C.

[0041] In addition, argon (Ar), nitrogen (N 2 ), helium (He), and hydrogen (H 2 It is preferred to use a single gas or a mixture of gases selected from the group consisting of:

[0042] Furthermore, the method of supplying the film-forming composition containing the Group 4 metal element-containing precursor compound to the reaction chamber may be at least one method selected from the group consisting of a bubbling method in which the film-forming composition containing the Group 4 metal element-containing precursor compound is forcibly vaporized using a carrier gas or a dilution gas, a liquid delivery system (LDS) method in which the film-forming composition is supplied in a liquid phase at room temperature and vaporized through a vaporizer, a vaporization flow control (VFC) method in which the film-forming composition containing the precursor compound is directly supplied using its vapor pressure, and a bypass method. Furthermore, a method of supplying a gaseous film-forming composition in chemical vapor deposition (CVD) or ALD can be applied to the present invention.

[0043] The method for forming a Group 4 metal element-containing film according to the embodiment of the present invention may include a step (third step) of supplying a reaction gas to the reaction chamber.

[0044] According to the method for forming a Group 4 metal element-containing film, a Group 4 metal element-containing oxide film (ZrO 2 , HfO 2 ) or a composite metal oxide film containing a Group 4 metal element (ZrSiO x , ZrAlO x , ZrHfOx , ZrHfSiO x , ZrHfAlO x , ZrHfSiAlO x To deposit the SiO2 (ZrON, etc.), water vapor (H 2 O), oxygen (O 2 ), oxygen plasma (O 2 plasma), nitric oxide (NO, N 2 O), nitric oxide plasma (N 2 O plasma), oxygen nitrate (N 2 O 2 ), hydrogen peroxide (H 2 O 2 ), and ozone (O 3 ) can be used as the reaction gas.

[0045] Further, in order to deposit a Group 4 metal element-containing nitride film or a Group 4 metal element-containing composite metal nitride film, ammonia (NH 3 ), ammonia plasma (NH 3 Plasma), Hydrazine (N 2 H 4 ), and nitrogen plasma (N 2 At least one selected from the group consisting of a plasma may be used during the deposition.

[0046] According to an embodiment of the present invention, a film-forming composition containing a Group 4 metal element-containing precursor compound is supplied in a gaseous state to form at least one film selected from the group consisting of a Group 4 metal element-containing nitride film, a Group 4 metal element-containing carbide film, and a Group 4 metal element-containing composite metal film on a substrate.

[0047] For example, a film-forming composition containing a Group 4 metal element-containing precursor compound is supplied in a gaseous state, and a Group 4 metal element-containing film, in particular a Group 4 metal element-containing oxide film, a Group 4 metal element-containing composite metal oxide film, a Group 4 metal element-containing nitride film, or a Group 4 metal element-containing composite metal nitride film is formed on at least a portion of the surface of a substrate by CVD or ALD.

[0048] The method for forming the Group 4 metal element-containing film may use any method and / or apparatus known in the art to which the present invention pertains, and may be carried out using one or more additional reaction gases, etc., as necessary.

[0049] The deposition method of the Group 4 metal element-containing film may be performed by CVD, such as metal-organic chemical vapor deposition (MOCVD), or by ALD. MOCVD or ALD may be performed using deposition equipment, deposition conditions, and reaction gases known in the art.

[0050] [Group 4 metal element-containing film] According to an embodiment of the present invention, there is provided a Group 4 metal element-containing film formed by a method for forming a Group 4 metal element-containing film.

[0051] The Group 4 metal element-containing film may have a thickness of about 1 nanometer (nm) to several micrometers (μm) and may be applied in various ways depending on the intended use. Specifically, the Group 4 metal element-containing film may be formed to a thickness in the range of 1 nm to 500 nm.

[0052] The Group 4 metal element-containing film may be formed on a substrate (or a circuit board).

[0053] The substrate is as described above.

[0054] The Group 4 metal element-containing films according to the embodiments of the present invention are formed using a composition including a Group 4 metal element-containing precursor compound having a specific structure, and thus have high quality with stable and consistent physical properties and excellent step coverage.

[0055] The Group 4 metal element-containing film may be at least one selected from the group consisting of a Group 4 metal element-containing oxide film, a Group 4 metal element-containing complex metal oxide film, a Group 4 metal element-containing nitride film, and a Group 4 metal element-containing complex metal nitride film. Specifically, the Group 4 metal element-containing film may include at least one selected from the group consisting of a Group 4 metal element-containing oxide film and a Group 4 metal element-containing complex metal oxide film.

[0056] Furthermore, the Group 4 metal element-containing film is, for example, Zr-Si-O, Hf-Si-O, Hf-Zr-O, ZrO 2 / Al 2 O 3 / ZrO 2 , or ZrO 2 / Al 2 O 3 / TiO 2 The nano-laminate film may include

[0057] Furthermore, the Group 4 metal element-containing film can have extremely good step coverage.

[0058] For example, when an oxide or nitride film having a thickness of about 5 nm to 20 nm is formed in a trench having an aspect ratio of 10:1 or more by ALD at a process temperature of about 300° C. or more using a film forming composition according to an embodiment of the present invention, the thickness deviation calculated by measuring the film thickness at the top, center, and bottom is very small, indicating an extremely excellent step coverage (%). In this case, the step coverage refers to the ratio of the bottom thickness to the top thickness (bottom thickness / top thickness)×100).

[0059] Specifically, film forming compositions according to embodiments of the present invention may have a step coverage of 80% or more, 82% or more, 85% or more, 90% or more, 92% or more, 93% or more, 95% or more, or 96% or more.

[0060] In particular, when forming an oxide or nitride film in a trench having a large aspect ratio, it is difficult to form a film of a uniform thickness because the thickness deviation of the film formed from the top to the bottom is large. However, the film forming composition according to the embodiment of the present invention can form a film of a uniform thickness even in a trench having a large aspect ratio. Therefore, it is more effective in manufacturing various semiconductor devices such as DRAM and 3D NAND flash memory.

[0061] More specifically, when a hafnium (Hf)-containing oxide film having a thickness of about 6 to 7 nm is formed on a substrate having a titanium nitride (TiN) film formed in a groove having an aspect ratio of 11:1 by ALD at process temperatures of about 350° C. and about 400° C. using a film-forming composition according to an embodiment of the present invention, the step coverage (%) calculated by measuring the thickness of the hafnium (Hf)-containing oxide film in the transmission electron microscope (TEM) photographs of the top, center, and bottom of the groove shown in FIG. 6 can be extremely excellent and equal to or greater than a specific value.

