Film deposition composition comprising precursor compound containing group 4 metal element and method for forming film using same

Abstract

The present invention relates to a film deposition composition comprising a precursor compound containing a Group 4 metal element and a method for forming a film using the same. Using the film deposition composition comprising the precursor compound containing the Group 4 metal element of the present invention, self-limiting film growth of ALD is achieved in a wide temperature range from low temperature to high temperature, enabling formation of Group 4 metal element containing films for different purposes at different process temperatures. In particular, according to the method for forming a film containing a Group 4 metal element of the present invention, the growth per cycle (GPC) of ALD remains unchanged over a wide temperature range, and thus a film containing a Group 4 metal element having a uniform thickness can be formed even on the surface of a trench having a large aspect ratio. Therefore, the method can be advantageously used for manufacturing various semiconductor devices such as a DRAM (Dynamic Random Access Memory), a 3D NAND flash memory and the like.

Description

[0001] The present invention is a divisional application of a Chinese patent application with application number 202380013367.4, application date May 11, 2023, and invention name “Film deposition composition comprising a precursor compound containing a Group IV metal element and a method for forming a film using the same”. Technical Field

[0002] The present invention relates to a composition for film deposition comprising a precursor compound containing a Group IV metal element, and a method for forming a film using the composition. Background Art

[0003] Films containing Group IV metal elements (especially Group IV metal oxide films with high dielectric constants) are one of the thin films necessary for driving non-storage semiconductor devices (such as logic devices) and storage semiconductor devices (such as DRAM, flash memory, resistive memory (ReRAM), ferroelectric memory (FeRAM) and phase change memory (PCRAM)).

[0004] In particular, such films containing Group IV metal elements are used in the most advanced organic light-emitting diode (OLED) technology in the display field, as well as gate insulating films in memory devices, capacitor high-k dielectric films, etc.

[0005] Meanwhile, products having complex shapes such as high aspect ratios and three-dimensional structures are being developed in various ways in the semiconductor field and the non-semiconductor field. Therefore, there is a need for a composition for film deposition comprising a precursor compound containing a Group IV metal element for forming a film containing a Group IV metal element, the composition being applicable to atomic layer deposition (ALD), being suitable for a process temperature in various application fields, and being able to overcome a high step ratio.

[0006] [Prior art literature]

[0007] [Non-patent literature]

[0008] J. "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. Summary of the invention

[0009] Technical issues

[0010] The technical problem to be solved by the present invention is to provide a method for forming a film containing a Group IV metal element, wherein the film growth amount per ALD gas supply cycle (growth per cycle (GPC)) does not change within a wide temperature range, and a uniform film with excellent step coverage can be achieved even on a substrate with a complex shape.

[0011] Another technical problem to be solved by the present invention is to provide a composition for film deposition, wherein the composition comprises a precursor compound containing a metal element of Group IV, wherein the precursor compound has a specific structure.

[0012] However, the problems to be solved by the present invention are not limited to the above problems, and those skilled in the art can clearly understand other unmentioned problems through the following description.

[0013] Solution to the problem

[0014] In order to achieve the above object, the present invention provides a method for forming a film containing a fourth group metal element, the method comprising reacting a composition for film deposition with a reaction gas to form a film containing a fourth group metal element on a substrate, wherein the composition comprises a precursor compound containing a fourth group metal element represented by the following formula 1:

[0015] [Formula 1]

[0016]

[0017] In Formula 1, M is Zr or Hf, R 1 is a methyl group, R 2 Selected from linear or branched C 3 -C 4 Alkyl group, R 3 To R 8 Each independently selected from linear or branched C 1 -C 4 Alkyl group.

[0018] In addition, a composition for film deposition is also provided, the composition comprising a precursor compound represented by the above Formula 1 containing a metal element of Group IV.

[0019] Advantageous Effects of the Invention

[0020] Due to the use of the composition for film deposition containing a precursor compound containing a Group IV metal element of the present invention, self-limiting film growth of ALD can be achieved within a wide temperature range (especially at high temperatures); therefore, films containing Group IV metal elements for different applications can be formed at different process temperatures.

[0021] In particular, according to the method for forming a film containing a Group IV metal element of the present invention, since GPC does not change in a wide temperature range not only at low temperatures but also at high temperatures, a film containing a Group IV metal element having a uniform thickness can be formed even on a surface of a groove having a large aspect ratio. Therefore, it can be advantageously used to manufacture various semiconductor devices such as DRAM and 3D NAND flash memory. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The hafnium (Hf)-containing precursor compounds prepared according to Example 3 and Comparative Example 5 of the present invention are 1 H-NMR spectra for comparison.

[0023] Figure 2 A graph of GPC at a temperature ranging from 250° C. to 400° C. when a zirconium (Zr)-containing film was deposited using the composition for film deposition of Inventive Example 1 and Comparative Examples 1, 3, and 4 is shown.

[0024] Figure 3 A graph of GPC at a temperature ranging from 250° C. to 450° C. when a hafnium (Hf)-containing film was deposited using the compositions for film deposition of Inventive Example 3 and Comparative Example 2 is shown.

[0025] Figure 4 Transmission electron microscope (TEM) images determining the step coverage of films deposited at 300° C. using each of the compositions for film deposition of Inventive Example 1 and Comparative Examples 1, 3, and 4 are shown.

[0026] Figure 5 Transmission electron microscope (TEM) images determining the step coverage of films deposited at 340° C. and 360° C. using each of the compositions for film deposition of Inventive Example 1 and Comparative Examples 3 and 4 are shown.

[0027] Figure 6 Transmission electron microscope (TEM) images determining the step coverage of films deposited using each of the compositions for film deposition of Inventive Example 3 and Comparative Example 2 at 350° C. and 400° C. are shown. DETAILED DESCRIPTION

[0028] The present application will be described in more detail below.

[0029] The advantages and features of the present invention and methods for achieving these advantages and features will become apparent with reference to the embodiments described below. However, the present invention is not limited to the embodiments described below, but may be embodied in various forms. These embodiments are provided to make the disclosure of the present invention comprehensive and complete and to fully convey the scope of the present invention to those skilled in the art. The present invention is limited only by the scope of the claims.

[0030] Furthermore, in the present specification, when it is mentioned that one element is formed “on” another element, it not only means that the one element is formed directly “on” the other element but also means that other elements are interposed therebetween.

[0031] In this specification, when a component is referred to as “comprising” an element, unless otherwise specified, it should be understood that the component may also include other elements, rather than excluding other elements.

[0032] Unless otherwise indicated, all numbers and expressions relating to amounts of components, reaction conditions, and so forth used herein are to be understood as modified by the term "about."

[0033] In the present specification, unless otherwise specified, the terms "film" and "thin film" each refer to "film" and "thin film".

[0034] In this specification, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups and all possible isomers thereof. For example, alkyl or alkyl groups include not only methyl (Me), ethyl (Et), n-propyl ( n Pr), isopropyl ( i Pr), n-butyl ( n Bu), isobutyl ( i Bu), tert-butyl (tert-Bu, t Bu), sec-butyl ( sec Bu), etc., and also include isomers thereof, but are not limited thereto.

[0035] [Method for forming a film containing a Group IV metal element]

[0036] According to an embodiment of the present invention, there is provided a method for forming a film containing a Group IV metal element, the method comprising reacting a composition for film deposition with a reaction gas to form a film containing a Group IV metal element on a substrate, the composition comprising a precursor compound containing a Group IV metal element represented by the following Formula 1:

[0037] [Formula 1]

[0038]

[0039] In Formula 1, M is Zr or Hf, R1 is a methyl group, R 2 Selected from linear or branched C 3 -C 4 Alkyl group, R 3 To R 8 Each independently selected from linear or branched C 1 -C 4 Alkyl group.

