Method for manufacturing a patterned substrate and method for manufacturing a semiconductor device

Abstract

To provide an excellent manufacturing method for patterned substrates that enables easy patterning of the insulating layer to obtain the patterned substrate even when a difficult-to-etch material is used as the insulating layer, the patterned substrate obtained thereby, and a patterned substrate intermediate thereof.SOLUTION: A method for manufacturing a patterned substrate in which an insulating layer 11 and an electrode layer 12 are stacked in this order on a substrate 10, includes the processes of forming an organic resist material layer 13, patterning the organic resist material layer 13 by EUV irradiation to obtain a first patterning layer 13a, developing the first patterning layer 13a, and removing the first patterning layer 13a.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a patterned substrate used in various semiconductor devices, a patterned substrate obtained by the method, and a patterned substrate intermediate used to obtain the patterned substrate. [Background technology]

[0002] In recent years, against the backdrop of a paradigm shift toward an advanced information society, there is a demand for faster, larger amounts of information to be handled with greater precision, and semiconductor device technology, such as integrated circuits using semiconductors, is advancing remarkably every day.

[0003] The manufacturing process for the above semiconductor device is explained as follows, taking a simple schematic diagram of a MOS device as an example. First, as shown in Figure 3(a), a silicon oxide film 2 that will become a gate insulating film is formed on a silicon substrate 1 using thermal oxidation or the like. Then, as shown in Figure 3(b), a polysilicon film 3 that will become a gate electrode is formed on the silicon oxide film 2 using a method such as CVD (chemical vapor deposition).

[0004] 3(c) and (d), the polysilicon film 3 is covered with a photoresist film 4, and then exposed and developed using a desired mask by lithography, thereby performing max-patterning of the gate electrode. Then, as shown in FIGS. 4(a) and 4(b), the polysilicon film 3 and silicon oxide film 2 are etched by, for example, RIE (reactive ion etching) using the patterned photoresist film 4 as a mask.

[0005] Next, as shown in Fig. 4(c), the photoresist film 4 is removed by ashing using oxygen gas. After obtaining a patterned substrate having a concave-convex pattern as shown in Fig. 4(d) in this way, predetermined wiring and elements are formed by repeating processes such as forming an interlayer insulating film, patterning, embedding metal, and planarizing, and the like, to form the circuits required for the device.

[0006] As in the above example, silicon oxide films are often used as gate insulating films in semiconductor devices using such patterned substrates. However, in recent years, in order to meet the demand for even higher integration and higher speed of semiconductor devices, the use of so-called "high-κ" metal oxides having a higher dielectric constant, such as hafnium oxide, hafnium silicate oxinide, and hafnium aluminate, as gate insulating films has been considered.

[0007] In other words, the use of these materials with high dielectric constants is expected to suppress gate leakage current, enabling further thinning of gate insulating films and finer patterns, and several semiconductor devices using such high-κ materials have been proposed (see Patent Document 1, etc.). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2022-8336 Summary of the Invention [Problem to be solved by the invention]

[0009] However, because the high-κ materials are difficult to etch, it is not easy to directly etch insulating layers made of high-κ materials to form patterns. Therefore, there is a strong demand for the development of an efficient etching method for such insulating layers. In Patent Document 1, a high-κ film is used as the first insulating layer, and a general insulating film such as silicon oxide is used as the second insulating film. The two are combined to form a laminated structure, and only the second insulating film is etched and patterned, thereby increasing the dielectric constant of the entire insulating layer. However, the patent document did not succeed in patterning the insulating film itself made of a high-κ film.

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an excellent method for producing a patterned substrate, which allows a patterned substrate to be obtained by easily patterning an insulating layer, even when a difficult-to-etch material such as a high-κ material is used as the insulating layer, as well as the patterned substrate and patterned substrate intermediate obtained thereby. [Means for solving the problem]

[0011] In view of the above circumstances, the present inventors have discovered that when patterning an insulating layer on a substrate, an insulating layer made of a material that is difficult to etch can be efficiently patterned by devising a manufacturing process using an organic resist material layer, and have arrived at the present invention.