[0062] According to one embodiment, when forming a Group 4 metal element-containing film on a substrate having an aspect ratio of 11:1 at a temperature of about 350° C., the Group 4 metal element-containing film, e.g., a hafnium (Hf)-containing oxide film, can have a step coverage (%) of, for example, 80% or more, 82% or more, 85% or more, 90% or more, 92% or more, 93% or more, 95% or more, or 96% or more.

[0063] Furthermore, when forming a Group 4 metal element-containing film on a substrate having an aspect ratio of 11:1 at a temperature of about 400° C., the Group 4 metal element-containing film, e.g., a hafnium (Hf)-containing oxide film, can have a step coverage (%) of, for example, 85% or more, 90% or more, 92% or more, 93% or more, 95% or more, 96% or more, 97% or more, or 98% or more.

[0064] Furthermore, when a zirconium (Zr)-containing oxide film having a thickness of about 12 to 15 nm is formed on a substrate having a silicon oxide film formed in a groove having an aspect ratio of 20:1 by ALD at process temperatures of about 340° C. and about 360° C. using the film-forming composition according to an embodiment of the present invention, the step coverage (%) calculated by measuring the thickness of the zirconium (Zr)-containing oxide film in the transmission electron microscope (TEM) photographs of the upper, middle, and lower parts of the groove shown in FIG. 4 and FIG. 5 can be extremely excellent and equal to or greater than a specific value.

[0065] According to one embodiment, when forming a Group 4 metal element-containing film on a substrate having an aspect ratio of 20:1 at a temperature of about 300° C., the Group 4 metal element-containing film, e.g., a zirconium (Zr)-containing oxide film, can have a step coverage (%) of, for example, 80% or more, 82% or more, 85% or more, 90% or more, 92% or more, 93% or more, 95% or more, or 96% or more.

[0066] Furthermore, when forming a Group 4 metal element-containing film on a substrate having an aspect ratio of 20:1 at a temperature of about 340° C., the Group 4 metal element-containing film, e.g., a zirconium (Zr)-containing oxide film, can have a step coverage (%) of, for example, 80% or more, 82% or more, 85% or more, 90% or more, 92% or more, 93% or more, 95% or more, or 96% or more.

[0067] Furthermore, when forming a Group 4 metal element-containing film on a substrate having an aspect ratio of 20:1 at a temperature of about 360° C., the Group 4 metal element-containing film, e.g., a zirconium (Zr)-containing oxide film, can have a step coverage (%) of, for example, 85% or more, 90% or more, 92% or more, 93% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.

[0068] When the Group 4 metal element-containing film has a step coverage rate (%) that satisfies the above range, a high step ratio and fine thickness control become possible, and the film can be advantageously used for manufacturing various semiconductor devices such as DRAMs and 3D NAND flash memories.

[0069] [Film forming composition] The film-forming composition according to the embodiment of the present invention may contain a Group 4 metal element-containing precursor compound represented by the following formula 1:

[0070] [ka]

[0071] In formula 1, M is Zr or Hf, R 1 is a methyl group, and R 2 is a linear or branched chain C 3 ~C 4 alkyl groups; R 3 ~R 8 each independently represents a linear or branched chain C 1 ~C 4 The alkyl group is selected from the group consisting of:

[0072] Since the film-forming composition according to the embodiment of the present invention contains the compound represented by formula 1, when forming a film at a process temperature in a wide range of temperatures, such as 250°C to 400°C, the rate of change in GPC with respect to temperature, represented by the following formula A (ΔGPC, %), may be small, such as 30% or less, less than 30%, 25% or less, 20% or less, 18% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 10% or less, 8% or less, 7% or less, 6% or less, or 5% or less.

[0073]

number

[0074] In formula A, GPC 250 is GPC at 250 °C, and GPC temp is the GPC at process temperature.

[0075] Specifically, according to an embodiment of the present invention, when a film is formed using the film-forming composition at a process temperature of, for example, 250°C to 320°C, the rate of change of GPC with respect to temperature (ΔGPC, %) may be small, for example, 30% or less, less than 30%, 25% or less, 20% or less, 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1.5% or less, or 1% or less.

[0076] According to another embodiment of the present invention, when a film is formed using the film-forming composition at a process temperature of, for example, 250°C to 340°C, the rate of change of GPC with respect to temperature (ΔGPC, %) may be small, for example, 30% or less, less than 30%, 25% or less, 20% or less, less than 20%, 18% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 10% or less, 8% or less, 7% or less, or 6% or less.

[0077] According to another embodiment of the present invention, when a film is formed using the film-forming composition at a process temperature of, for example, 250°C to 360°C, the rate of change of GPC with respect to temperature (ΔGPC, %) may be small, for example, 30% or less, less than 30%, 25% or less, 20% or less, 18% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 10% or less, or 9% or less.

[0078] According to another embodiment of the present invention, when a film is formed using the film-forming composition at a process temperature of, for example, 250°C to 380°C, the rate of change in GPC with respect to temperature (ΔGPC, %) may be small, for example, 30% or less, less than 30%, 25% or less, 20% or less, 18% or less, 15% or less, 13% or less, or 12% or less.

[0079] According to another embodiment of the present invention, when a film is formed using the film-forming composition at a process temperature of, for example, 300° C. to 360° C., the rate of change in GPC with respect to temperature (ΔGPC, %) may be as small as 30% or less, less than 30%, 25% or less, 20% or less, 18% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 10% or less, 8% or less, 7% or less, 6% or less, or 5% or less. 250 Instead of GPC 300 (i.e., GPC at 300° C.) may be used for the calculation.

[0080] According to another embodiment of the present invention, when a film is formed using the film-forming composition at a process temperature of, for example, 330° C. to 390° C., the rate of change in GPC with respect to temperature (ΔGPC, %) may be small, for example, 30% or less, less than 30%, 25% or less, 20% or less, 18% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 8% or less, 7% or less, 6% or less, or 5% or less. 250 Instead of GPC 330 (i.e., GPC at 330° C.) may be used for the calculation.

[0081] According to another embodiment of the present invention, when a film is formed using the film-forming composition at a process temperature of, for example, 360° C. to 400° C., the rate of change in GPC with respect to temperature (ΔGPC, %) may be small, for example, 30% or less, less than 30%, 25% or less, 20% or less, 18% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, or 3% or less. 250 Instead of GPC 360 (i.e., GPC at 360° C.) may be used for the calculation.