[0040] Since a composition for film deposition containing a Group IV metal element represented by Formula 1 is used in the method for forming a film containing a Group IV metal element according to an embodiment of the present invention, a film containing a Group IV metal element can be formed by chemical vapor deposition (CVD) or ALD with a constant GPC over a wide temperature range including high and low temperatures.

[0041] In particular, the precursor compound containing the fourth group metal element represented by Formula 1 may be a structure having a single composition. Here, the term "single composition" refers to a substance that does not contain structural isomers. It may not mean a 100% pure substance. For example, it may contain 5% or less impurities. In addition, the term "impurity" may refer to all substances other than the precursor compound containing the fourth group metal element represented by Formula 1.

[0042] Specifically, the precursor compound containing the fourth group metal element represented by Formula 1 is 1 H-NMR spectrum analysis may be a structure with a single composition (single material structure), wherein no structural isomers or mixtures thereof are contained, and the content of impurities 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 the metal element of the fourth group represented by Formula 1 has a high purity of 95% or more, is in a liquid state at room temperature (which is advantageous in the preparation process), and has excellent thermal stability; therefore, various films containing the metal element of the fourth group can be easily formed.

[0043] Furthermore, even on a substrate having a pattern (groove) on the surface, a porous substrate, a plastic substrate, or a substrate having a complex shape with a three-dimensional structure, a uniform film with excellent coverage can be formed, thereby providing a high-quality film containing a Group IV metal element. Therefore, its technical significance lies in that it can be advantageously used in various applications in the field of semiconductor devices and can exhibit excellent characteristics.

[0044] Specifically, according to an embodiment of the present invention, when a film containing a Group IV metal element (specifically, a zirconium-containing film) is formed by ALD 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., 250° C. to 350° C., or 250° C. to 340° C., the film may be formed by ALD at a temperature of, for example, 150° 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., 250° C. to 350° C., or 250° C. to 340° C. In the case of a Zr-containing film or a hafnium (Hf)-containing film), the change in GPC (ΔGPC, %) is close to zero, or is as small as, 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.

[0045] The precursor compound containing the Group IV metal element represented by Formula 1 is described in detail in the section "Composition for film deposition" below.

[0046] A method for forming a film containing a Group IV metal element according to an embodiment of the present invention includes: providing at least a portion of a substrate to a reaction chamber (a first step); supplying a gaseous composition for film deposition to the reaction chamber (a second step); and supplying a reaction gas to the reaction chamber (a third step).

[0047] Furthermore, according to the method for forming a film containing a Group IV metal element, the gas supply cycle including the second step and the third step may be repeated multiple times, for example, several times, tens of times, hundreds of times, or thousands of times, to form a film containing a Group IV metal element having a desired thickness.

[0048] In addition, the process may further include supplying an inert gas such as argon (Ar) or nitrogen (N) to the reaction chamber between the second step and the third step. 2 ) to remove the composition (gas) for film deposition remaining in the reaction chamber. In addition, the process may further include supplying an inert gas such as argon (Ar) or nitrogen (N) to the reaction chamber after the third step. 2 ) to remove the residual reaction gas in the reaction chamber.

[0049] Specifically, a method for forming a film containing a Group IV metal element may include providing at least a portion of a substrate to a reaction chamber (a first step).

[0050] The substrate may be one selected from conventional semiconductor wafers, compound semiconductor wafers and plastic substrates (PI, PET, PES and PEN), but may not be limited thereto. In addition, a substrate having holes or grooves may be used, and a porous substrate having a large surface area may be used.

[0051] In particular, the following excellent effects can be produced: within various temperature ranges, for example, from 150°C to 500°C, a film containing Group IV metal elements having a uniform thickness of several nanometers (nm) to several micrometers (μm) can be formed even on a substrate with a pattern (groove) on the surface, a porous substrate or a plastic substrate; and a film containing Group IV metal elements is uniformly formed on the substrate, the film covering the deepest surface of the fine pattern (groove) and the upper surface having at least one fine groove, wherein the aspect ratio of the fine groove is 1 or greater (for example, about 1 to 50 or greater) and the width is 1 μm or less (for example, about 1 μm to 10 nm or less).

[0052] The method for forming a film containing a Group IV metal element may include supplying a composition for film deposition in a gaseous state, the composition including a precursor compound containing a Group IV metal element, to a reaction chamber (a second step).

[0053] The composition for film deposition containing a precursor compound containing a metal element of the fourth group is delivered in a gaseous state to form an oxide film containing a metal element of the fourth group on a substrate. In addition, a composition for film deposition containing other elements can be used together with the composition for film deposition to form a composite metal oxide film or nanolaminated material containing a metal element of the fourth group, such as 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 membrane.

[0054] Specifically, when a composition for film deposition containing a precursor compound containing a Group IV metal element is supplied to a reaction chamber, a transport gas or a dilution gas can be used to transport the composition for film deposition containing a precursor compound containing a Group IV metal element to a substrate to form a film containing a Group IV metal element at a deposition temperature of 150°C to 500°C.

[0055] In addition, it is preferred to use a gas selected from argon (Ar), nitrogen (N 2 ), helium (He) and hydrogen (H 2 ) as a conveying gas or a diluent gas.

[0056] In addition, the method of delivering the composition for film deposition containing a precursor compound containing a metal element of the fourth group to the reaction chamber may be at least one method selected from the following: a bubbling method, in which a delivery gas or a diluent gas is used to forcibly vaporize the composition for film deposition containing a precursor compound containing a metal element of the fourth group; a liquid delivery system (LDS) method, in which the composition is supplied in a liquid phase at room temperature, which is vaporized by a vaporizer; a vapor flow control (VFC) method, in which the composition for film deposition containing a precursor compound is directly supplied using the vapor pressure of the composition; and a bypass method. In addition, a method of supplying a composition for film deposition in a gaseous state in chemical vapor deposition (CVD) or ALD can also be applied to the present invention.

[0057] The method for forming a film containing a Group 4 metal element according to an embodiment of the present invention may include supplying a reaction gas to a reaction chamber (third step).

[0058] According to the method for forming a film containing a Group IV metal element, in order to deposit an oxide film (ZrO 2 , HfO 2 ) or a composite metal oxide film containing a Group IV metal element (ZrSiO x 、ZrAlO x 、ZrHfO x 、ZrHfSiO x 、ZrHfAlO x 、ZrHfSiAlO x , ZrON, etc.), water vapor (H 2 O), oxygen (O 2 ), oxygen plasma (O 2 plasma), nitrogen oxides (NO, N 2 O), nitrogen oxide plasma (N 2 O plasma), nitrogen dioxide (N 2 O 2 ), hydrogen peroxide (H 2 O 2 ) and ozone (O 3 ) as a reaction gas.

[0059] In addition, in order to deposit a nitride film containing a Group IV metal element or a composite metal nitride film containing a Group IV metal element, a catalyst selected from ammonia (NH 3 ), ammonia plasma (NH 3 plasma), hydrazine (N 2 H 4 ) and nitrogen plasma (N 2plasma).

[0060] According to an embodiment of the present invention, a composition for film deposition containing a precursor compound containing a Group IV metal element is transported in a gaseous state to form at least one selected from a nitride film containing a Group IV metal element, a carbide film containing a Group IV metal element, and a composite metal film containing a Group IV metal element on a substrate.

