Group iv metal element-containing compound, method for producing same, precursor composition for film formation containing same, and method for film formation using same
阅读说明：本技术 含第ⅳ族金属元素化合物、其制备方法、含其的膜形成用前体组合物及用其的膜形成方法 (Group iv metal element-containing compound, method for producing same, precursor composition for film formation containing same, and method for film formation using same ) 是由 韩元锡 高元勇 朴明镐 于 2019-02-01 设计创作，主要内容包括：本发明提供新型含第Ⅳ族金属元素的化合物、所述含第Ⅳ族金属元素的化合物的制备方法、包含所述含第Ⅳ族金属元素的化合物的膜形成用前体组合物、以及利用所述含第Ⅳ族金属元素的化合物的含第Ⅳ族金属元素膜的形成方法。具有如下优点：能够通过使用本申请的实现例所涉及的新型含第Ⅳ族金属元素的化合物的原子层沉积法而与以往已知的含第Ⅳ族金属元素的化合物相比在更高的温度下形成含第Ⅳ族金属元素膜。(The present invention provides a novel group iv metal element-containing compound, a method for producing the group iv metal element-containing compound, a precursor composition for film formation containing the group iv metal element-containing compound, and a method for forming a group iv metal element-containing film using the group iv metal element-containing compound. Has the following advantages: a group iv metal element-containing film can be formed at a higher temperature than a conventionally known group iv metal element-containing compound by an atomic layer deposition method using a novel group iv metal element-containing compound according to an embodiment of the present application.)
1. A group iv metal element-containing compound represented by the following chemical formula I:
[ chemical formula I ]
(R1C5H4)MA3，
In the chemical formula I, the compound represented by the formula I,
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
a is-NR2R3OR-OR4，
R2And R3Each independently being a methyl group or an ethyl group,
R4is a straight chain or branched chain alkyl with 1 to 4 carbon atoms.
2. The group iv metal element-containing compound according to claim 1, which is represented by the following chemical formula 1:
[ chemical formula 1]
(R1C5H4)M(NR2R3)3，
In the chemical formula 1, the first and second organic solvents,
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
R2and R3Each independently being methyl or ethyl.
3. The group iv metal element-containing compound according to claim 1, which is represented by the following chemical formula 2:
[ chemical formula 2]
(R1C5H4)M(OR4)3，
In the chemical formula 2,
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
R4is a straight chain or branched chain alkyl with 1 to 4 carbon atoms.
4. The group IV metal element-containing compound according to claim 1,
the compound containing a group IV metal element is [ alpha ]nPrCpZr(NMe2)3]、[nPrCpZr(NEtMe)3]、[nPrCpZr(NEt2)3]、[nBuCpZr(NMe2)3]、[nBuCpZr(NEtMe)3]、[nBuCpZr(NEt2)3]、[isoBuCpZr(NMe2)3]、[isoBuCpZr(NEtMe)3]、[isoBuCpZr(NEt2)3]、[secBuCpZr(NMe2)3]、[secBuCpZr(NEtMe)3]、[secBuCpZr(NEt2)3]、[neoPeCpZr(NMe2)3]、[neoPeCpZr(NEtMe)3]、[neoPeCpZr(NEt2)3]、[nPrCpHf(NMe2)3]、[nPrCpHf(NEtMe)3]、[nPrCpHf(NEt2)3]、[nBuCpHf(NMe2)3]、[nBuCpHf(NEtMe)3]、[nBuCpHf(NEt2)3]、[isoBuCpHf(NMe2)3]、[isoBuCpHf(NEtMe)3]、[isoBuCpHf(NEt2)3]、[secBuCpHf(NMe2)3]、[secBuCpHf(NEtMe)3]、[secBuCpHf(NEt2)3]、[neoPeCpHf(NMe2)3]、[neoPeCpHf(NEtMe)3]、[neoPeCpHf(NEt2)3]、[nPrCpTi(NMe2)3]、[nPrCpTi(NEtMe)3]、[nPrCpTi(NEt2)3]、[nBuCpTi(NMe2)3]、[nBuCpTi(NEtMe)3]、[nBuCpTi(NEt2)3]、[isoBuCpTi(NMe2)3]、[isoBuCpTi(NEtMe)3]、[isoBuCpTi(NEt2)3]、[secBuCpTi(NMe2)3]、[secBuCpTi(NEtMe)3]、[secBuCpTi(NEt2)3]、[neoPeCpTi(NMe2)3]、[neoPeCpTi(NEtMe)3]、[neoPeCpTi(NEt2)3]、[nPrCpZr(OMe)3]、[nPrCpZr(OEt)3]、[nPrCpZr(OiPr)3]、[nBuCpZr(OMe)3]、[nBuCpZr(OEt)3]、[nBuCpZr(OiPr)3]、[isoBuCpZr(OMe)3]、[isoBuCpZr(OEt)3]、[isoBuCpZr(OiPr)3]、[secBuCpZr(OMe)3]、[secBuCpZr(OEt)3]、[secBuCpZr(OiPr)3]、[neoPeCpZr(OMe)3]、[neoPeCpZr(OEt)3]、[neoPeCpZr(OiPr)3]、[nPrCpZr(OMe)3]、[nPrCpZr(OEt)3]、[nPrCpZr(OiPr)3]、[nBuCpZr(OMe)3]、[nBuCpZr(OEt)3]、[nBuCpZr(OiPr)3]、[isoBuCpZr(OMe)3]、[isoBuCpZr(OEt)3]、[isoBuCpZr(OiPr)3]、[secBuCpZr(OMe)3]、[secBuCpZr(OEt)3]、[secBuCpZr(OiPr)3]、[neoPeCpZr(OMe)3]、[neoPeCpZr(OEt)3]、[neoPeCpZr(OiPr)3]、[nPrCpHf(OMe)3]、[nPrCpHf(OEt)3]、[nPrCpHf(OiPr)3]、[nBuCpHf(OMe)3]、[nBuCpHf(OEt)3]、[nBuCpHf(OiPr)3]、[isoBuCpHf(OMe)3]、[isoBuCpHf(OEt)3]、[isoBuCpHf(OiPr)3]、[secBuCpHf(OMe)3]、[secBuCpHf(OEt)3]、[secBuCpHf(OiPr)3]、[neoPeCpHf(OMe)3]、[neoPeCpHf(OEt)3]、[neoPeCpHf(OiPr)3]、[nPrCpTi(OMe)3]、[nPrCpTi(OEt)3]、[nPrCpTi(OiPr)3]、[nBuCpTi(OMe)3]、[nBuCpTi(OEt)3]、[nBuCpTi(OiPr)3]、[isoBuCpTi(OMe)3]、[isoBuCpTi(OEt)3]、[isoBuCpTi(OiPr)3]、[secBuCpTi(OMe)3]、[secBuCpTi(OEt)3]、[secBuCpTi(OiPr)3]、[neoPeCpTi(OMe)3]、[neoPeCpTi(OEt)3]Or [ alpha ], [ alphaneoPeCpTi(OiPr)3]。
5. The group IV metal element-containing compound according to claim 1,
the compound containing the group IV metal element is liquid at normal temperature.