[0082] More specifically, the film-forming composition according to the embodiment of the present invention contains a Group 4 metal element-containing precursor compound represented by the following formula 2. When a zirconium (Zr)-containing film is formed by ALD at a process temperature of 250° C. to 380° C., the rate of change of GPC with respect to temperature represented by the above formula A (ΔGPC, %) may be small, for example, 30% or less, less than 30%, 25% or less, 20% or less, 18% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, or 4% or less.

[0083] [ka]

[0084] In formula 2, R 1 is a methyl group, and R 2 is a linear or branched chain C 3 ~C 4 alkyl groups; R 3 ~R 8 each independently represents a linear or branched chain C 1 ~C 4 The alkyl group is selected from the group consisting of:

[0085] Furthermore, when a film is formed using the compound represented by formula 2 at process temperatures of, for example, 250°C to 340°C, 250°C to 360°C, 250°C to 380°C, 300°C to 360°C, 330°C to 390°C, or 360°C to 400°C, the rate of change in GPC with respect to temperature (ΔGPC, %) is small, as described above, of 30% or less. In other words, since the GPC does not change significantly over a wide temperature range, from low temperatures to high temperatures, a Group 4 metal element-containing film of uniform thickness can be formed even on a surface having grooves with a large aspect ratio.

[0086] The Group 4 metal element-containing precursor compound may be a compound represented by any one of the following formulas 2-1 to 2-3.

[0087] [ka]

[0088] Furthermore, the film-forming composition includes a Group 4 metal element-containing precursor compound represented by the following formula 3. When a hafnium (Zr)-containing film is formed by ALD at a process temperature of 250°C to 400°C, the rate of change of GPC with respect to temperature represented by the above formula A (ΔGPC, %) may be small, for example, 30% or less, less than 30%, 25% or less, 20% or less, 18% or less, 15% or less, 13% or less, 12% or less, 11% or less, less than 11%, 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 1% or less, less than 1%, 0% or less, or less than 0%.

[0089] [ka]

[0090] In formula 3, R 1 is a methyl group, and R 2 is a linear or branched chain C 3 ~C 4 alkyl groups; R 3 ~R 8 each independently represents a linear or branched chain C 1 ~C 4 The alkyl group is selected from the group consisting of:

[0091] Furthermore, when a film is formed using the compound represented by formula 3 at process temperatures of, for example, 250°C to 340°C, 250°C to 360°C, 250°C to 380°C, 250°C to 400°C, 250°C to 420°C, 250°C to 430°C, 300°C to 360°C, 330°C to 390°C, or 360°C to 400°C, the rate of change of GPC with respect to temperature (ΔGPC,%) is small, as described in 3. That is, since the GPC does not change significantly over a wide temperature range, from low temperatures to high temperatures, a Group 4 metal element-containing film of uniform thickness can be formed even on a surface having grooves with a large aspect ratio.

[0092] The Group 4 metal element-containing precursor compound may be a compound represented by any one of the following formulas 3-1 to 3-3.

[0093] [ka]

[0094] The rate of change of GPC with respect to temperature (ΔGPC, %) can be measured during film formation in increments of 1° C. to 50° C. Specifically, the rate of change of GPC with respect to temperature (ΔGPC, %) can be measured in increments of, for example, 5° C., 10° C., 15° C., 20° C., 25° C., or 30° C.

[0095] On the other hand, a precursor compound containing a Group 4 metal element is used and ozone (O 3 When a Group 4 metal element-containing film is formed by ALD using a tertiary amine compound, it is possible to achieve a GPC of 0.5 to 1.0 Å / cycle, 0.6 to 1.0 Å / cycle, 0.7 to 1.0 Å / cycle, 0.8 to 1.0 Å / cycle, 0.6 to 0.9 Å / cycle, 0.7 to 0.9 Å / cycle, 0.8 to 0.9 Å / cycle, 0.6 to 0.8 Å / cycle, or 0.7 to 0.8 Å / cycle at 150° C. to 400° C.

[0096] For example, the Group 4 metal element-containing precursor compound is a Group 4 metal element-containing precursor compound represented by Formula 2, and ozone (O 3 When a zirconium (Zr)-containing film is formed by ALD using ), the GPC may be 0.5 to 0.9 Å / cycle, 0.6 to 0.9 Å / cycle, 0.7 to 0.9 Å / cycle, or 0.8 to 0.9 Å / cycle at 150° C. to 400° C., for example, 200° C. to 400° C. or 250° C. to 400° C.

[0097] In another example, the Group 4 metal element-containing precursor compound is a Group 4 metal element-containing precursor compound represented by Formula 3, and ozone (O 3When a hafnium (Hf)-containing film is formed by ALD using ), the GPC may be 0.5 to 0.9 Å / cycle, 0.6 to 0.9 Å / cycle, 0.7 to 0.9 Å / cycle, 0.6 to 0.8 Å / cycle, or 0.7 to 0.8 Å / cycle at 150° C. to 410° C., for example, 150° C. to 400° C. or 250° C. to 400° C.

[0098] The Group 4 metal element-containing precursor compound has a specific structure represented by Formula 1, for example, Formula 2 or Formula 3. By using a film-forming composition containing the precursor compound, a Group 4 metal element-containing film can be formed uniformly by ALD over a wide temperature range.

[0099] The Group 4 metal element-containing precursor compound represented by formula 1, for example, formula 2 or formula 3, is generally known as CpZr(NMe 2 ) 3 Compound or CpHf(NMe 2 ) 3 In the synthesis of the compound, cyclopentadiene (C 5 H 6 The compound can be synthesized by using an alkyl-substituted cyclopentadiene instead of the compound of formula (I).

[0100] The present invention will be described in detail below with reference to examples. The following examples are merely illustrative of the present invention, and are not intended to limit the scope of the present invention.

[0101] Preparation Example <Preparation Example 1> Preparation of 1-methyl-3-propylcyclopenta-1,3-diene [ka]

[0102] A flame-dried 1-L Schlenk flask was charged with approximately 27 g (approximately 0.281 mol) of 3-methyl-2-cyclopenten-1-one (MCPO) and approximately 100 mL of tetrahydrofuran (THF, C 4 H 8Approximately 40.4 g (approximately 0.393 mol) of n-propyl magnesium chloride ( n PrMgCl) was slowly added dropwise to the flask, and then the reaction solution was stirred at room temperature for about 4 hours.