[0061] For example, a composition for film deposition containing a precursor compound containing a Group IV metal element is delivered in a gaseous state to form a film containing a Group IV metal element, specifically, an oxide film containing a Group IV metal element, a composite metal oxide film containing a Group IV metal element, a nitride film containing a Group IV metal element, or a composite metal nitride film containing a Group IV metal element, on a surface of at least a portion of a substrate by CVD or ALD.

[0062] The deposition method of the film containing the Group IV metal element may be performed using any method and / or apparatus known in the art to which the present invention pertains; if necessary, one or more additional reaction gases may be used.

[0063] The deposition method of the film containing the fourth group metal element can be performed by CVD (such as metal organic chemical vapor deposition (MOCVD)) or ALD. MOCVD or ALD can be performed using deposition equipment, deposition conditions and reaction gases known in the art.

[0064] [Film containing a Group IV metal element]

[0065] According to an embodiment of the present invention, there is provided a film containing a Group IV metal element, which is formed by a method for forming a film containing a Group IV metal element.

[0066] The film containing the Group IV metal element may have a thickness of about 1 nanometer (nm) to several micrometers (μm), and may be variously applied according to the application purpose. Specifically, the film containing the Group IV metal element may be formed with a thickness ranging from 1 nm to 500 nm.

[0067] A film containing a Group IV metal element can be formed on a substrate (plate).

[0068] The substrate is as described above.

[0069] The film containing the Group IV metal element according to an embodiment of the present invention has high quality with stable and consistent physical properties and excellent step coverage by using a composition for film deposition containing a precursor compound containing the Group IV metal element, the precursor compound having a specific structure.

[0070] The film containing the metal element of Group IV may be at least one selected from an oxide film containing the metal element of Group IV, a composite metal oxide film containing the metal element of Group IV, a nitride film containing the metal element of Group IV, and a composite metal nitride film containing the metal element of Group IV. Specifically, the film containing the metal element of Group IV may include at least one selected from an oxide film containing the metal element of Group IV and a composite metal oxide film containing the metal element of Group IV.

[0071] In addition, the film containing the fourth group metal element may include nano-laminated materials such as 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 membrane.

[0072] Furthermore, films containing Group IV metal elements can be very good in terms of step coverage.

[0073] For example, when an oxide film or a 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, the thickness deviation calculated by measuring the film thickness at the top, middle, and bottom is very small, indicating a very 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)).

[0074] Specifically, the composition for film deposition according to an embodiment 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.

[0075] In particular, when an oxide film or a nitride film is formed in a groove with a large aspect ratio, it is difficult to form a film with a constant thickness due to the large thickness deviation of the film formed at the top and bottom. However, the composition for film deposition according to an embodiment of the present invention can form a film with uniform thickness even in a groove with a large aspect ratio. Therefore, it is more effective in manufacturing various semiconductor devices (such as DRAM and 3D NAND flash memory).

[0076] More specifically, when a hafnium (Hf) oxide film having a thickness of about 6 nm to 7 nm is formed on a substrate having a titanium nitride (TiN) film formed in a trench having an aspect ratio of 11:1 by ALD at a process temperature of about 350° C. and about 400° C. using the composition for film deposition according to an embodiment of the present invention, the thickness of the film is measured by Figure 6 The step coverage (%) calculated from the thickness of the hafnium (Hf) oxide film at the top, middle, and bottom of the trench in the transmission electron microscope (TEM) photograph may have a specific value or more and be excellent.

[0077] According to an embodiment, when a film containing a Group IV metal element is formed on a substrate having an aspect ratio of 11:1 at a temperature of about 350°C, the step coverage (%) of the film containing a Group IV metal element (e.g., a hafnium (Hf) oxide film) can be, 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.

[0078] In addition, when a film containing a Group IV metal element is formed on a substrate having an aspect ratio of 11:1 at a temperature of about 400°C, the step coverage (%) of the film containing a Group IV metal element (e.g., a hafnium (Hf) oxide film) can be, for example, 85% or greater, 90% or greater, 92% or greater, 93% or greater, 95% or greater, 96% or greater, 97% or greater, or 98% or greater.

[0079] Furthermore, when a zirconium (Zr) oxide film having a thickness of about 12 nm to 15 nm was formed on a substrate having a silicon oxide film formed in a trench having an aspect ratio of 20:1 by ALD at a process temperature of about 340° C. and about 360° C. using the composition for film deposition according to an embodiment of the present invention, the thickness of the zirconium (Zr) oxide film was measured by Figure 4 and Figure 5 The step coverage (%) calculated from the thickness of the zirconium (Zr) oxide film at the top, middle, and bottom of the trench in the transmission electron microscope (TEM) photograph may have a specific value or more and be excellent.

[0080] According to an embodiment, when a film containing a Group IV metal element is formed on a substrate having an aspect ratio of 20:1 at a temperature of about 300°C, the step coverage (%) of the film containing a Group IV metal element (e.g., a zirconium (Zr) oxide film) can be, for example, 80% or greater, 82% or greater, 85% or greater, 90% or greater, 92% or greater, 93% or greater, 95% or greater, or 96% or greater.

[0081] In addition, when a film containing a Group IV metal element is formed on a substrate having an aspect ratio of 20:1 at a temperature of about 340°C, the step coverage (%) of the film containing a Group IV metal element (e.g., a zirconium (Zr) oxide film) can be, for example, 80% or greater, 82% or greater, 85% or greater, 90% or greater, 92% or greater, 93% or greater, 95% or greater, or 96% or greater.

[0082] In addition, when a film containing a Group IV metal element is formed on a substrate having an aspect ratio of 20:1 at a temperature of about 360°C, the step coverage (%) of the film containing a Group IV metal element (e.g., a zirconium (Zr) oxide film) can be, for example, 85% or greater, 90% or greater, 92% or greater, 93% or greater, 95% or greater, 96% or greater, 97% or greater, 98% or greater, or 99% or greater.

[0083] If the film containing the fourth group metal element has a step coverage (%) satisfying the above range, a high step ratio and precise thickness control can be achieved, and thus it can be advantageously used to manufacture various semiconductor devices such as DRAM and 3D NAND flash memory.

[0084] [Composition for film deposition]

[0085] The composition for film deposition according to an embodiment of the present invention may include a precursor compound containing a Group 4 metal element represented by Formula 1 below.

[0086] [Formula 1]

[0087]

[0088] In Formula 1, M is Zr or Hf, R 1 is a methyl group, R 2 Selected from linear or branched C 3 -C 4 Alkyl group, R 3 To R 8 Each independently selected from linear or branched C 1 -C 4 Alkyl group.

[0089] Since the composition for film deposition according to an embodiment of the present invention includes the compound represented by Formula 1, when a film is deposited in a wide temperature range (e.g., a process temperature of 250°C to 400°C), a change in GPC with respect to temperature (ΔGPC, %) represented by the following Equation A can 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.

[0090] [Equation A]

[0091]

[0092] In equation A, GPC 250 It is GPC at 250℃. temp is the GPC at process temperature.

[0093] Specifically, according to an embodiment of the present invention, when a film is deposited using a composition for film deposition at a process temperature of, for example, 250°C to 320°C, a change in GPC with respect to temperature (ΔGPC, %) may be as small as, 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.

[0094] According to another embodiment of the present invention, when a film is deposited using the composition for film deposition at a process temperature of, for example, 250°C to 340°C, a change in GPC with respect to temperature (ΔGPC, %) may be as small as, 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.

[0095] According to another embodiment of the present invention, when a film is deposited using the composition for film deposition at a process temperature of, for example, 250°C to 360°C, a change in GPC with respect to temperature (ΔGPC, %) may be as small as, 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.