[0012] That is, the present invention has the following aspects. [1] A method for producing a patterned substrate having an insulating layer and an electrode layer stacked in this order on a substrate, the method comprising the steps of: forming an organic resist material layer; patterning the organic resist material layer by EUV irradiation to obtain a first patterning layer; developing the first patterning layer; forming an insulating layer on the substrate having the developed first patterning layer; forming an electrode layer on the insulating layer; forming a second organic resist material layer on the electrode layer; patterning the second organic resist material layer by EUV irradiation to obtain a second patterning layer; developing the second patterning layer; patterning the electrode layer by removing the electrode layer in areas where the developed second patterning layer does not exist; removing the first patterning layer and the insulating layer on the first patterning layer in areas where the developed second patterning layer does not exist; and removing the developed second patterning layer. [2] The method for producing a patterned substrate according to [1], wherein the steps of patterning the electrode layer by removing the electrode layer in the areas where the developed second patterning layer does not exist, removing the first patterning layer and the insulating layer on the first patterning layer in the areas where the developed second patterning layer does not exist, and removing the developed second patterning layer are carried out sequentially or simultaneously. [3] The method for producing a patterned substrate according to [1] or [2], wherein the organic resist material layer is an organic hydroxyoxotin layer. [4] The method for producing a patterned substrate according to [3], wherein the organic hydroxyoxotin layer is formed using an organic hydroxyoxotin precursor represented by the following general formula (1): [C3] RSnX3…(1) [R represents a hydrocarbon group having 1 to 30 carbon atoms, and X represents a hydrolyzable substituent.] [5] A method for producing a patterned substrate having an insulating layer and an electrode layer laminated in this order on a substrate, the method comprising the steps of: forming an organic hydroxyoxotin layer; patterning the organic hydroxyoxotin layer by EUV irradiation to obtain a first patterned layer; developing the first patterned layer; and removing the first patterned layer. A method for manufacturing a patterned substrate having the above structure. [6] The method for producing a patterned substrate according to [5], further comprising the step of forming an insulating layer on the substrate having the developed first patterning layer. [7] A method for producing a patterned substrate according to [6], comprising the steps of: forming an electrode layer on the insulating layer; forming a second organic hydroxyoxotin layer on the electrode layer; patterning the second organic hydroxyoxotin layer by EUV irradiation to obtain a second patterned layer; developing the second patterned layer; and removing the developed second patterned layer. [8] The method for producing a patterned substrate according to [7], wherein the step of removing the developed second patterning layer and the step of removing the insulating layer on the patterning layer are carried out sequentially or simultaneously. [9] The method for producing a patterned substrate according to any one of [5] to [8], wherein the organic hydroxyoxotin layer is formed using an organic hydroxyoxotin precursor represented by the following general formula (1): [C4] RSnX3…(1) [R represents a hydrocarbon group having 1 to 30 carbon atoms, and X represents a hydrolyzable substituent.]

[10] The method for producing a patterned substrate according to any one of [1] to [9], wherein in the step of developing the first patterning layer, the non-EUV irradiated portion of the patterning layer is removed with an acid.

[11] The method for producing a patterned substrate according to

[10] , wherein the non-EUV irradiated portion is removed by a gas phase treatment using an acidic gas.

[12] The method for producing a patterned substrate according to any one of [1] to

[11] , wherein the insulating layer is formed from a material that is difficult to etch.

[13] The method for producing a patterned substrate according to

[12] , wherein the etch-resistant material is a high-κ material having a relative dielectric constant κ of 9 or more.

[14] The method for producing a patterned substrate according to

[13] , wherein the high-κ material having a relative dielectric constant κ of 9 or more is at least one compound selected from the group consisting of hafnium oxide, hafnium oxinide silicate, hafnium aluminate, zirconium oxide, tantalum oxide, zirconium aluminum oxide, aluminum oxide, lanthanum oxide, and compounds of any of these with silica aluminum.

[15] The method for producing a patterned substrate according to any one of [1] to [4] and [7] to

[13] , wherein in the step of developing the second patterning layer, the non-EUV irradiated portion of the second patterning layer is removed with acid.

[16] The method for producing a patterned substrate according to

[15] , wherein the removal of the non-EUV irradiated portion is carried out by a gas phase treatment using an acidic gas.

[17] A patterned substrate obtained by the method for manufacturing a patterned substrate according to any one of [1] to

[15] , wherein an insulating layer having a pattern configuration including traces of removed patterning layer and an electrode layer are formed in this order on the substrate.

[18] An intermediate for obtaining the patterned substrate according to

[17] , which has a first patterning layer on a substrate and an insulating layer on the substrate in a form that includes the first patterning layer.

[19] The patterned substrate intermediate according to

[18] , having an electrode layer on the insulating layer.