[0103] Approximately 33.7 g (approximately 0.562 mol) of acetic acid (CH) mixed with approximately 200 mL of distilled water (DI water) was 3 COOH) was slowly added dropwise to the flask, and the reaction solution was then stirred at room temperature for one day. The aqueous layer was removed using a separatory funnel. Then, about 14.9 g (about 0.140 moles) of sodium carbonate (Na 2 COOH) mixed with about 150 mL of distilled water (DI water) was added. 2 CO 3 ) was slowly added dropwise, and the reaction solution was stirred at room temperature for about 2 hours. The aqueous layer was removed using a separatory funnel. Then, magnesium sulfate (MgSO 4 The water was removed using a solvent such as hexane. The solvent was removed under reduced pressure, and the resulting product was distilled under reduced pressure to obtain about 17 g (yield 49.5%) of 1-methyl-3-n-propylcyclopenta-1,3-diene represented by formula 4-1 as a colorless transparent liquid compound, which was used to prepare a film-forming composition.

[0104] <Preparation Example 2> Preparation of 3-butyl-1-methylcyclopenta-1,3-diene [ka]

[0105] n-Propyl magnesium chloride ( n n-Butyl magnesium chloride (PrMgCl) n Using the same method as in Preparation Example 1 except that BuMgCl was used, about 18 g (yield 47%) of 3-butyl-1-methylcyclopenta-1,3-diene represented by formula 4-2 was obtained as a colorless transparent liquid compound, and a film-forming composition was synthesized using this.

[0106] <Preparation Example 3> Preparation of methylpropylcyclopentadiene mixed composition [ka]

[0107] A flame-dried 1000 mL Schlenk flask was charged with approximately 50.0 g (0.624 mol) of methylcyclopentadiene and approximately 400 mL of tetrahydrofuran (THF, C 4 H 8 2O) and cooled to -20°C. n BuLi) was slowly added dropwise to the flask while keeping the temperature at -20°C, and then the reaction solution was stirred at room temperature for about 4 hours.

[0108] After the reaction was completed, 67.07 g (0.562 mol) of 1-bromopropane (C 3 H 7 Br) was slowly added dropwise while keeping the temperature at -20°C, and then the reaction solution was slowly warmed to room temperature and stirred for 12 hours.

[0109] After the reaction was completed, the salt formed during the reaction was removed by a filtration process, and the organic layer was dissolved in diethyl ether ((C 2 H 5 ) 2 O) and magnesium sulfate (MgSO 4 ) to remove water, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 28.12 g (37.2%) of colorless and transparent liquid mixture compositions represented by formulas 4-1, 4-3, and 4-4. The film-forming composition of Comparative Example 5 was synthesized using this.

[0110] Preparation Example 4: Preparation of diethylcyclopentadiene mixed composition [ka]

[0111] A flame-dried 1-L Schlenk flask was charged with approximately 41.88 g (approximately 1.074 mol) of sodium amide (NaNH 2 ) and about 500 mL of tetrahydrofuran (THF, C 4HO) and then stirred. 7 H 10 ) was slowly added at about -20°C, and then the temperature was gradually raised to room temperature while stirring, after which it was stirred for 17 hours. After the reaction was completed, about 116.98g (about 1.074mol) of 1-bromoethane (C 2 H 5 Br) was slowly added at about -20°C, and then the temperature was gradually raised to room temperature while stirring, and then it was stirred for 17 hours. After the reaction was completed, the salt formed during the reaction was removed by a filtration process, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 62g (47.7% yield) of colorless and transparent liquid mixture compositions represented by formulas 4-5, 4-6, and 4-7. The film-forming composition of Comparative Example 4 was synthesized using this.

[0112] Working Example <Example 1> [(Me, n Pr)Cp]Zr(NMe 2 ) 3 and preparation of a film-forming composition containing the same [ka]

[0113] A flame-dried 1-L Schlenk flask was charged at room temperature with approximately 80 g (approximately 0.300 mol) of tetrakis(dimethylamido)zirconium(VI) and approximately 500 mL of n-hexane (C 6 H 14 About 39 g (about 0.315 mol) of 1-methyl-3-propylcyclopenta-1,3-diene obtained in Preparation Example 1 was slowly added dropwise to the flask, and then the reaction solution was stirred at room temperature for about 3 hours.

[0114] After the reaction was completed, the solvent was removed under reduced pressure, and the resultant was distilled under reduced pressure to obtain about 61 g (yield 60%) of a pale yellow liquid compound represented by formula 2-1, which was used to prepare a film-forming composition.

[0115] Boiling point (bp): 100℃ (0.3Torr) 1 H-NMR(400MHz,C 6 D 6 ,25℃): δ5.797,5.763(m,3H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H * 3 )]Zr[N(CH 3 ) 2 ] 3 、 δ3.033(s,18H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH * 3 ) 2 ] 3 、 δ2.448(t,2H,[(CH 3 CH 2 CH * 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 、 δ2.094(s,3H,[(CH 3 CH 2 CH 2 )(CH * 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 、 δ1.577(m,2H,[(CH 3 CH * 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 、 δ0.923(t,3H,[(CH * 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3

[0116] Example 2 [(Me,nBu)Cp]Zr(NMe 2 ) 3 and preparation of a film-forming composition containing the same [ka]

[0117] The same method as in Example 1 was used except that 3-butyl-1-methylcyclopenta-1,3-diene obtained in Preparation Example 2 was used instead of 1-methyl-3-propylcyclopenta-1,3-diene, to obtain about 65 g (yield 60%) of a pale yellow liquid compound represented by formula 2-2, and a film-forming composition was synthesized using this compound.

[0118] Boiling point (bp): 110℃ (0.3Torr) 1 H-NMR (400MHz, C 6 D 6 ,25℃): δ5.818, 5.777(m, 3H, [(CH 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H * 3 )]Zr[N(CH 3 ) 2 ] 3 , δ2.973(s,18H,[(CH 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H 3)]Zr[N(CH * 3 ) 2 ] 3 、 δ2.493(t,2H,[(CH 3 CH 2 CH 2 CH * 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 、 δ2.102(s,3H,[(CH 3 CH 2 CH 2 CH 2 )(CH * 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 、 δ1.547(m,2H,[(CH 3 CH 2 CH * 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 、 δ1.338(m,2H,[(CH 3 CH * 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 、 δ0.904(t,3H,[(CH * 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H 3)]Zr[N(CH 3 ) 2 ] 3

[0119] Example 3 [(Me,nPr)Cp]Hf(NMe 2 ) 3 and preparation of a film-forming composition containing the same [ka]

[0120] A flame-dried 1-L Schlenk flask was charged at room temperature with approximately 65 g (approximately 0.184 mol) of tetrakis(dimethylamido)hafnium(VI) and approximately 400 mL of n-hexane (C 6 H 14 About 27 g (about 0.220 mol) of 1-methyl-3-propylcyclopenta-1,3-diene obtained in Preparation Example 1 was slowly added dropwise to the flask, and then the reaction solution was stirred at room temperature for about 3 hours.