[0096] According to another embodiment of the present invention, when a film is deposited using the composition for film deposition at a process temperature of, for example, 250°C to 380°C, a change in GPC with respect to temperature (ΔGPC, %) may be as small as, 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.

[0097] According to another embodiment of the present invention, when a film is deposited at a process temperature of, for example, 300° C. to 360° C. using the composition for film deposition, a 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. Here, in Equation A, GPC may be used. 300 (i.e. GPC at 300°C) rather than GPC 250 to calculate.

[0098] According to another embodiment of the present invention, when a film is deposited at a process temperature of, for example, 330° C. to 390° C. using the composition for film deposition, a change in GPC (ΔGPC, %) with respect to temperature may be as small as, 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. Here, in Equation A, GPC may be used. 330 (i.e. GPC at 330°C) rather than GPC 250 to calculate.

[0099] According to another embodiment of the present invention, when a film is deposited at a process temperature of, for example, 360° C. to 400° C. using the composition for film deposition, a change in GPC with respect to temperature (ΔGPC, %) may be as small as, 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. Here, in Equation A, GPC may be used. 360 (i.e. GPC at 360°C) rather than GPC 250 to calculate.

[0100] More specifically, the composition for film deposition according to an embodiment of the present invention includes a precursor compound containing a Group IV metal element represented by the following Formula 2. When a zirconium (Zr)-containing film is deposited by ALD at a process temperature of 250° C. to 380° C., a change in GPC with respect to temperature represented by the above equation A (ΔGPC, %) may be as small as, 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.

[0101] [Formula 2]

[0102]

[0103] In formula 2, R 1 is a methyl group, R 2 Selected from linear or branched C 3 -C 4 Alkyl group, R 3 To R 8 Each independently selected from linear or branched C 1 -C 4 Alkyl group.

[0104] In addition, when a film is formed at a process temperature 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 using the compound represented by Formula 2, the change in GPC (ΔGPC, %) with respect to temperature is as small as 30% or less, as described above. That is, since GPC does not change significantly in a wide temperature range of not only low temperatures but also high temperatures, a film containing a Group IV metal element having a uniform thickness can be formed even on a surface having a groove with a large aspect ratio.

[0105] The precursor compound containing the Group IV metal element may be a compound represented by any one of the following Formulae 2-1 to 2-3.

[0106] [Formula 2-1]

[0107]

[0108] [Formula 2-2]

[0109] and

[0110] [Formula 2-3]

[0111]

[0112] In addition, the composition for film deposition includes a precursor compound containing a Group IV metal element represented by the following Formula 3. When a hafnium (Hf)-containing film is deposited by ALD at a process temperature of 250° C. to 400° C., a change in GPC with respect to temperature (ΔGPC, %) represented by the above equation A may be as small as, 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%.

[0113] [Formula 3]

[0114]

[0115] In formula 3, R 1 is a methyl group, R 2 Selected from linear or branched C 3 -C 4 Alkyl group, R 3 To R 8 Each independently selected from linear or branched C 1 -C 4 Alkyl group.

[0116] In addition, when a film is formed at a process temperature 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 using the compound represented by Formula 3, the change in GPC (ΔGPC, %) with respect to temperature is as small as 30% or less, as described above. That is, since GPC does not change significantly in a wide temperature range of not only low temperature but also high temperature, a film containing a Group IV metal element having a uniform thickness can be formed even on a surface having a groove with a large aspect ratio.

[0117] The precursor compound containing the Group IV metal element may be a compound represented by any one of the following Formulae 3-1 to 3-3.

[0118] [Formula 3-1]

[0119]

[0120] [Formula 3-2]

[0121] and

[0122] [Formula 3-3]

[0123]

[0124] During film deposition, the change in GPC with respect to temperature (ΔGPC, %) may be measured in units of 1° C. to 50° C. Specifically, the change in GPC with respect to temperature (ΔGPC, %) may be measured in units of, for example, 5° C., 10° C., 15° C., 20° C., 25° C., or 30° C.

[0125] At the same time, when ozone (O 3 ) is used as a reaction gas, and when a precursor compound containing a Group IV metal element is used to form a film containing a Group IV metal element by ALD, the temperature at which the film is formed can be 150°C to 400°C. to to to to to to to to or to of GPC.

[0126] For example, when the precursor compound containing a metal element of the fourth group is a precursor compound containing a metal element of the fourth group represented by Formula 2, and it is used to generate a precursor compound containing a metal element of the fourth group using ozone (O 3 ) as a reaction gas to form a zirconium (Zr)-containing film by ALD, the GPC at 150° C. to 400° C. (e.g., 200° C. to 400° C. or 250° C. to 400° C.) may be to to to or to

[0127] As another example, when the precursor compound containing the fourth group metal element is a precursor compound containing the fourth group metal element represented by Formula 3, and it is used to generate a precursor compound containing the fourth group metal element using ozone (O 3 ) as a reaction gas to form a hafnium (Hf)-containing film by ALD, the GPC may be to to to to or to

[0128] Since the precursor compound containing the Group IV metal element has a specific structure of Formula 1 (e.g., Formula 2 or Formula 3), and a composition for film deposition containing the precursor compound is used, a film containing the Group IV metal element can be uniformly formed by ALD within a wide temperature range.

[0129] In the commonly known CpZr(NMe 2 ) 3 Compound or CpHf(NMe 2 ) 3 In the synthesis method of the compound, alkyl-substituted cyclopentadiene can be used instead of cyclopentadiene (C 5 H 6 ) to synthesize a precursor compound containing a Group IV metal element represented by Formula 1 (eg, Formula 2 or Formula 3).

[0130] Mode for Carrying Out the Invention

[0131] Hereinafter, the present invention will be described in detail with reference to Examples. The following Examples merely illustrate the present invention, and the scope of the present invention is not limited thereto.

[0132] Preparation Example

[0133] <Preparation Example 1> Preparation of 1-methyl-3-propylcyclopenta-1,3-diene

[0134] [Formula 4-1]

[0135]

[0136] At room temperature, about 27 g (about 0.281 mole) of 3-methyl-2-cyclopentene-1-one (MCPO) and about 100 ml of tetrahydrofuran (THF, C 4 H 8 O). Slowly drop about 40.4 g (about 0.393 mol) of n-propylmagnesium chloride ( n The reaction solution was then stirred at room temperature for about 4 hours.

[0137] About 33.7 g (about 0.562 mol) of acetic acid (CH4) mixed with about 200 ml of distilled water (deionized water) was slowly added dropwise to the bottle. 3 COOH), and then the reaction solution was stirred at room temperature for one day. The water layer was removed using a separatory funnel. Then, about 14.9 g (about 0.140 mol) of sodium carbonate (Na2COOH) mixed with about 150 ml of distilled water (deionized water) was slowly added dropwise. 2 CO 3), 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 ) to remove moisture. The solvent was removed under reduced pressure, and then the resultant was distilled under reduced pressure to obtain about 17 g (yield 49.5%) of a colorless transparent liquid compound represented by Formula 4-1, 1-methyl-3-n-propylcyclopenta-1,3-diene, which was used to synthesize a composition for film deposition.

[0138] <Preparation Example 2> Preparation of 3-butyl-1-methylcyclopenta-1,3-diene

[0139] [Formula 4-2]

[0140]

[0141] In addition to using n-butylmagnesium chloride ( n BuMgCl) instead of n-propylmagnesium chloride ( n In addition to PrMgCl), the same method as in Preparation Example 1 was used to obtain about 18 g (yield 47%) of a colorless transparent liquid compound 3-butyl-1-methylcyclopenta-1,3-diene represented by Formula 4-2, which was used to synthesize a composition for film deposition.