6. A method for preparing a compound containing a group IV metal element, comprising the steps of:
a compound containing a group IV metal element represented by the following chemical formula 1 is obtained by reacting a compound of the following chemical formula 3 with a compound of the following chemical formula 4,
[ chemical formula 3]
R1C5H4，
[ chemical formula 4]
M(NR2R3)3，
[ chemical formula 1]
(R1C5H4)M(NR2R3)3，
In each of the chemical formula 3, the chemical formula 4, and the chemical formula 1,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
m is Ti, Zr or Hf,
R2and R3Each independently being methyl or ethyl.
7. The method for producing a group iv metal element-containing compound according to claim 6, comprising the steps of:
a group IV metal element-containing compound represented by the following chemical formula 2 obtained by reacting the group IV metal element-containing compound represented by the following chemical formula 1 obtained in claim 6 with a compound of the following chemical formula 5,
[ chemical formula 1]
(R1C5H4)M(NR2R3)3，
[ chemical formula 5]
R4OH，
[ chemical formula 2]
(R1C5H4)M(OR4)3，
In each of the chemical formula 1, the chemical formula 5, and the chemical formula 2,
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
R2and R3Each independently being a methyl group or an ethyl group,
R4is a straight chain or branched chain alkyl with 1 to 4 carbon atoms.
8. The method for producing a group IV metal element-containing compound according to claim 6 or 7, wherein,
the reaction is carried out in an organic solvent.
9. The method for producing a group IV metal element-containing compound according to claim 6 or 7, wherein,
the reaction is performed at normal temperature.
10. A precursor composition for forming a film, comprising the group iv metal element-containing compound according to any one of claims 1 to 5.
11. The precursor composition for forming a film of claim 10, wherein,
the precursor composition is used to form a group iv metal element-containing film.
12. The precursor composition for forming a film of claim 10, wherein,
the precursor composition is used for forming an oxide film, a nitride film, an oxynitride film, a carbide film or a carbonitride film containing a group IV metal element.
13. The precursor composition for forming a film of claim 10, wherein,
the precursor composition is used to form a group iv metal element-containing film by vapor deposition.
14. A method for forming a group iv metal element-containing film, comprising the steps of:
forming a group iv metal element-containing film on a substrate by reacting a precursor containing the group iv metal element-containing compound according to any one of claims 1 to 5 with a reaction gas.
15. The method for forming a group IV metal element-containing film according to claim 14,
forming a group IV metal element-containing film on the substrate by vapor deposition.
16. The method for forming a group IV metal element-containing film according to claim 14,
the film containing the metal element of the group IV is an oxide film, a nitride film, an oxynitride film, a carbide film or a carbonitride film containing the metal element of the group IV.
17. The method for forming a group IV metal element-containing film according to claim 14,
the method comprises the following steps:
providing one or more surfaces of the substrate to a reaction chamber;
introducing a precursor comprising the group iv metal element-containing compound into the reaction chamber; and
introducing a reaction gas into the reaction chamber,
wherein a group IV metal element-containing film is formed on one or more surfaces of the substrate by vapor deposition.
18. The method for forming a group IV metal element-containing film according to claim 14,
the reactant gas is selected from the group consisting of an oxygen-containing supply, a nitrogen-containing supply, a carbon supply, a reductant, and combinations thereof.
19. The method for forming a group IV metal element-containing film according to claim 14,
forming a film containing the group iv metal element and one or more additional metal elements by supplying, simultaneously or sequentially, one or more additional precursors containing a metal element which is the same as or different from the first precursor with the first precursor containing the group iv metal element-containing compound.
20. The method for forming a group IV metal element-containing film according to claim 15,
the vapor deposition is one or more selected from the group consisting of chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition, plasma enhanced cyclic chemical vapor deposition, atomic layer deposition, and plasma enhanced atomic layer deposition.
Technical Field
The present invention relates to a novel group iv metal element-containing compound, a method for producing the group iv metal element-containing compound, a precursor composition for film formation containing the group iv metal element-containing compound, and a method for forming a group iv metal element-containing film using the group iv metal element-containing compound.
Background
Compounds containing group iv metal elements such as titanium (Ti), zirconium (Zr), and hafnium (Hf), films (e.g., zirconium oxide films, titanium nitride films, etc.) containing oxides or nitrides of the group iv metal elements, and the like are used for manufacturing semiconductor devices as high dielectric substances, electrodes, and the like. In order to form a film containing a group iv metal element by a Chemical Vapor Deposition (CVD) method or an Atomic Layer Deposition (ALD) method, various group iv metal compounds are used. In addition, a compound containing a group IV metal element is also used as a catalyst for polymer formation [ Korean patent laid-open No. 10-0852234 ]. However, there is still a need to develop a novel group iv metal element-containing compound that can be effectively used as a precursor capable of forming a uniform film, particularly a uniform group iv metal element-containing film or thin film on the entire surface of a substrate or a porous substrate having irregularities (grooves).