[0121] After the reaction was completed, the solvent was removed under reduced pressure, and the resultant was distilled under reduced pressure to obtain about 42 g (yield 53%) of a pale yellow liquid compound represented by formula 3-1, which was used to prepare a film-forming composition.

[0122] Boiling point (bp): 100℃ (0.3Torr) 1 H-NMR (400MHz, C 6 D 6 ,25℃): δ5.750, 5.724(m, 3H, [(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H * 3 )]Hf[N(CH 3 ) 2 ] 3 , δ2.987(s,18H,[(CH 3 CH 2 CH 2 )(CH 3 )(C5 H 3 )]Hf[N(CH * 3 ) 2 ] 3 , δ2.466(t,2H,[(CH 3 CH 2 CH * 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 , δ2.119(s,3H,[(CH 3 CH 2 CH 2 )(CH * 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 , δ1.541(m,2H,[(CH 3 CH * 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 , δ0.909(t,3H,[(CH * 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3

[0123] Example 4 [(Me,nBu)Cp]Hf(NMe 2 ) 3 and preparation of a film-forming composition containing the same [ka]

[0124] The same method as in Example 3 was used except that 3-butyl-1-methylcyclopenta-1,3-diene obtained in Preparation Example 2 was used instead of 1-methyl-3-propylcyclopenta-1,3-diene, to obtain about 65 g (yield 60%) of a pale yellow liquid compound represented by formula 3-2, which was used to synthesize a film-forming composition.

[0125] Boiling point (bp): 110℃ (0.3Torr) 1 H-NMR (400MHz, C 6 D 6 ,25℃): δ5.767, 5.759(m, 3H, [(CH 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H * 3 )]-Hf[N(CH 3 ) 2 ] 3 , δ3.011(s,18H,[(CH 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH * 3 ) 2 ] 3 , δ2.524(t,2H,[(CH 3 CH 2 CH 2 CH * 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 , δ2.132(s,3H,[(CH 3 CH 2 CH 2 CH 2 )(CH* 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 , δ1.537(m,2H,[(CH 3 CH 2 CH * 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 , δ1.330(m,2H,[(CH 3 CH * 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 , δ0.901(t,3H,[(CH * 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3

[0126] <Comparative Example 1> Cyclopentadienyl-tris(dimethylamido)zirconium (CpZr(NMe 2 ) 3 or CpZr) products were used.

[0127] <Comparative Example 2> Cyclopentadienyl-tris(dimethylamido)hafnium (CpHf(NMe 2 ) 3 or CpHf) products were used.

[0128] <Comparative Example 3> UP Chemical n Propylcyclopentadienyl-tris(dimethylamido)zirconium ( n PrCp)Zr(NMe 2 ) 3 or n The product used was PrCpZr.

[0129] <Comparative example 4> [(Et) 2 Cp]Zr(NMe 2 ) 3 Preparation of Mixed Composition [ka]

[0130] Using the same method as in Example 1, except that the diethylcyclopentadiene mixed composition represented by formulas 4-5 to 4-7 obtained in Preparation Example 4 was used instead of 1-methyl-3-propylcyclopenta-1,3-diene, about 49 g (yield 71.1%) of a pale yellow liquid mixed composition represented by formulas 2-4 and 2-5 was obtained. A film-forming composition was synthesized using this.

[0131] <Comparative example 5> [(nPr,Me)Cp]Hf(NMe 2 ) 3 Preparation of Mixed Composition [ka]

[0132] A flame-dried 1-L Schlenk flask was charged at room temperature with approximately 54 g (approximately 0.152 mol) of tetrakis(dimethylamido)hafnium(VI) and approximately 500 mL of n-hexane (C 6 H 14 About 27 g (about 0.220 mol) of the methylpropylcyclopentadiene mixture represented by formulae 4-1, 4-3, and 4-4 obtained in Preparation Example 3 was slowly added dropwise to the flask, and then the reaction solution was stirred at room temperature for about 3 hours.

[0133] After the reaction was completed, the solvent was removed under reduced pressure, and the resulting product was distilled under reduced pressure to obtain about 42.2 g (yield 64%) of a pale yellow liquid mixture composition represented by formulas 3-1 and 3-4 having a composition of about 1:1.87. The ratio of the two isomers having the same molecular weight was: 1 H-NMR (400 MHz, C 6 D 6 , 25 °C) spectrum, the methyl (CH 3 ) hydrogen at 2.119 ppm (formula 3-1) and 2.043 ppm (formula 3-4) 1 The ratio was determined as the relative integral value of the NMR peak.

[0134] Boiling point (bp): 100℃ (0.3Torr) 1 H-NMR (400MHz, C 6 D 6 ,25℃): Compound represented by formula 3-1: [(1- n Pr,3-Me)Cp]Hf(NMe 2 ) 3 δ5.750, 5.724(m, 3H, [(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H * 3 )]Hf[N(CH 3 ) 2 ] 3 , δ2.987(s,18H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH * 3 ) 2 ] 3 , δ2.466(t,2H,[(CH 3 CH 2 CH * 2 )(CH3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 3 、 δ2.119(s,3H,[(CH 3 CH 2 CH 2 )(CH * 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 3 、 δ1.541(m,2H,[(CH 3 CH * 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 3 、 δ0.909(t,3H,[(CH * 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 3 Compound represented by Formula 3-4: [(1- n Pr,2-Me)Cp]Hf(NMe 2 ) 3 δ5.913,5.842(m,3H [(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H * 3 )]Hf[N(CH 3 ) 2 3 、 δ2.995(s,18H,[(CH 3 CH 2 CH 2 )(CH​​​​​3 )(C 5 H 3 )]Hf[N(CH * 3 ) 2 ] 3 , δ2.408(t,2H,[(CH 3 CH 2 CH * 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 , δ2.043(s,3H,[(CH 3 CH 2 CH 2 )(CH * 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 , δ1.498(m,2H,[(CH 3 CH * 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 , δ0.886(t,3H,[(CH * 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3

[0135] Test Example <Test Example 1> Structural analysis of precursor compound 1 H-NMR (400 MHz, C 6 D 6The structures of the Group 4 metal element-containing precursor compounds prepared in the Examples and Comparative Examples were analyzed. The results are shown in the above Examples and Comparative Examples.