[0142] <Preparation Example 3> Preparation of a Methylpropylcyclopentadiene Mixture Composition

[0143] [Formula 4-1]

[0144]

[0145] [Formula 4-3]

[0146]

[0147] [Formula 4-4]

[0148]

[0149] In a flame-dried 1000 ml Schlenk bottle, add about 50.0 g (0.624 mol) of methylcyclopentadiene and about 400 ml of tetrahydrofuran (THF, C 4 H 8 O) and cooled to -20°C. While maintaining -20°C, about 173.79 g (0.624 mol) of n-butyl lithium ( n BuLi), and then the reaction solution was stirred at room temperature for about 4 hours.

[0150] After the reaction was completed, 67.07 g (0.562 mol) of 1-bromopropane (C 3 H7 Br), and then the reaction solution was slowly warmed to room temperature and stirred for 12 hours.

[0151] After the reaction was completed, the salt formed during the reaction was removed by filtration and the mixture was washed with diethyl ether (C 2 H 5 ) 2 O) to extract the organic layer, and then use magnesium sulfate (MgSO 4 ) to remove moisture, and then remove the solvent and volatile by-products by distillation under reduced pressure to obtain 28.12g (37.2%) of a colorless transparent liquid mixture composition represented by Formula 4-1, Formula 4-3 and Formula 4-4. It was used to synthesize the composition for film deposition of Comparative Example 5.

[0152] <Preparation Example 4> Preparation of diethylcyclopentadiene mixture composition

[0153] [Formula 4-5]

[0154]

[0155] [Formula 4-6]

[0156]

[0157] [Formula 4-7]

[0158]

[0159] In a flame-dried 1-liter Schlenk bottle, add about 41.88 g (about 1.074 moles) of sodium amide (NaNH 2 ) and about 500 ml of tetrahydrofuran (THF, C 4 H 8 O), and then stirred. Slowly add about 100 g (about 1.074 moles) of ethylcyclopentadiene (C 7 H 10 ), and then the temperature was gradually raised to room temperature under stirring, and then stirred for another 17 hours. After the reaction was completed, about 116.98 g (about 1.074 moles) of 1-bromoethane (C 2 H 5 Br), then gradually raising the temperature to room temperature under stirring, and then stirring for 17 hours. After the reaction is completed, the salt formed during the reaction is removed by filtration, and then the solvent and volatile by-products are removed by distillation under reduced pressure to obtain 62g (yield 47.7%) of a colorless transparent liquid mixture composition represented by Formula 4-5, Formula 4-6 and Formula 4-7. It is used to synthesize the composition for film deposition of Comparative Example 4.

[0160] Example

[0161] <Example 1> [(Me, n Pr)Cp]Zr(NMe 2 ) 3 Preparation and composition for film deposition containing the same

[0162] [Formula 2-1]

[0163]

[0164] At room temperature, about 80 g (about 0.300 mol) of tetrakis(dimethylamino)zirconium(VI) and about 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 bottle, and then the reaction solution was stirred at room temperature for about 3 hours.

[0165] After the reaction was completed, the solvent was removed under reduced pressure, and then 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 composition for film deposition.

[0166] Boiling point (bp): 100°C (0.3 Torr)

[0167] 1 H-NMR (400 MHz, C 6 D 6 , 25℃):

[0168] δ5.797,5.763(m,3H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 ,

[0169] δ3.033(s,18H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(C H 3 ) 2 ] 3 ,

[0170] δ2.448(t,2H,[(CH 3 CH 2 C H 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 ,

[0171] δ2.094(s,3H,[(CH 3 CH 2 CH 2 )(C H 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 ,

[0172] δ1.577(m,2H,[(CH 3 C H 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 ,

[0173] δ0.923(t,3H,[(C H 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 .

[0174] <Example 2> [(Me, n Bu)Cp]Zr(NMe 2 ) 3 Preparation and composition for film deposition containing the same

[0175] [Formula 2-2]

[0176]

[0177] Using the same method as Example 1, 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, about 65 g (yield 60%) of a light yellow liquid compound represented by Formula 2-2 was obtained, which was used to synthesize a composition for film deposition.

[0178] Boiling point (bp): 110°C (0.3 Torr)

[0179] 1 H-NMR (400 MHz, C 6 D 6 , 25℃):

[0180] 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 ,

[0181] δ2.973(s,18H,[(CH 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(C H 3 ) 2 ] 3 ,

[0182] δ2.493(t,2H,[(CH 3 CH 2 CH 2 C H 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 ,

[0183] δ2.102(s,3H,[(CH 3 CH 2 CH 2 CH 2 )(C H 3 )(C 5H 3 )]Zr[N(CH 3 ) 2 ] 3 ,

[0184] δ1.547(m,2H,[(CH 3 CH 2 C H 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 ,

[0185] δ1.338(m,2H,[(CH 3 C H 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 ,

[0186] δ0.904(t,3H,[(C H 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Zr[N(CH 3 ) 2 ] 3 .

[0187] <Example 3> [(Me, n Pr)Cp]Hf(NMe 2 ) 3 Preparation and composition for film deposition containing the same

[0188] [Formula 3-1]

[0189]

[0190] At room temperature, about 65 g (about 0.184 mol) of tetrakis(dimethylamino)hafnium(VI) and about 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 bottle, and then the reaction solution was stirred at room temperature for about 3 hours.

[0191] After the reaction was completed, the solvent was removed under reduced pressure, and then 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 composition for film deposition.

[0192] Boiling point (bp): 100°C (0.3 Torr)

[0193] 1 H-NMR (400 MHz, C 6 D 6 , 25℃)

[0194] δ5.750,5.724(m,3H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 ,

[0195] δ2.987(s,18H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(C H 3 ) 2 ] 3 ,

[0196] δ2.466(t,2H,[(CH 3 CH 2 C H 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 ,

[0197] δ2.119(s,3H,[(CH 3 CH 2 CH 2 )(C H 3 )(C 5 H3 ))Hf[N(CH 3 ) 2 ] 3 ,

[0198] δ1.541(m,2H,[(CH 3 C H 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 ,

[0199] δ0.909(t,3H,[(C H 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 .

[0200] <Example 4> [(Me, n Bu)Cp]Hf(NMe 2 ) 3 Preparation and composition for film deposition containing the same

[0201] [Formula 3-2]

[0202]

[0203] Using the same method as Example 3, 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, about 65 g (yield 60%) of a light yellow liquid compound represented by Formula 3-2 was obtained, which was used to synthesize a composition for film deposition.

[0204] Boiling point (bp): 110°C (0.3 Torr)

[0205] 1 H-NMR (400 MHz, C 6 D 6 , 25℃):

[0206] δ5.767,5.759(m,3H,[(CH 3 CH 2 CH 2 CH 2 )(CH 3 )(C5 H 3 )]-Hf[N(CH 3 ) 2 ] 3 ,

[0207] δ3.011(s,18H,[(CH 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(C H 3 ) 2 ] 3 ,

[0208] δ2.524(t,2H,[(CH 3 CH 2 CH 2 C H 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 ,

[0209] δ2.132(s,3H,[(CH 3 CH 2 CH 2 CH 2 )(C H 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 ,

[0210] δ1.537(m,2H,[(CH 3 CH 2 C H 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 ,

[0211] δ1.330(m,2H,[(CH 3 C H 2 CH 2 CH 2 )(CH3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 ,

[0212] δ0.901(t,3H,[(C H 3 CH 2 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 ] 3 .