Disclosure of Invention
Technical problem
An object of the present invention is to provide a novel group iv metal element-containing compound, a method for producing the group iv metal element-containing compound, a precursor composition for film formation containing the group iv metal element-containing compound, and a method for forming a group iv metal element-containing film using the group iv metal element-containing compound.
However, the technical problems to be solved by the present application are not limited to the above-mentioned technical problems, and other technical problems not mentioned can be clearly understood by those skilled in the art from the following descriptions.
Means for solving the problems
A first aspect of the present application provides a group iv metal element-containing compound represented by the following chemical formula I,
[ chemical formula I ]
(R1C5H4)MA3，
In the chemical formula I above, the compound of formula I,
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
a is-NR2R3OR-OR4，
R2And R3Each independently being a methyl group or an ethyl group,
R4is a straight chain or branched chain alkyl with 1 to 4 carbon atoms.
A second aspect of the present application provides a method for producing a group iv metal element-containing compound according to the first aspect of the present application.
A third aspect of the present application provides a precursor composition for film formation comprising the group iv metal element-containing compound according to the first aspect of the present application.
A fourth aspect of the present application provides a method of forming a group iv metal element-containing film, comprising the steps of: a group iv metal element-containing film is formed using the group iv metal element-containing compound according to the first aspect of the present application as a precursor.
Advantageous effects
The novel group iv metal element-containing compound according to the embodiment of the present application is a hitherto unknown novel compound. The novel group iv metal element-containing compound according to the embodiment of the present application is liquid at normal temperature and has thermal stability.
The novel group iv metal element-containing compound according to the embodiment of the present application has high thermal stability and can be used as a precursor for vapor deposition, and for example, a group iv metal element-containing film can be formed by using the compound as a precursor for an atomic layer deposition method or a chemical vapor deposition method. For example, the novel group iv metal element-containing compound according to the embodiment of the present application has the following excellent effects: a substrate having fine irregularities (grooves) with an aspect ratio of about 1 or more and a width of about 1 μm or less on the surface thereof includes the surface of the fine irregularities (grooves) including the deepest surface of the fine irregularities (grooves) and the upper surface of the fine irregularities (grooves), and a group iv metal element-containing film having a thickness of several to several tens nm can be uniformly formed on the entire surface of the substrate.
The composition containing the group iv metal element-containing compound precursor according to the embodiment of the present application and the method for forming a group iv metal element-containing film using the precursor can be applied to the commercial production of semiconductor devices. In particular, in order to produce a DRAM semiconductor device, it is necessary to form a high dielectric substance having a thickness of several nm on a substrate having a groove width narrower than about 100nm or about 50nm and an aspect ratio of about 10:1, about 20:1, or about 30:1 or a substrate having a groove deeper and narrower than the groove, and particularly, it is necessary to form a high dielectric position film having a uniform thickness also at a temperature of about 280 ℃, about 300 ℃, or more, and therefore, a precursor composition capable of forming a film having a uniform thickness in a very narrow and deep groove by an atomic layer deposition method (ALD) even at a high temperature is required, and a Ti, Zr, or Hf compound having very high thermal stability is required for use as such a precursor composition. Thus, the group iv metal element-containing compound according to the examples of the present application can be effectively used as a precursor satisfying the above-described required characteristics.
The group iv metal element-containing compound according to the embodiments of the present application is used as a precursor used in ALD, CVD, or the like, and can provide properties required in the production of next-generation devices such as semiconductors, such as improved thermal stability, high volatility, and/or increased deposition rate, and thus can be effectively used for the formation of a group iv metal element-containing film or thin film.
The group iv metal element-containing compound according to an embodiment of the present application can be applied to various fields such as a catalyst and the like.
Drawings
FIG. 1 is compound 1[ prepared from an embodiment of the present applicationnPrCpZr(NMe2)3]And thermogravimetric analysis charts of respective comparative examples of compounds.
FIG. 2 is a representation of
FIG. 3 is a graph showing the utilization of Compound 1[ prepared by an example of the present application ] according to the substrate temperaturenPrCpZr(NMe2)3]And Compound 2[ alpha ], [ alphanBuCpZr(NMe2)3]The film growth by the atomic layer deposition method of (1).
FIG. 4 is a graph showing the utilization of Compound 1[ prepared by an example of the present application ] according to the precursor supply timenPrCpZr(NMe2)3]And a film growth of the comparative example compound.
FIG. 5 is a view showing the observation by a Transmission Electron Microscope (TEM) of using Compound 1[ prepared by an example of the present application ]nPrCpZr(NMe2)3]The cross-section of the film formed on the substrate containing the narrow trench.
FIG. 6 isThe use of Compound 1[ prepared by an example of the present application ] is expressed in terms of the substrate temperaturenPrCpZr(NMe2)3]And a film growth by the plasma atomic layer deposition method of (1) and a film growth using a compound of comparative example.
FIG. 7 is a graph showing the temperature of a substrate prepared using an embodiment of the present applicationnPrCpTi(OMe)3The film growth by the atomic layer deposition method of (1).
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that those skilled in the art can easily practice the invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In addition, in order to clearly explain the present invention, portions that are not related to the description are omitted in the drawings, and like reference numerals are used for like portions throughout the specification.
Throughout the specification of the present invention, when a certain portion is described as being "connected" to another portion, the description includes not only the case of "directly connected" but also the case of "electrically connected" with another device interposed therebetween.
Throughout the specification of the present invention, when a certain component is described as being "on" another component, it includes not only a case where the certain component is in contact with the another component but also a case where the other component exists between the two components.
In the present invention, when a part is described as "including" a certain component throughout the specification, unless explicitly stated to the contrary, it does not mean that other components are excluded, and it means that other components may be included. The terms "about", "substantially", and the like, as used throughout the specification to indicate a degree of deviation inherent in the meaning of the reference, are used in the meaning of the value or close to the value when manufacturing and material tolerances are allowed, and are used to prevent the unscrupulous infringer from misusing the disclosure that refers to the exact or absolute value in order to aid in the understanding of the invention. The term "step of …" used throughout the description of the invention does not mean "step for …".