[0136] Furthermore, as can be seen from FIG. 1, the hafnium (Hf)-containing precursor compound of Comparative Example 5 had a composition of two structures (mixed structure) resulting from structural isomers. 1 In the H-NMR spectrum, the methyl (CH 3 ) hydrogen appears at 2.119 ppm (formula 3-1) and 2.043 ppm (formula 3-4) 1 H-NMR peaks were observed (the ratio of Formula 3-1 to Formula 3-4 (relative ratio of peak integrals) was about 1:1.87). On the other hand, the hafnium (Hf)-containing precursor compound prepared in Example 3 of the present invention was 1 H-NMR analysis confirmed that it had a single composition.

[0137] The results of the structural analysis confirm that the hafnium (Hf)-containing precursor compound of Example 3 is a precursor of sufficiently high purity to be applied in the ALD process. Therefore, the Group 4 metal element-containing precursor compound prepared by the method of the example can be used to form various films.

[0138] <Test Example 2> Evaluation of Zr-containing oxide film formed by atomic layer deposition (ALD) and GPC against temperature A film-forming composition containing a zirconium (Zr)-containing precursor compound prepared by the method of Example 1 and ozone (O 3 ) was used to form a zirconium (Zr)-containing oxide film by ALD on a silicon substrate heated to a temperature (process temperature) of about 250°C to 400°C.

[0139] Specifically, first, a silicon substrate was prepared in an ALD reaction chamber.

[0140] Then, the film-forming composition prepared by the method of Example 1 was filled into a stainless steel canister and heated to about 120°C. Argon (Ar) carrier gas was flowed into the stainless steel canister at a flow rate of about 200 to 500 sccm to supply the gaseous film-forming composition to the reaction chamber. The temperature of the gas supply pipe connected from the stainless steel canister to the reaction chamber was about 120°C to 150°C. The temperature was higher the closer to the reaction chamber. Oxygen gas (O 2 ) at a flow rate of 500 to 1000 sccm. 3 ) to the generator, and approximately 180-220g / m 3 Ozone (O 3 ) was generated and supplied to the reaction chamber to be used as a reaction gas. The zirconium (Zr)-containing precursor and ozone (O 3 In order to remove the SiO 2 and reaction by-products, argon (Ar) gas was supplied to the reaction chamber at a flow rate of about 500 to 2000 sccm. The process pressure of the reaction chamber was maintained at 0.9 to 1.2 Torr.

[0141] The ALD gas supply cycle was repeated 100 times to form a zirconium (Zr)-containing oxide film. Here, each ALD gas supply cycle includes a step of supplying a gaseous film-forming composition for about 5 to 30 seconds, a step of supplying argon (Ar) gas for about 5 to 30 seconds to remove the film-forming composition (gas) remaining in the reactor, and a step of supplying ozone (O) as a reactive gas. 3 ) for about 5 to 30 seconds, and argon (Ar) gas is supplied for about 5 to 30 seconds to remove ozone (O 3 ) removal of the

[0142] Using the compositions containing the zirconium (Zr)-containing precursor compounds of Comparative Example 1, Comparative Example 3, and Comparative Example 4, a stainless steel canister was heated to 100°C, 110°C, and 120°C, respectively, to vaporize each of the compositions containing the zirconium (Zr)-containing precursor compounds of Comparative Example 1, Comparative Example 3, and Comparative Example 4. A zirconium (Zr) oxide film was formed under the same conditions as those of the film formation method of Test Example 2.

[0143] The thickness of each of the zirconium (Zr) oxide films formed using the film-forming compositions prepared by the methods of Example 1, Comparative Example 1, Comparative Example 3, and Comparative Example 4 was measured using an ellipsometer (M-2000, JA Woollam).

[0144] Then, the measured thickness was divided by the number of gas supply cycles (100 times) to calculate the GPC. Specifically, the GPC was calculated for temperatures (process temperatures) in the range of 250° C. to 400° C. The results are shown in FIG. 2 and Table 1.

[0145] Furthermore, the rate of change in GPC versus process temperature (ΔGPC, %) was calculated using the following formula A. The results are shown in Table 1.

[0146]

number

[0147] In formula A, GPC 250 is GPC at 250 °C, and GPC temp is the GPC at process temperature.

[0148] <Test Example 3> Evaluation of hafnium (Hf)-containing oxide film formed by atomic layer deposition (ALD) and GPC against temperature A film-forming composition containing a hafnium (Hf)-containing precursor compound prepared by the method of Example 3 and ozone (O 3 ) was used to form a hafnium (Hf)-containing oxide film by ALD on a silicon substrate heated to a process temperature of about 250°C to 400°C.

[0149] Specifically, first, a silicon substrate was prepared in an ALD reaction chamber.

[0150] Then, the film-forming composition prepared by the method of Example 3 was filled into a stainless steel canister and heated to about 120°C. Argon (Ar) carrier gas was flowed into the stainless steel canister at a flow rate of about 200 to 500 sccm to supply the gaseous film-forming composition to the reaction chamber. The temperature of the gas supply pipe connected from the stainless steel canister to the reaction chamber was about 120°C to 150°C. The temperature was higher the closer to the reaction chamber. Oxygen gas (O 2 ) at a flow rate of 500 to 1000 sccm. 3 ) to the generator, and approximately 180-220g / m 3 Ozone (O 3 ) was generated and supplied to the reaction chamber to be used as a reaction gas. The hafnium (Hf)-containing precursor and ozone (O 3 In order to remove the SiO 2 and reaction by-products, argon (Ar) gas was supplied to the reaction chamber at a flow rate of about 500 to 2000 sccm. The process pressure of the reaction chamber was maintained at 0.9 to 1.2 Torr.

[0151] The ALD gas supply cycle was repeated 100 times to form a hafnium (Hf)-containing oxide film. Each ALD gas supply cycle included a step of supplying a gaseous film-forming composition for about 5 to 30 seconds, a step of supplying argon (Ar) gas for about 5 to 30 seconds to remove the film-forming composition (gas) remaining in the reactor, and a step of supplying ozone (O) as a reactive gas. 3 ) for about 5 to 30 seconds, and argon (Ar) gas is supplied for about 5 to 30 seconds to remove ozone (O 3 ) removal of the

[0152] A hafnium (Hf) oxide film was formed under the same conditions as those of the film formation method of Test Example 3, except that a stainless steel canister was heated to 100°C using the film-forming composition containing the hafnium (Hf)-containing precursor compound of Comparative Example 2 to vaporize the film-forming composition containing the hafnium (Hf)-containing precursor compound of Comparative Example 2.

[0153] The thickness of each of the hafnium (Hf) oxide films formed using the film-forming compositions prepared by the methods of Example 3 and Comparative Example 2 was measured using an ellipsometer (M-2000, JA Woollam).