[0213] <Comparative Example 1>

[0214] UP Chemical's cyclopentadienyl-tris(dimethylamino)zirconium (CpZr(NMe 2 ) 3 or CpZr) products.

[0215] <Comparative Example 2>

[0216] UP Chemical's cyclopentadienyl-tris(dimethylamino)hafnium (CpHf(NMe 2 ) 3 or CpHf) products.

[0217] <Comparative Example 3>

[0218] UP Chemical's n-propylcyclopentadienyl-tris(dimethylamino)zirconium ( n PrCp)Zr(NMe 2 ) 3 or n PrCpZr) products.

[0219] <Comparative Example 4> [(Et) 2 Cp]Zr(NMe 2 ) 3 Preparation of mixture composition

[0220] [Formula 2-4]

[0221]

[0222] [Formula 2-5]

[0223]

[0224] Except for replacing 1-methyl-3-propylcyclopenta-1,3-diene with the diethylcyclopentadiene mixture composition represented by Formulas 4-5 to 4-7 obtained in Preparation Example 4, about 49 g (yield 71.1%) of a pale yellow liquid mixture composition represented by Formulas 2-4 and 2-5 was obtained using the same method as Example 1. It was used to synthesize a composition for film deposition.

[0225] <Comparative Example 5> [( n Pr,Me)Cp]Hf(NMe 2 ) 3 Preparation of mixture composition

[0226] [Formula 3-1]

[0227]

[0228] [Formula 3-4]

[0229]

[0230] At room temperature, about 54 g (about 0.152 mole) of tetrakis(dimethylamino)hafnium(VI) and about 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 bottle, and the reaction solution was stirred at room temperature for about 3 hours.

[0231] After the reaction was completed, the solvent was removed under reduced pressure, and then the resultant was distilled under reduced pressure to obtain about 42.2 g (yield 64%) of a pale yellow liquid mixture composition represented by formula 3-1 and 3-4 with a composition of about 1:1.87. The ratio of the two isomers having the same molecular weight is based on 1 H-NMR (400 MHz, C 6 D 6 , 25℃) spectrum of the methyl group (CH 3 ) where the hydrogen is located at 2.119ppm (Formula 3-1) and 2.043ppm (Formula 3-4) 1 The relative ratio of the integrated values ​​of the H-NMR peaks was determined.

[0232] Boiling point (bp): 100°C (0.3 Torr)

[0233] 1 H-NMR (400 MHz, C 6 D 6 , 25℃):

[0234] Compound represented by Formula 3-1: [(1- n Pr,3-Me)Cp]Hf(NMe 2 ) 3

[0235] δ5.750,5.724(m,3H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 3 ,

[0236] δ2.987(s,18H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(C H 3 ) 2 3 ,

[0237] δ2.466(t,2H,[(CH 3 CH 2 C H 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 3 ,

[0238] δ2.119(s,3H,[(CH 3 CH 2 CH 2 )(C H 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 3 ,

[0239] δ1.541(m,2H,[(CH 3 C H 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ​​​​3 ,

[0240] δ0.909(t,3H,[(C H 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 3 .

[0241] The compound represented by Formula 3-4: [(1- n Pr,2-Me)Cp]Hf(NMe 2 ) 3

[0242] δ5.913,5.842(m,3H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(CH 3 ) 2 3 ,

[0243] δ2.995(s,18H,[(CH 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 )]Hf[N(C H 3 ) 2 3 ,

[0244] δ2.408(t,2H,[(CH 3 CH 2 C H 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 3 ,

[0245] δ2.043(s,3H,[(CH 3 CH 2 CH 2 )(C H 3 )(C 5 H​​​​​3 ))Hf[N(CH 3 ) 2 ] 3 ,

[0246] δ1.498(m,2H,[(CH 3 C H 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 ,

[0247] δ0.886(t,3H,[(C H 3 CH 2 CH 2 )(CH 3 )(C 5 H 3 ))Hf[N(CH 3 ) 2 ] 3 .

[0248] Test Example

[0249] <Test Example 1> Structural Analysis of Precursor Compounds

[0250] conduct 1 H-NMR (400 MHz, C 6 D 6 , 25° C.) analysis was performed to analyze the structures of the precursor compounds containing the metal elements of Group IV prepared in Examples and Comparative Examples. The results are shown in the Examples and Comparative Examples above.

[0251] In addition, from Figure 1 It can be seen that the hafnium (Hf)-containing precursor compound of Comparative Example 5 has a composition of two structures (mixed structure) belonging to structural isomers. 1 In the H-NMR spectrum, the methyl group (CH 3 ) was observed at 2.119 ppm (Formula 3-1) and 2.043 ppm (Formula 3-4) of hydrogen 1 H-NMR peak (the ratio of Formula 3-1 to Formula 3-4 (relative ratio of the integral value of the peak) is about 1:1.87). On the other hand, the hafnium (Hf)-containing precursor compound prepared in Example 3 of the present invention is 1 H-NMR analysis confirmed that the product had a single composition.

[0252] The results of structural analysis confirmed that the hafnium (Hf)-containing precursor compound in Example 3 was a precursor having a high purity sufficient for application to the ALD process. Therefore, the precursor compound containing a Group IV metal element prepared by the method of the example can be used for the purpose of forming various films.

[0253] <Test Example 2> Zirconium (Zr)-containing oxide film formed by atomic layer deposition (ALD) and evaluation of GPC with respect to temperature

[0254] The composition for film deposition containing a zirconium (Zr) precursor compound prepared by the method of Example 1 and ozone (O 3 ) to form a zirconium (Zr) oxide film on a silicon substrate heated to a temperature (process temperature) of about 250° C. to 400° C. by ALD.

[0255] Specifically, a silicon substrate is first provided to an ALD reaction chamber.

[0256] Then, the composition for film deposition prepared by the method of Example 1 is added to a stainless steel tank and heated to about 120° C. Argon (Ar) delivery gas flows to the stainless steel tank at a flow rate of about 200 sccm to 500 sccm to supply the gaseous composition for film deposition to the reaction chamber. The temperature of the gas delivery pipe connected from the stainless steel tank to the reaction chamber is about 120° C. to 150° C. The closer to the reaction chamber, the higher the temperature. Oxygen (O 2 ) is supplied to the ozone (O 3 ) generator, producing a concentration of about 180g / m 3 Up to 220g / m 3 Ozone (O 3 ), ozone (O 3 ) is supplied to the reaction chamber and used as a reaction gas. In order to remove the zirconium (Zr)-containing precursor, ozone (O 3 ) and reaction byproducts, argon (Ar) is supplied to the reaction chamber at a flow rate of about 500 sccm to 2000 sccm. The process pressure of the reaction chamber is maintained at 0.9 Torr to 1.2 Torr.

[0257] The ALD gas supply cycle was repeated 100 times to form a zirconium (Zr) oxide film, wherein each ALD gas supply cycle included the following steps: supplying a composition for film deposition in a gaseous state for about 5 seconds to 30 seconds; supplying argon (Ar) gas for about 5 seconds to 30 seconds to remove the composition for film deposition (gas) remaining in the reactor; supplying ozone (O 3 ) for about 5 to 30 seconds; supply argon (Ar) for about 5 to 30 seconds to remove the remaining ozone (O 3 ).

[0258] A zirconium (Zr) oxide film was formed using the compositions for film deposition containing zirconium (Zr) precursor compounds of Comparative Example 1, Comparative Example 3 and Comparative Example 4 under the same conditions as the above-mentioned film formation method of Test Example 2, except that the stainless steel tank was heated to 100°C, 110°C and 120°C, respectively, to evaporate each composition containing a zirconium (Zr) precursor compound of Comparative Example 1, Comparative Example 3 and Comparative Example 4.