Throughout the description of the present invention, the term "combination thereof" included in the expression of markush form means a mixture or combination of one or more selected from the group consisting of the constituent elements described in the expression of markush form, and means including one or more selected from the group consisting of the constituent elements described above.
Throughout the description of the present invention, the expression "a and/or B" means "a or B, or a and B".
Throughout the description of the present invention, the term "alkyl" may include straight or branched chain alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, or 1 to 4 carbon atoms, or all possible isomers thereof. For example, the alkyl group may be methyl (Me), ethyl (Et), n-propyl (n-propyl)nPr), isopropyl group (iPr), n-butyl (nBu), tert-butyl group (tBu), isobutyl (b)iBu), sec-butyl (sBu), neopentyl (neoPe), hexyl, isohexyl, heptyl, 4-dimethylpentyl, octyl, 2, 4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, isomers thereof, and the like, but may not be limited thereto.
Throughout the present specification, the term "group IV metal element" refers to a chemical element belonging to group IV of the periodic Table of elements, and may include Ti, Zr or Hf.
Throughout the specification of the present application, the term "Cp" is defined by-C5H4The expression "cyclopentadienyl" refers to an abbreviation of "cyclopentadienyl".
Hereinafter, an embodiment of the present application will be described in detail, but the present application is not limited thereto.
A first aspect of the present application provides a group iv metal element-containing compound represented by the following chemical formula I.
[ chemical formula I ]
(R1C5H4)MA3，
In the chemical formula I, the compound represented by the formula I,
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
a is-NR2R3OR-OR4，
R2And R3Each independently being a methyl group or an ethyl group,
R4is a straight chain or branched chain alkyl with 1 to 4 carbon atoms.
In one embodiment of the present application, the group iv metal element-containing compound may be a compound represented by the following
[ chemical formula 1]
(R1C5H4)M(NR2R3)3，
In the above-described
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
R2and R3Each independently being methyl or ethyl.
In one embodiment of the present application, the group iv metal element-containing compound may be a compound represented by the following
[ chemical formula 2]
(R1C5H4)M(OR4)3，
In the above-described
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
R4is a straight chain or branched chain alkyl with 1 to 4 carbon atoms.
In one embodiment of the present application, R1There may be mentioned, but not limited to, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl or neopentyl.
In one embodiment of the present application, R4Can be methyl, ethyl, n-propyl or iso-propylPropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, but is not limited thereto. In one embodiment of the present application, as examples of the group iv metal element-containing compound represented by the above chemical formula I, the following Ti, Zr, or Hf compounds may be mentioned, but not limited thereto.
(n-propylcyclopentadienyl) tris (dimethylamino) zirconium (, (n-propylcyclopentadienyl) tris (dimethylamino)nPrCpZr(NMe2)3])；
(n-propylcyclopentadienyl) tris (ethylmethylamino) zirconium (, (n-propylcyclopentadienyl)nPrCpZr(NEtMe)3])；
(n-propylcyclopentadienyl) tris (diethylamino) zirconium (, (N-propylcyclopentadienyl)nPrCpZr(NEt2)3])；
(n-butylcyclopentadienyl) tris (dimethylamino) zirconium (nBuCpZr(NMe2)3])；
(n-butylcyclopentadienyl) tris (ethylmethylamino) zirconium (, (n-butylcyclopentadienyl)nBuCpZr(NEtMe)3])；
(n-butylcyclopentadienyl) tris (diethylamino) zirconium (, (+), N-butylcyclopentadienyl)nBuCpZr(NEt2)3])；
(isobutylcyclopentadienyl) tris (dimethylamino) zirconium (isoBuCpZr(NMe2)3])；
(isobutylcyclopentadienyl) tris (ethylmethylamino) zirconium (, (ethylmethylamino)isoBuCpZr(NEtMe)3])；
(isobutylcyclopentadienyl) tris (diethylamino) zirconium (, (diethylamino)isoBuCpZr(NEt2)3])；
(sec-butylcyclopentadienyl) tris (dimethylamino) zirconium (secBuCpZr(NMe2)3])；
(sec-butylcyclopentadienyl) tris (ethylmethylamino) zirconium (, (sec-butylcyclopentadienyl)secBuCpZr(NEtMe)3])；
(sec-butylcyclopentadienyl) tris (diethylamino) zirconium (, ("sec-butylcyclopentadienyl"))secBuCpZr(NEt2)3])；
(neopentyl cyclopentadienyl) tris (dimethylamino) zirconium (, (dimethylamino)neoPeCpZr(NMe2)3])；
(neopentyl cyclopentadienyl) tris (ethylmethylamino) zirconium (, (neopentyl) cyclopentadienyl)neoPeCpZr(NEtMe)3])；
(neopentyl cyclopentadienyl) tris (diethylamino) zirconium (, (neopentyl) cyclopentadienyl)neoPeCpZr(NEt2)3])；
(n-propylcyclopentadienyl) tris (dimethylamino) hafnium (, (N-propylcyclopentadienyl) tris (dimethylamino)nPrCpHf(NMe2)3])；
(n-propylcyclopentadienyl) tris (ethylmethylamino) hafnium (, (n-propylcyclopentadienyl) tris (ethylmethylamino)nPrCpHf(NEtMe)3])；