[0154] Then, the measured thickness was divided by the number of gas supply cycles (100 times) to calculate the GPC. Specifically, the GPC was calculated for temperatures (process temperatures) in the range of 250° C. to 450° C. The results are shown in FIG. 3 and Table 2.

[0155] Furthermore, the rate of change in GPC with respect to temperature (ΔGPC, %) was calculated using the above formula A. The results are shown in Table 2.

[0156] [Table 1]

[0157] As can be seen from Figure 2 and Table 1, the film-forming composition containing the zirconium (Zr)-containing precursor compound of the present invention can achieve self-limiting ALD film growth over a wide temperature range, especially at high temperatures. Furthermore, the GPC does not change when the film-forming composition of Example 1 is used.

[0158] Specifically, when the film-forming compositions of Comparative Example 1 and Comparative Example 4 were used, the precursor compounds had low thermal stability, and as the temperature increased, the GPC changed rapidly, resulting in a GPC change rate (ΔGPC) exceeding 100% at 330°C or 360°C, respectively.

[0159] This is believed to be because the film grew by a gas phase reaction other than a surface reaction due to the thermal decomposition of the precursor compound used in Comparative Example 1 and Comparative Example 4. That is, when the film grows by a gas phase reaction, the film grows rapidly in the upper part of the groove, while the film grows slowly in the lower part (lower part) of the narrow and deep groove. In such a case, the advantage of ALD, that a film of uniform thickness can be formed by a surface reaction even on a surface with deep grooves, cannot be obtained.

[0160] On the other hand, when the film-forming composition of Example 1 of the present invention was used, the zirconium (Zr)-containing precursor compound contained in the film-forming composition had excellent thermal stability without thermal decomposition. Therefore, even when high temperatures were used in ALD, the GPC did not change, and the rate of change in GPC (ΔGPC) was maintained at 10% or less up to about 370°C.

[0161] Furthermore, when the film-forming composition of Comparative Example 3 was used, the GPC change rate (ΔGPC) at 380°C was approximately 22%, which showed a significant difference from Example 1, in which the GPC change rate (ΔGPC) was approximately 12% at the same temperature.

[0162] [Table 2]

[0163] As can be seen from Figure 3 and Table 2, the film-forming composition including the hafnium (Hf)-containing precursor compound of the present invention can achieve self-limiting ALD film growth over a wide temperature range, especially at high temperatures. Furthermore, the GPC does not change when the film-forming composition of Example 3 is used.

[0164] Specifically, in Comparative Example 2, the precursor compound had low thermal stability, which resulted in a rapid change in GPC as the temperature increased, resulting in a GPC change rate (ΔGPC) of over 100% at 400°C.

[0165] This is believed to be because the film grew by a gas-phase reaction other than a surface reaction due to the thermal decomposition of the precursor compound used in Comparative Example 2. That is, when the film grows by a gas-phase reaction, the film grows rapidly in the upper part of the groove, while the film grows slowly in the lower part (lower part) of the narrow and deep groove. In such a case, the advantage of ALD, that a film of uniform thickness can be formed by a surface reaction even on a surface with deep grooves, cannot be obtained.

[0166] On the other hand, in Example 3 of the present invention, the hafnium (Hf)-containing precursor compound contained in the film-forming composition had excellent thermal stability without thermal decomposition. Therefore, even when high temperatures were used in ALD, the GPC did not change, and the rate of change in GPC (ΔGPC) was maintained at 8% or less up to about 440°C.

[0167] <Test Example 4> Evaluation of step coverage of zirconium (Zr)-containing oxide film The step coverage of the zirconium (Zr)-containing oxide films formed using the film-forming compositions of Example 1, Comparative Example 1, Comparative Example 3, and Comparative Example 4 was evaluated.

[0168] Specifically, silicon oxide (SiO ) films were formed by ALD at process temperatures of about 300° C., 340° C., and 360° C. using the film-forming compositions of Example 1, Comparative Example 1, Comparative Example 3, and Comparative Example 4, respectively. 2 A zirconium (Zr)-containing oxide film having a thickness of approximately 12 to 15 nm was formed on a substrate having a groove with an aspect ratio of 20:1 in the film.

[0169] The thickness and step coverage (%) of the zirconium (Zr)-containing oxide film were measured in the transmission electron microscope (TEM) images of the top, center, and bottom of the groove shown in FIGS.

[0170] [Table 3]

[0171] [Table 4]

[0172] As can be seen from FIGS. 4 and 5 and Tables 3 and 4, when a zirconium (Zr)-containing oxide film was formed on a substrate having a groove with an aspect ratio of 20:1 at 300° C., 340° C., and 360° C. using the film-forming composition of Example 1 of the present invention, the step coverage rate (%) was superior to that of Comparative Example 1, Comparative Example 3, and Comparative Example 4.

[0173] Furthermore, it was confirmed that when the film-forming composition of Example 1 was used, a zirconium (Zr)-containing oxide film having an extremely uniform thickness and a step coverage rate of about 99.3% was formed even at a high temperature of about 360°C.

[0174] From the above results, it was confirmed that by using the film-forming composition containing the zirconium (Zr)-containing precursor compound of the present invention, self-limiting film growth by ALD can be achieved over a wide temperature range, particularly at a high temperature of about 360° C., and that it is possible to form zirconium (Zr)-containing films for various applications over a wide range of process temperatures.

[0175] In particular, according to the method for forming a zirconium (Zr)-containing film of the present invention, since the GPC does not change over a wide temperature range, it is possible to form a zirconium (Zr)-containing film of uniform thickness even on a surface having a groove with a large aspect ratio. Therefore, it can be advantageously used for manufacturing various semiconductor devices such as DRAM and 3D NAND flash memory.

[0176] <Test Example 5> Evaluation of step coverage of hafnium (Hf)-containing oxide film The step coverage of the hafnium (Hf)-containing oxide films formed using the film-forming compositions of Example 3 and Comparative Example 2 was evaluated.

[0177] Specifically, using the film-forming compositions of Example 3 and Comparative Example 2, respectively, a hafnium (Hf)-containing oxide film having a thickness of about 6 to 7 nm was formed by ALD at process temperatures of about 350°C and about 400°C on a substrate having a titanium nitride (TiN) film formed in a groove having an aspect ratio of 11:1.

[0178] The thickness and step coverage (%) of the hafnium (Hf)-containing oxide film were measured in transmission electron microscope (TEM) images of the top, center, and bottom of the trench shown in FIG.