[0259] The thickness of each zirconium (Zr) oxide film formed using the composition for film deposition prepared by the method of Example 1, Comparative Example 1, Comparative Example 3 and Comparative Example 4 was measured using an ellipsometer (M-2000, JA Woollam).

[0260] Then, the measured thickness was divided by the number of gas supply cycles (100 times) to calculate the GPC. Specifically, the GPC at a temperature (process temperature) ranging from 250° C. to 400° C. was calculated. The results are shown in Figure 2 and Table 1.

[0261] In addition, the change in GPC (ΔGPC, %) with respect to the process temperature was calculated according to the following equation A. The results are shown in Table 1.

[0262] [Equation A]

[0263]

[0264] In equation A, GPC 250 It is GPC at 250℃. temp is the GPC at process temperature.

[0265] <Test Example 3> Formation of Hafnium (Hf)-Containing Oxide Film by Atomic Layer Deposition (ALD) and Evaluation of GPC with Respect to Temperature

[0266] The composition for film deposition containing the hafnium (Hf) precursor compound prepared by the method of Example 3 and ozone (O 3 ) to form a hafnium (Hf) oxide film on a silicon substrate heated to a process temperature of about 250° C. to 400° C. by ALD.

[0267] Specifically, a silicon substrate is first provided to an ALD reaction chamber.

[0268] Then, the composition for film deposition prepared by the method of Example 3 is added to a stainless steel tank and heated to about 120° C. Argon (Ar) delivery gas flows to the stainless steel tank at a flow rate of about 200 sccm to 500 sccm to supply the gaseous composition for film deposition to the reaction chamber. The temperature of the gas delivery pipe connected from the stainless steel tank to the reaction chamber is about 120° C. to 150° C. The closer to the reaction chamber, the higher the temperature. Oxygen (O 2 ) is supplied to the ozone (O 3 ) generator, producing a concentration of about 180g / m 3 Up to 220g / m 3 Ozone (O 3 ), ozone (O 3 ) is supplied to the reaction chamber and used as a reaction gas. In order to remove the hafnium (Hf)-containing precursor, ozone (O 3 ) and reaction byproducts, argon (Ar) is supplied to the reaction chamber at a flow rate of about 500 sccm to 2000 sccm. The process pressure of the reaction chamber is maintained at 0.9 Torr to 1.2 Torr.

[0269] The ALD gas supply cycle was repeated 100 times to form a hafnium (Hf) oxide film, wherein each ALD gas supply cycle included the following steps: supplying a composition for film deposition in a gaseous state for about 5 seconds to 30 seconds; supplying argon (Ar) gas for about 5 seconds to 30 seconds to remove the composition for film deposition (gas) remaining in the reactor; supplying ozone (O 3 ) for about 5 to 30 seconds; supply argon (Ar) for about 5 to 30 seconds to remove the remaining ozone (O 3 ).

[0270] A hafnium (Hf) oxide film was formed using the composition for film deposition containing a hafnium (Hf) precursor compound of Comparative Example 2 under the same conditions as the above-mentioned film formation method of Test Example 3, except that the stainless steel tank was heated to 100°C to evaporate the composition for film deposition containing a hafnium (Hf) precursor compound of Comparative Example 2.

[0271] The thickness of each hafnium (Hf) oxide film formed using the composition for film deposition prepared by the method of Example 3 and Comparative Example 2 was measured using an ellipsometer (M-2000, JA Woollam).

[0272] Then, the measured thickness was divided by the number of gas supply cycles (100 times) to calculate the GPC. Specifically, the GPC at a temperature (process temperature) ranging from 250° C. to 450° C. was calculated. The results are shown in Figure 3 and Table 2.

[0273] In addition, the change in GPC (ΔGPC, %) with respect to temperature was calculated according to the above equation A. The results are shown in Table 2.

[0274]

[0275] from Figure 2 As can be seen from Table 1, since the composition for film deposition containing the zirconium (Zr)-containing precursor compound of the present invention is used, self-limiting film growth of ALD can be achieved in a wide temperature range (especially at high temperatures). In addition, when the composition for film deposition of Example 1 is used, GPC does not change.

[0276] Specifically, when the compositions for film deposition of Comparative Examples 1 and 4 were used, the precursor compounds had low thermal stability. Therefore, GPC changed drastically with increasing temperature, such that the change in GPC (ΔGPC) was greater than 100% at 330° C. or 360° C., respectively.

[0277] This may mean that the film is grown by a gas phase reaction rather than a surface reaction due to thermal decomposition of the precursor compounds used in Comparative Example 1 and Comparative Example 4. That is, when the film is grown by a gas phase reaction, the film grows rapidly in the upper portion of the trench, while the film grows slowly in the lower portion (bottom) of the narrow and deep trench. In this case, the advantage of ALD that a film having a uniform thickness can be formed by a surface reaction even on a surface having deep trenches cannot be achieved.

[0278] On the other hand, when the composition for film deposition of Example 1 of the present invention is used, the zirconium (Zr)-containing precursor compound contained in the composition for film deposition has excellent thermal stability and does not undergo thermal decomposition. Therefore, even if ALD is performed at a high temperature, GPC does not change, and the change in GPC (ΔGPC) is maintained at 10% or less up to about 370°C.

[0279] In addition, when the composition for film deposition of Comparative Example 3 was used, the change in GPC (ΔGPC) at 380° C. was about 22%, showing a significant difference from Example 1 in which the change in GPC (ΔGPC) at the same temperature was about 12%.

[0280]

[0281] from Figure 3As can be seen from Table 2, since the composition for film deposition containing the hafnium (Hf)-containing precursor compound of the present invention is used, self-limiting film growth of ALD can be achieved in a wide temperature range (especially at high temperatures). In addition, when the composition for film deposition of Example 3 is used, GPC does not change.

[0282] Specifically, the precursor compound has low thermal stability in Comparative Example 2. Therefore, as the temperature increases, GPC changes drastically, so that the change in GPC (ΔGPC) at 400° C. is greater than 100%.

[0283] This may mean that the film grew by a gas phase reaction rather than a surface reaction due to thermal decomposition of the precursor compound used in Comparative Example 2. That is, when the film grew by a gas phase reaction, the film grew rapidly in the upper portion of the trench, while the film grew slowly in the lower portion (bottom) of the narrow and deep trench. In this case, the advantage of ALD that a film having a uniform thickness can be formed by a surface reaction even on a surface having deep trenches cannot be achieved.

[0284] On the other hand, in Example 3 of the present invention, the hafnium (Hf)-containing precursor compound contained in the composition for film deposition has excellent thermal stability and does not undergo thermal decomposition. Therefore, even if ALD is performed at a high temperature, GPC does not change, and the change in GPC (ΔGPC) is maintained at 8% or less up to about 440°C.

[0285] <Test Example 4> Evaluation of step coverage of zirconium (Zr) oxide-containing film

[0286] The step coverage of the zirconium (Zr) oxide-containing films formed using the compositions for film deposition of Example 1, Comparative Example 1, Comparative Example 3, and Comparative Example 4 were evaluated, respectively.

[0287] Specifically, the compositions for film deposition of Example 1, Comparative Example 1, Comparative Example 3, and Comparative Example 4 were used to form a zirconium (Zr) oxide film having a thickness of about 12 nm to 15 nm on a substrate having a silicon oxide (SiO 2) formed in a trench having an aspect ratio of 20:1 by ALD at process temperatures of about 300° C., 340° C., and 360° C., respectively. 2 )membrane.