(n-propylcyclopentadienyl) tris (diethylamino) hafnium (,)nPrCpHf(NEt2)3])；
(n-butylcyclopentadienyl) tris (dimethylamino) hafnium ([ 2], [ 2]nBuCpHf(NMe2)3])；
(n-butylcyclopentadienyl) tris (ethylmethylamino) hafnium (, (n-butylcyclopentadienyl) tris (ethylmethylamino)nBuCpHf(NEtMe)3])；
(n-butylcyclopentadienyl) tris (diethylamino) hafnium ([ alpha ], [ beta ]nBuCpHf(NEt2)3])；
(isobutylcyclopentadienyl) tris (dimethylamino) hafnium (,)isoBuCpHf(NMe2)3])；
(isobutylcyclopentadienyl) tris (ethylmethylamino) hafnium (, (ethylmethylamino)isoBuCpHf(NEtMe)3])；
(isobutylcyclopentadienyl) tris (diethylamino) hafnium ([ 2 ])isoBuCpHf(NEt2)3])；
(sec-butylcyclopentadienyl) tris (dimethylamino) hafnium (,)secBuCpHf(NMe2)3])；
(sec-butylcyclopentadienyl) tris (ethylmethylamino) hafnium (, (sec-butylcyclopentadienyl) tris (ethylmethylamino)secBuCpHf(NEtMe)3])；
(sec-butylcyclopentadienyl) tris (diethylamino) hafnium ([ 2 ])secBuCpHf(NEt2)3])；
(neopentyl cyclopentadienyl) tris (dimethylamino) hafnium (, (dimethylamino)neoPeCpHf(NMe2)3])；
(neopentyl cyclopentadienyl) tris (ethylmethylamino) hafnium (, (neopentyl) cyclopentadienyl) tris (ethylmethylamino)neoPeCpHf(NEtMe)3])；
(neopentyl cyclopentadienyl) tris (diethylamino) hafnium (, (N-ethyl-amino)neoPeCpHf(NEt2)3])；
(n-propylcyclopentadienyl) tris (dimethylamino) titanium (, etcnPrCpTi(NMe2)3])；
(n-propylcyclopentadienyl) tris (ethylmethylamino) titanium (, (n-propylcyclopentadienyl) tris (ethylmethylamino)nPrCpTi(NEtMe)3])；
(n-propylcyclopentadienyl) tris (diethylamino) titanium (, etc.)nPrCpTi(NEt2)3])；
(n-butylcyclopentadienyl) tris (dimethylamino) titanium ([ alpha ], [nBuCpTi(NMe2)3])；
(n-butylcyclopentadienyl) tris (ethylmethylamino) titanium (, etcnBuCpTi(NEtMe)3])；
(n-butylcyclopentadienyl) tris (diethylamino) titanium ([ alpha ], [ beta ], [ alpha ], [ beta ], [ alpha ], [ beta ]nBuCpTi(NEt2)3])；
(isobutylcyclopentadienyl) tris (dimethylamino) titanium (isoBuCpTi(NMe2)3])；
(isobutylcyclopentadienyl) tris (ethylmethylamino) titanium (, (i) butylcyclopentadienyl) tris (ethylmethylamino)isoBuCpTi(NEtMe)3])；
(isobutylcyclopentadienyl) tris (diethylamino) titanium ([ 2 ])isoBuCpTi(NEt2)3])；
(sec-butylcyclopentadienyl) tris (dimethylamino) titanium (secBuCpTi(NMe2)3])；
(sec-butylcyclopentadienyl) tris (ethylmethylamino) titanium (, etc.)secBuCpTi(NEtMe)3])；
(sec-butylcyclopentadienyl) tris (diethylamino) titanium ([ alpha ], [ beta ], [ alpha ], [ beta ], [ alpha ]secBuCpTi(NEt2)3])；
(neopentyl cyclopentadienyl) tris (dimethylamino) titanium ([ 2], ]neoPeCpTi(NMe2)3])；
(neopentyl cyclopentadienyl) tris (ethylmethylamino) titanium (, (neopentyl) aminoneoPeCpTi(NEtMe)3])；
(neopentyl cyclopentadienyl) tris (diethylamino) titanium ([ 2], [ 2]neoPeCpTi(NEt2)3])；
(n-propylcyclopentadienyl) trimethoxyzirconium (, (n-propylcyclopentadienyl) trimethoxynPrCpZr(OMe)3])；
(n-propylcyclopentadienyl) triethoxy zirconium ([ 2]nPrCpZr(OEt)3])；
(n-propylcyclopentadienyl) triisopropoxzirconium ([ 2]nPrCpZr(OiPr)3])；
(n-butylcyclopentadienyl) trimethoxyzirconium (nBuCpZr(OMe)3])；
(n-butylcyclopentadienyl) triethoxy zirconium ([ 2]nBuCpZr(OEt)3])；
(n-butylcyclopentadienyl) triisopropoxzirconium ([ 2]nBuCpZr(OiPr)3])；
(isobutyl cyclopentadienyl) trimethoxy zirconium (, (isobutyl cyclopentadienyl)isoBuCpZr(OMe)3])；
(isobutyl cyclopentadienyl) triethoxy zirconium ([ 2]isoBuCpZr(OEt)3])；
(isobutyl cyclopentadienyl) triisopropoxzirconium ([ 2]isoBuCpZr(OiPr)3])；
(sec-butylcyclopentadienyl) trimethoxyzirconium ([ 2 ])secBuCpZr(OMe)3])；
(sec-butylcyclopentadienyl) zirconium triethoxide ([ 2]secBuCpZr(OEt)3])；
(sec-butylcyclopentadienyl) triisopropoxzirconium ([ 2]secBuCpZr(OiPr)3])；
(neopentyl cyclopentadienyl) trimethoxy zirconium ([ 2]neoPeCpZr(OMe)3])；
(neopentyl cyclopentadienyl) zirconium triethoxide ([ 2]neoPeCpZr(OEt)3])；
(neopentyl cyclopentadienyl) zirconium triisopropoxide ([ 2]neoPeCpZr(OiPr)3])；
(n-propylcyclopentadienyl) trimethoxyhafnium (nPrCpHf(OMe)3])；
(n-propylcyclopentadienyl) hafnium triethoxide ([ 2]nPrCpHf(OEt)3])；
(n-propylcyclopentadienyl) triisopropoxhafnium (nPrCpHf(OiPr)3])；
(n-butylcyclopentadienyl) trimethoxyhafnium (nBuCpHf(OMe)3])；
(n-butylcyclopentadienyl) hafnium triethoxide (nBuCpHf(OEt)3])；
(n-butylcyclopentadienyl) triisopropoxhafnium (nBuCpHf(OiPr)3])；
(isobutylcyclopentadienyl) trimethoxyhafnium (, (isoBuCpHf(OMe)3])；
(isobutylcyclopentadienyl) hafnium triethoxide (, (isoBuCpHf(OEt)3])；
(isobutylcyclopentadienyl) hafnium triisopropoxide (isoBuCpHf(OiPr)3])；
(sec-butylcyclopentadienyl) trimethoxyhafnium ([ 2]secBuCpHf(OMe)3])；
(sec-butylcyclopentadienyl) hafnium triethoxide (secBuCpHf(OEt)3])；
(sec-butylcyclopentadienyl) triisopropoxhafnium (secBuCpHf(OiPr)3])；
(neopentyl cyclopentadienyl) trimethoxyhafnium (, (neopentyl) hafniumneoPeCpHf(OMe)3])；
(neopentyl cyclopentadienyl) hafnium triethoxide (, (neopentyl) cyclopentadienyl)neoPeCpHf(OEt)3])；
(neopentyl cyclopentadienyl) hafnium triisopropoxide (, (neopentyl cyclopentadienyl)neoPeCpHf(OiPr)3])；