[0179] [Table 5]

[0180] As can be seen from FIG. 6 and Table 5, when a hafnium (Hf)-containing oxide film was formed on a substrate having a step with an aspect ratio of 11:1 at 350° C. and 400° C. using the film-forming composition of Example 3 of the present invention, the step coverage rate (%) was good.

[0181] Specifically, it was confirmed that when the film-forming composition of Example 3 was used, a hafnium (Hf)-containing oxide film having an extremely uniform thickness and a step coverage rate of approximately 98.7% was formed even at a high temperature of approximately 400°C.

[0182] From the above results, it was confirmed that by using a film-forming composition containing a hafnium (Hf)-containing precursor compound of the present invention, self-limiting ALD film growth can be achieved over a wide temperature range, particularly at a high temperature of about 400° C., and that it is possible to form hafnium (Hf)-containing films for various applications over a wide range of process temperatures.

[0183] In particular, according to the method for forming a hafnium (Hf)-containing film of the present invention, since the GPC does not change over a wide temperature range, it is possible to form a hafnium (Hf)-containing film of uniform thickness even on a surface having a groove with a large aspect ratio. Therefore, it can be advantageously used for manufacturing various semiconductor devices such as DRAM and 3D NAND flash memory.

Claims

1. A method for forming a Group 4 metal element-containing film, comprising the step of reacting a film-forming composition containing a Group 4 metal element-containing precursor compound represented by the following formula 1 with a reactive gas to form a Group 4 metal element-containing film on a substrate: 【Chemistry 1】 [In formula 1, M is Zr or Hf, and R １ is a methyl group, R ２ is a linear or branched chain C ３ ~C ４ alkyl groups; R ３ ~R ８ are each independently a straight or branched chain C １ ~C ４ is selected from the group consisting of alkyl groups.

2. The method for forming a Group 4 metal element-containing film comprises the steps of: providing at least a portion of the substrate in a reaction chamber; supplying the film forming composition in a gaseous state to the reaction chamber; and providing the reaction gas to the reaction chamber; 2. The method for forming a Group 4 metal element-containing film according to claim 1, wherein the Group 4 metal element-containing film is formed on at least a portion of the surface of the substrate by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

3. 2. The method for forming a Group 4 metal element-containing film according to claim 1, wherein deposition is carried out at a temperature range of 150°C to 500°C.

4. 2. The method for forming a Group 4 metal element-containing film according to claim 1, wherein the Group 4 metal element-containing precursor compound is a single composition structure.

5. 2. The method for forming a Group 4 metal element-containing film according to claim 1, wherein the Group 4 metal element-containing precursor compound is a compound represented by the following formula 2: 【Chemistry 2】 [In formula 2, R １ is a methyl group, R ２ is a linear or branched chain C ３ ~C ４ alkyl groups; R ３ ~R ８ are each independently a straight or branched chain C １ ~C ４ is selected from the group consisting of alkyl groups.

6. 6. The method for forming a Group 4 metal element-containing film according to claim 5, wherein the Group 4 metal element-containing precursor compound is a compound represented by one of the following formulas 2-1 to 2-3. 【Chemistry 3】

7. 6. The method for forming a Group 4 metal element-containing film according to claim 5, wherein, when a zirconium (Zr)-containing film is formed by atomic layer deposition (ALD) at a process temperature of 250° C. to 380° C. using the compound represented by formula 2, the rate of change (ΔGPC, %) of the film formation rate (GPC) with respect to temperature represented by the following formula A is 30% or less. [0010] [In formula A, GPC ２５０ is GPC at 250°C, GPC ｔｅｍｐ is the GPC at process temperature.

8. The method for forming a Group 4 metal element-containing film according to claim 7, wherein when the compound represented by formula 2 is used to form a zirconium (Zr)-containing film by atomic layer deposition (ALD) at a process temperature of 250°C to 400°C, the change rate of GPC (ΔGPC,%) is 30% or less.

9. The method for forming a Group 4 metal element-containing film according to claim 7, wherein when the compound represented by formula 2 is used to form a zirconium (Zr)-containing film by atomic layer deposition (ALD) at a process temperature of 250°C to 360°C, the change rate of GPC (ΔGPC,%) is 30% or less.

10. 2. The method for forming a Group 4 metal element-containing film according to claim 1, wherein the Group 4 metal element-containing precursor compound is a compound represented by the following formula 3: 【Chemistry 4】 [In formula 3, R １ is a methyl group, R ２ is a linear or branched chain C ３ ~C ４ alkyl groups; R ３ ~R ８ are each independently a straight or branched chain C １ ~C ４ is selected from the group consisting of alkyl groups.

11. 11. The method for forming a Group 4 metal element-containing film according to claim 10, wherein the Group 4 metal element-containing precursor compound is a compound represented by one of the following formulas 3-1 to 3-3. 【Chemistry 5】

12. The method for forming a Group 4 metal element-containing film according to claim 10, wherein when a hafnium (Hf)-containing film is formed by atomic layer deposition (ALD) at a process temperature of 250° C. to 400° C. using the compound represented by formula 3, the rate of change (ΔGPC, %) of the film formation rate (GPC) with respect to temperature represented by the following formula A is 30% or less. [0025] [In formula A, GPC ２５０ is GPC at 250°C, GPC ｔｅｍｐ is the GPC at process temperature.

13. 2. The method for forming a Group 4 metal element-containing film according to claim 1, wherein the Group 4 metal element-containing film is formed on a substrate having at least one groove having an aspect ratio of 1 or more and a width of 1 μm or less.

14. 2. The method for forming a Group 4 metal element-containing film according to claim 1, wherein the Group 4 metal element-containing film is formed to a thickness in the range of 1 nm to 500 nm.

15. A film-forming composition comprising a Group 4 metal element-containing precursor compound represented by the following formula 1: 【Chemistry 6】 [In formula 1, M is Zr or Hf, and R １ is a methyl group, R ２ is a linear or branched chain C ３ ~C ４ alkyl groups; R ３ ~R ８ are each independently a straight or branched chain C １ ~C ４ is selected from the group consisting of alkyl groups.

16. The film-forming composition according to claim 15, wherein the Group 4 metal element-containing precursor compound is a compound represented by one of the following formulas 2-1 to 2-3. 【Chemistry 7】

17. The film-forming composition according to claim 15, wherein the Group 4 metal element-containing precursor compound is a compound represented by one of the following formulas 3-1 to 3-3: 【Chemistry 8】

18. The film-forming composition according to claim 15 , wherein the Group 4 metal element-containing precursor compound has a single composition structure.

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