[0288] exist Figure 4 and Figure 5 In transmission electron microscope (TEM) images of the top, middle, and bottom of the trench shown, the thickness and step coverage (%) of the zirconium (Zr) oxide-containing film were measured.

[0289] [Table 3]

[0290]

[0291] [Table 4]

[0292]

[0293] from Figure 4 and Figure 5 As can be seen from Tables 3 and 4, when the composition for film deposition of Example 1 of the present invention is used to form a zirconium (Zr) oxide film on a substrate having a groove with an aspect ratio of 20:1 at 300°C, 340°C and 360°C, the step coverage (%) is excellent compared with Comparative Example 1, Comparative Example 3 and Comparative Example 4.

[0294] Furthermore, when the composition for film deposition of Example 1 was used, it was confirmed that a zirconium (Zr) oxide-containing film having a very uniform thickness and a step coverage of about 99.3% could be formed even at a high temperature of about 360°C.

[0295] The above results confirm that, due to the use of the composition for film deposition comprising a zirconium (Zr)-containing precursor compound of the present invention, self-limiting film growth of ALD can be achieved over a wide temperature range (especially at a high temperature of about 360°C); therefore, zirconium (Zr)-containing films for various applications can be formed over a wide process temperature range.

[0296] In particular, according to the method for forming a zirconium (Zr)-containing film of the present invention, since GPC does not change in a wide temperature range, a zirconium (Zr)-containing film having a uniform thickness can be formed even on a surface of a groove having a large aspect ratio. Therefore, it can be advantageously used in manufacturing various semiconductor devices such as DRAM and 3D NAND flash memory.

[0297] <Test Example 5> Evaluation of step coverage of hafnium (Hf) oxide film

[0298] The step coverage of the hafnium (Hf) oxide films formed using the compositions for film deposition of Example 3 and Comparative Example 2 were evaluated, respectively.

[0299] Specifically, the compositions for film deposition of Example 3 and Comparative Example 2 were used to form a hafnium (Hf) oxide film having a thickness of about 6 nm to 7 nm on a substrate by ALD at process temperatures of about 350° C. and about 400° C., respectively, wherein a titanium nitride (TiN) film was formed in a trench having an aspect ratio of 11:1.

[0300] exist Figure 6In transmission electron microscope (TEM) images of the top, middle, and bottom of the trench shown, the thickness and step coverage (%) of the hafnium (Hf) oxide film were measured.

[0301] [Table 5]

[0302]

[0303] from Figure 6 As can be seen from Table 5, when the composition for film deposition of Example 3 of the present invention is used to form a hafnium (Hf) oxide film on a substrate having a step with an aspect ratio of 11:1 at 350° C. and 400° C., the step coverage (%) is excellent.

[0304] Specifically, when the composition for film deposition of Example 3 was used, it was confirmed that a hafnium (Hf) oxide film having a very uniform thickness and a step coverage of about 98.7% could be formed even at a high temperature of about 400°C.

[0305] The above results confirm that, due to the use of the composition for film deposition comprising a hafnium (Hf)-containing precursor compound of the present invention, self-limiting film growth of ALD can be achieved over a wide temperature range (especially at a high temperature of about 400°C); therefore, hafnium (Hf)-containing films for various applications can be formed over a wide process temperature range.

[0306] In particular, according to the method for forming a hafnium (Hf)-containing film of the present invention, since GPC does not change in a wide temperature range, a hafnium (Hf)-containing film having a uniform thickness can be formed even on a surface of a groove having a large aspect ratio. Therefore, it can be advantageously used in manufacturing various semiconductor devices such as DRAM and 3D NAND flash memory.

Claims

1. A method for forming a film containing a Group IV metal element, the method comprising reacting a composition for film deposition with a reaction gas to form a film containing a Group IV metal element on a substrate, the composition comprising a precursor compound containing a Group IV metal element represented by the following Formula 1: [Formula 1] In Formula 1, M is Zr or Hf, R1 is a methyl group, R2 is selected from a linear or branched C3-C4 alkyl group, and R3 to R8 are each independently selected from a linear or branched C1-C4 alkyl group.

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

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

4. The method for forming a film containing a Group IV metal element according to claim 1, wherein: The precursor compound containing the Group IV metal element has a structure having a single composition.

5. The method for forming a film containing a Group IV metal element according to claim 1, wherein: The precursor compound containing the Group IV metal element is a compound represented by the following Formula 2: [Formula 2] In Formula 2, R1 is a methyl group, R2 is selected from a linear or branched C3-C4 alkyl group, and R3 to R8 are each independently selected from a linear or branched C1-C4 alkyl group.

6. The method for forming a film containing a Group IV metal element according to claim 5, wherein: The precursor compound containing a Group IV metal element is a compound represented by one of the following formulae 2-1 to 2-3: [Formula 2-1] [Formula 2-2] and [Formula 2-3] 7. The method for forming a film containing a Group IV metal element 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, a change in GPC with respect to temperature (ΔGPC, %) represented by the following Equation A is 30% or less: [Equation A] In equation A, GPC 250 It is GPC at 250℃. temp is the GPC at process temperature.

8. The method for forming a film containing a Group IV metal element according to claim 7, wherein: When a zirconium (Zr)-containing film was formed by atomic layer deposition (ALD) at a process temperature of 250° C. to 400° C. using the compound represented by Formula 2, a change in GPC (ΔGPC, %) was 30% or less.

9. The method for forming a film containing a Group IV metal element according to claim 7, wherein: When a zirconium (Zr)-containing film was formed by atomic layer deposition (ALD) at a process temperature of 250° C. to 360° C. using the compound represented by Formula 2, a change in GPC (ΔGPC, %) was 30% or less.

10. The method for forming a film containing a Group IV metal element according to claim 1, wherein: The precursor compound containing the Group IV metal element is a compound represented by the following Formula 3: [Formula 3] In Formula 3, R1 is a methyl group, R2 is selected from a linear or branched C3-C4 alkyl group, and R3 to R8 are each independently selected from a linear or branched C1-C4 alkyl group.

11. The method for forming a film containing a Group IV metal element according to claim 10, wherein: The precursor compound containing a Group IV metal element is a compound represented by one of the following formulae 3-1 to 3-3: [Formula 3-1] [Formula 3-2] and [Formula 3-3] 12. The method for forming a film containing a Group IV metal element 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, a change in GPC (ΔGPC, %) with respect to temperature represented by the following Equation A is 30% or less: [Equation A] In equation A, GPC 250 It is GPC at 250℃. temp is the GPC at process temperature.

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

14. The method for forming a film containing a Group IV metal element according to claim 1, wherein: The film containing the Group IV metal element is formed to have a thickness ranging from 1 nm to 500 nm.

15. A composition for film deposition, comprising a precursor compound containing a Group IV metal element represented by the following Formula 1: [Formula 1] In Formula 1, M is Zr or Hf, R1 is a methyl group, R2 is selected from a linear or branched C3-C4 alkyl group, and R3 to R8 are each independently selected from a linear or branched C1-C4 alkyl group.

16. The composition for film deposition according to claim 15, wherein The precursor compound containing a Group IV metal element is a compound represented by one of the following formulae 2-1 to 2-3: [Formula 2-1] [Formula 2-2] and [Formula 2-3] 17. The composition for film deposition according to claim 15, wherein The precursor compound containing a Group IV metal element is a compound represented by one of the following formulae 3-1 to 3-3: [Formula 3-1] [Formula 3-2] and [Formula 3-3] 18. The composition for film deposition according to claim 15, wherein The precursor compound containing the Group IV metal element has a structure having a single composition.

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