(n-propylcyclopentadienyl) trimethoxytitanium ([ 2]nPrCpTi(OMe)3])；
(n-propylcyclopentadienyl) triethoxytitanium ([ 2]nPrCpTi(OEt)3])；
(n-propylcyclopentadienyl) triisopropoxytitanium ([ 2]nPrCpTi(OiPr)3])；
(n-butylcyclopentadienyl) trimethoxytitanium (nBuCpTi(OMe)3])；
(n-butylcyclopentadienyl) triethoxytitanium ([ 2]nBuCpTi(OEt)3])；
(n-butylcyclopentadienyl) triisopropoxytitanium ([ 2]nBuCpTi(OiPr)3])；
(isobutyl cyclopentadienyl) trimethoxy titanium (, (isobutyl cyclopentadienyl)isoBuCpTi(OMe)3])；
(isobutyl cyclopentadienyl) triethoxy titanium ([ 2]isoBuCpTi(OEt)3])；
(isobutyl cyclopentadienyl) titanium triisopropoxide ([ 2]isoBuCpTi(OiPr)3])；
(sec-butylcyclopentadienyl) trimethoxytitanium ([ 2 ])secBuCpTi(OMe)3])；
(sec-butylcyclopentadienyl) triethoxytitanium ([ 2]secBuCpTi(OEt)3])；
(sec-butylcyclopentadienyl) titanium triisopropoxide ([ 2]secBuCpTi(OiPr)3])；
(neopentyl cyclopentadienyl) trimethoxytitanium ([ 2]neoPeCpTi(OMe)3])；
(neopentyl cyclopentadienyl) triethoxy titanium ([ 2]neoPeCpTi(OEt)3])；
(neopentyl cyclopentadienyl) titanium triisopropoxide ([ 2]neoPeCpTi(OiPr)3])。
In one embodiment of the present application, the group iv metal element-containing compound is liquid and stable at normal temperature.
A second aspect of the present application provides a method for producing the above-mentioned group iv metal element-containing compound according to the first aspect of the present application.
In an embodiment of the present application, the preparation method may include the steps of: obtaining the group iv metal element-containing compound represented by the
[ chemical formula 3]
R1C5H4，
[ chemical formula 4]
M(NR2R3)3，
[ chemical formula 1]
(R1C5H4)M(NR2R3)3，
In each of the above chemical formula 3, the above chemical formula 4 and the
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
m is Ti, Zr or Hf,
R2and R3Each independently being methyl or ethyl.
In other embodiments of the present application, the preparation method may include the steps of: the group iv metal element-containing compound represented by the following
[ chemical formula 1]
(R1C5H4)M(NR2R3)3，
[ chemical formula 5]
R4OH，
[ chemical formula 2]
(R1C5H4)M(OR4)3，
In each of the
m is Ti, Zr or Hf,
R1is a linear or branched alkyl group having 3 to 5 carbon atoms,
R2and R3Each independently being a methyl group or an ethyl group,
R4is a straight chain or branched chain alkyl with 1 to 4 carbon atoms.
In an embodiment of the present application, the compound of chemical formula 3 and the compound of chemical formula 4 may be reacted or the compound of
In an embodiment of the present application, the step of reacting the compound of chemical formula 3 with the compound of chemical formula 4 or reacting the compound of
In one embodiment of the present invention, after mixing the compound of chemical formula 3 with an organic solvent, the compound of chemical formula 4 is slowly added dropwise and reacted at normal temperature (1 hour or more, 3 hours or less, or 5 hours or less), and then the solvent is removed under reduced pressure and distillation under reduced pressure is performed, thereby obtaining the compound containing the group iv metal element of
In one embodiment of the present invention, after mixing the compound of
The above-mentioned contents described in the first aspect of the present application are all applied to the second aspect of the present application.
A third aspect of the present application provides a precursor composition for film formation, which contains the above-mentioned group iv metal element-containing compound according to the first aspect of the present application.
In one embodiment of the present application, the film-forming precursor composition can be used for depositing a group iv metal element-containing film or thin film. The thickness of the group iv metal element-containing film or thin film may be about 1 nm to several micrometers, but is not limited thereto.
In an embodiment of the present invention, the group iv metal element-containing film may include a group iv metal element-containing oxide film, a nitride film, an oxynitride film, a carbide film, or a carbonitride film, but is not limited thereto.
In an embodiment of the present application, the group iv metal element-containing film may contain two or more of the group iv metal elements, or may contain one or more additional metal elements together with one or more of the group iv metal elements. The additional metal may include, without particular limitation, a metal known In the art, and may be, for example, one or more metals selected from the group consisting of magnesium (Mg), calcium (Ca), zinc (Zn), boron (B), aluminum (Al), indium (In), silicon (Si), germanium (Ge), tin (Sn), hafnium (Hf), zirconium (Zr), titanium (Ti), vanadium (V), niobium (Nb), tantalum (Ta), a lanthanide atom (more particularly, scandium (Sc), yttrium (Y), and lanthanum (La), and a rare earth metal atom), but is not limited thereto.
In an embodiment of the present application, the group iv metal element-containing film may be formed by vapor deposition. For example, the vapor deposition may be one or more deposition selected from the group consisting of chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition, plasma enhanced cyclic chemical vapor deposition, atomic layer deposition, and plasma enhanced atomic layer deposition, but is not limited thereto.
The above-mentioned contents described in the first aspect of the present application are all applied to the third aspect of the present application.
A fourth aspect of the present application provides a method for forming a film or thin film containing a group iv metal element, comprising the steps of: a group iv metal element-containing film or thin film is formed using the group iv metal element-containing compound according to the first aspect of the present application as a precursor. The group iv metal element-containing film may contain two or more group iv metal elements, or may contain one or more other additional metal elements together with one or more group iv metal elements.
In an embodiment of the present application, the method for forming a group iv metal element-containing film or thin film may include the steps of: the group iv metal element-containing film or thin film is formed by supplying and depositing a precursor composition for forming the group iv metal element-containing film or thin film to a substrate located in a deposition chamber, but may not be limited thereto. The film forming method may be performed by a method or an apparatus known in the art, and may be performed by using one or more additional reaction gases, if necessary. As the substrate, a silicon semiconductor wafer and a compound semiconductor wafer can be used, but not limited thereto. Substrates having pores or grooves may also be used, and for example, porous substrates having a wide surface area may be used for the purpose of using the substrates as catalysts.
In an embodiment of the present application, the group iv metal element-containing film may be formed by vapor deposition. For example, the vapor deposition may be one or more deposition selected from the group consisting of Chemical Vapor Deposition (CVD), low pressure vapor deposition (LPCVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), cyclic chemical vapor deposition (cyclic CVD), plasma enhanced cyclic chemical vapor deposition (PE cyclic CVD), Atomic Layer Deposition (ALD), and Plasma Enhanced Atomic Layer Deposition (PEALD), but is not limited thereto.
In an embodiment of the present application, the method for forming a group iv metal element-containing film or thin film may include, but is not limited to:
providing one or more surfaces of the substrate to a reaction chamber;
introducing a precursor comprising the group iv metal element-containing compound into the reaction chamber; and
introducing a reactant gas into the reaction chamber.
Here, a group iv metal element-containing film is formed on one or more surfaces of the substrate by vapor deposition.
In an embodiment of the present application, the group iv metal element-containing film may include a group iv metal element-containing oxide film, a nitride film, an oxynitride film, a carbide film, or a carbonitride film, but is not limited thereto.
In an embodiment of the present application, the group iv metal element-containing film may contain two or more of the group iv metal elements, or may contain one or more of other additional metal elements together with one or more of the group iv metal elements. In the method for forming a group iv metal element-containing film or thin film, a film containing the group iv metal element and another additional metal element may be formed by supplying one or more additional precursors containing the same or different metal elements as the first precursor of the group iv metal element-containing compound together with or sequentially with one or more additional precursors of the group iv metal element-containing compound, but the method is not limited thereto. In the case where the precursors are sequentially supplied, the reaction gas and/or the purge gas may be supplied during the supply of each precursor, but is not limited thereto, and a person skilled in the art can appropriately select to use a deposition process known in the art.
The additional metal may include, without particular limitation, a metal known In the art, and may be, for example, one or more metals selected from the group consisting of magnesium (Mg), calcium (Ca), zinc (Zn), boron (B), aluminum (Al), indium (In), silicon (Si), germanium (Ge), tin (Sn), hafnium (Hf), zirconium (Zr), titanium (Ti), vanadium (V), niobium (Nb), tantalum (Ta), a lanthanide atom (more particularly, scandium (Sc), yttrium (Y), and lanthanum (La), and a rare earth metal atom), but is not limited thereto. The precursor containing the additional metal element may use a precursor well known in the art without particular limitation.
In an embodiment of the present application, the reaction gas may be selected from the group consisting of an oxygen-containing supply source, a nitrogen-containing supply source, a carbon supply source, a reducing agent, and a combination thereof, but is not limited thereto.
In one embodiment of the present application, the nitrogen-containing source may be selected from the group consisting of nitrogen (N)2) Nitrogen-containing radicals, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen/hydrogen, ammonia plasma, nitrogen/hydrogen plasma, and mixtures thereof, but is not limited thereto.
In particular embodiments, the nitrogen-containing source comprises an ammonia plasma or a hydrogen/nitrogen plasma source gas introduced into the reactor at a flow rate in a range of about 1 to about 200 standard milliliters per minute (sccm) or in a range of about 1 to about 1000 sccm. The nitrogen-containing source may be introduced for a period of time ranging from about 0.1 to about 100 seconds. In embodiments where the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration in excess of about 0.01 seconds, the nitrogen-containing supply may have a pulse duration in excess of about 0.01 seconds, and the water pulse duration may have a pulse duration in excess of about 0.01 seconds. In yet another embodiment, the duration of the purge between pulses may be as low as 0 seconds, or the pulses may be continuous with no intervening purge.
In one embodiment of the present application, the oxygen-containing supply may be introduced into the reactor in the form of more than one oxygen-containing supply and/or may accompany precursors other than those utilized in the deposition process. A suitable oxygen containing source gas may comprise, for example, water (H)2O) (e.g., deionized, purified, and/or distilled water), H2O2Oxygen (O)2) Oxygen-containing radical, oxygen plasma, ozone (O)3)、NO、N2O、NO2Carbon monoxide (CO) and carbon dioxide (CO)2) And combinations thereof. In particular embodiments, the oxygen containing source comprises an oxygen containing source gas introduced into the reactor at a flow rate in a range of about 1 to about 2000sccm or in a range of about 1 to about 1000 sccm. The oxygen-containing supply may be introduced over a period of time ranging from about 0.1 to about 100 seconds. In a particular embodiment, the oxygen-containing supply comprises water at a temperature of 10 ℃ or above 10 ℃. In embodiments where the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration that exceeds about 0.01 seconds, and the oxygen-containing supply source may have a pulse duration that exceeds about 0.01 secondsAnd the water pulse duration may have a pulse duration exceeding about 0.01 second, but is not limited thereto.
In one embodiment of the present application, the reactive species may be a nitrogen-oxygen donor, more particularly selected from NO, NO2、N2O、N2O5、N2O4And mixtures thereof, but are not limited thereto.
The reactive species used in the method as described above may be, if necessary, an oxygen supply source, a mixture of oxygen supply sources, and a mixture of nitrogen supply sources, a nitrogen-oxygen supply source, or a mixture thereof, according to a desired N/O ratio, but is not limited thereto. In one embodiment of the present application, when the group iv metal element-containing film contains carbon, such as a carbonized film or a carbonitrided film, one or more carbon sources may be used, and for example, methane, ethane, propane, butane, ethylene, propylene, tert-butene, or the like may be used, but the present invention is not limited thereto.
In an embodiment of the present application, the reducing agent may include a substance selected from the group consisting of hydrogen, hydrogen plasma, and hydrogen chloride, but is not limited thereto.
The deposition methods disclosed herein may include more than one purge gas. The purge gas used to purge unconsumed reactants and/or reaction byproducts is an inert gas that is non-reactive with the precursor. Exemplary purge gases include argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H)2) Or a mixture thereof, but not limited thereto. In a particular embodiment, a purge gas, such as Ar, is supplied to the reactor at a flow rate in the range of about 10 to about 2000sccm for about 0.1 to 100 seconds, thereby purging unreacted species and any byproducts that may remain in the reactor.
The respective steps of supplying the precursor, the oxygen-containing supply source, the nitrogen-containing supply source and/or the other precursor, and the source gas and/or the reagent can be performed by varying the time for which they are supplied to vary the stoichiometric composition of the resulting group iv metal element-containing film.
In order to induce the above reaction and form a group iv metal element-containing film or coating on the substrate, energy is supplied to one or more of the precursor, the nitrogen-containing source, the reducing agent, the other precursor, or a combination thereof. Such energy may be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods, and combinations thereof. In a particular embodiment, a secondary RF source may be utilized on the substrate surface in order to alter the plasma characteristics. In embodiments where the deposition comprises a plasma, the plasma generation process may comprise a direct plasma generation process that occurs directly in the plasma reactor or, alternatively, a remote plasma generation process that generates a plasma outside of the reactor and feeds into the reactor.
In an embodiment of the present application, the temperature of the substrate may be above room temperature, above about 100 ℃, above about 150 ℃, above about 200 ℃, above about 250 ℃, above about 280 ℃, above about 300 ℃, or above about 350 ℃, but is not limited thereto. For example, the temperature of the substrate may be room temperature or more and about 500 ℃ or less, about 100 ℃ or more and about 500 ℃ or less, about 150 ℃ or more and about 500 ℃ or less, about 200 ℃ or more and about 500 ℃ or less, about 250 ℃ or more and about 500 ℃ or less, about 280 ℃ or more and about 500 ℃ or less, about 300 ℃ or more and about 500 ℃ or less, or about 350 ℃ or more and about 500 ℃ or less, but may not be limited thereto.
In one embodiment of the present application, a precursor comprising the group iv metal element-containing compound can be utilized to also form the group iv metal element-containing film with a uniform thickness at a temperature of about 280 ℃, about 300 ℃, or more. Such a group iv metal element-containing film can be effectively used as a high dielectric substance film.
In one embodiment of the present application, a group iv metal element-containing film may be used for deposition on at least a portion of the substrate shown. Examples of suitable such substrates include silicon, SiO2、Si3N4OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, anti-reflective coating,Photoresist, flexible substrate, organic polymer, organic and inorganic porous material, metal such as copper and aluminum, and a diffusion barrier layer such as TiN, Ti (C) N, TaN, Ta (C) N, Ta, W, or WN, but not limited thereto. The film can coexist with various subsequent processing steps such as Chemical Mechanical Planarization (CMP) and anisotropic etching processes.
In one embodiment of the present application, the thickness of the group iv metal element-containing film or thin film may be about 1 nm to several μm, but is not limited thereto.
In an embodiment of the present application, the group iv metal element-containing film or thin film may be used as a high dielectric film, a chemical reaction catalyst, or the like of a semiconductor device, but may not be limited thereto.
The above-mentioned contents of the first aspect of the present application are all cited in the fourth aspect of the present application.
In an embodiment of the present application, depositing the film may include steps performed by Metal Organic Chemical Vapor Deposition (MOCVD) or Atomic Layer Deposition (ALD), but may not be limited thereto. The Metal Organic Chemical Vapor Deposition (MOCVD) or Atomic Layer Deposition (ALD) may be performed using a deposition apparatus, deposition conditions, additional reaction gases, and the like, which are well known in the art.
The group iv metal element-containing compound used as the precursor is highly thermally stable, and therefore can be used as a precursor for an atomic layer deposition method or a chemical vapor deposition method to form a group iv metal element-containing film, and particularly, a group iv metal element-containing film having a thickness of several nm or several tens nm can be uniformly formed on a substrate having irregularities (grooves) on the surface or a porous substrate. For example, in a substrate in which fine irregularities (grooves) having an aspect ratio of about 1 or more, about 2 or more, about 5 or more, about 10 or more, about 20 or more, about 30 or more, or about 40 or more and a width of about 1 μm or less, about 500nm or less, about 400nm or less, about 300nm or less, about 200nm or less, about 100nm or less, about 80nm or less, about 60nm or less, about 50nm or less, about 40nm or less, about 30nm or less, about 20nm or less, or about 10nm or less are located on the surface of the group iv metal element-containing compound precursor, the following excellent effects are exhibited: a group iv metal element-containing film having a thickness of several nm to several tens nm can be uniformly formed on all surfaces of the substrate including the surface of the fine unevenness (groove) including the surface at the deepest portion of the fine unevenness (groove) and the surface of the fine unevenness (groove) at the upper surface of the fine unevenness (groove).
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