[20] The patterned substrate intermediate of

[19] , having a second patterning layer on the electrode layer. [Effects of the Invention]

[0013] According to the method for producing a patterned substrate of the present invention, since the insulating layer is patterned using an organic resist material layer, even if the insulating layer is made of a material that is difficult to etch, it can be patterned efficiently. Furthermore, since only a small amount of the insulating layer needs to be etched away, the cost of materials for forming the insulating layer can be reduced.

[0014] The patterned substrate of the present invention has the advantage of exhibiting excellent electrical properties because an insulating layer made of a hard-to-etch material such as a high-κ material is efficiently formed by the manufacturing method of the present invention. Furthermore, the amount of hard-to-etch material used can be reduced, thereby reducing material costs.

[0015] Furthermore, the patterned substrate intermediate of the present invention allows the patterned substrate to be produced efficiently. [Brief explanation of the drawings]

[0016] [Figure 1] 1(a) to 1(d) are explanatory views of a manufacturing process according to one embodiment of the present invention. [Figure 2] 1(a) to 1(d) are explanatory views of a manufacturing process according to one embodiment of the present invention. [Figure 3] 1(a) to 1(d) are explanatory diagrams of a conventional manufacturing process for a patterned substrate. [Figure 4] 1(a) to 1(d) are explanatory diagrams of a conventional manufacturing process for a patterned substrate. DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention will be described in more detail below based on the embodiments of the present invention, but the present invention is not limited to the following embodiments. In the present invention, when the expression "Y to Z" (Y and Z are any numbers) is used, unless otherwise specified, it includes the meaning of "Y or more and Z or less", as well as "preferably larger than Y" or "preferably smaller than Z". Furthermore, when it is expressed as "Y or more" (Y is any number) or "Z or less" (Z is any number), it also means that "it is preferably greater than Y" or "it is preferably less than Z." Furthermore, in the present invention, "y and / or z (y and z are any constitutions or components)" means three combinations: y only, z only, and y and z.

[0018] One embodiment of the present invention relates to a method for manufacturing a patterned substrate in which an insulating layer 11 and an electrode layer 12 are laminated in this order on a substrate 10, as shown in Figure 2(d), and this embodiment will be described in order using Figures 1(a) to (d) and Figures 2(a) to (d).

[0019] <1: Formation of an organic hydroxyoxotin layer> In this embodiment, first, as shown in FIG. 1(a), an organic hydroxyoxotin layer 13 is formed on a substrate 10 as an organic resist material layer.

[0020] There are no particular limitations on the substrate 10, and an appropriate material can be used depending on the application and required properties of the resulting patterned substrate. Examples include substrates made of Si, SiO2, SiN, SiON, SiC, BN, GaN, TiN, BPSG, SOG, Cr, CrO, CrON, MoSi, etc.

[0021] The surface of the substrate 10 (the surface on which the insulating layer 11 is formed) does not necessarily have to be made of a flat and uniform material, and a portion of the surface of the substrate 10 may be removed, for example, by etching to include a concave region. Conversely, a portion of the surface of the substrate 10 may be added, for example, by deposition to include a convex region. The thickness of the substrate 10 is also not particularly limited, and is set to an appropriate thickness depending on the use and type of the patterned substrate.

[0022] As will be described later, the organic hydroxyoxotin layer 13 formed on the substrate 10 is used to assist in the patterning by etching of the insulating layer 11 formed after the organic hydroxyoxotin layer 13, and can be easily patterned by EUV irradiation.

[0023] To form the organic hydroxyoxotin layer 13, a compound represented by the general formula "R p SnX m An organic hydroxyoxotin precursor represented by the formula: In the above formula, "R" is a hydrocarbon group having a beta hydrogen, preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms. Examples include saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and 1-methylcyclopentyl group, and unsaturated hydrocarbon groups such as vinyl group and 2-propenyl group. In the above formula, "X" represents a hydrolyzable substituent, such as a halogen atom, an amino group, an alkoxy group (-OR'), an alkynide (R'C≡C), an azide (N3-), a dialkylamino group (-NR'2) (-NR'R"), an alkylcarbonylamino group (-N(R')C(O)R') (-N(R')C(O)R") (-N(R")C(O)R'), a carbonyloxy group (-OCOR'), and a carbonylamino group (-N(H)C(O)R'). R' and R" are each independently a hydrocarbon group having 1 to 10 carbon atoms. Of these, X is preferably a dialkylamino group, an alkoxy group, an alkylcarbonylamino group, a halogen atom, or a carbonyloxy group, and particularly preferably a dialkylamino group or an alkoxy group, and further preferably a dialkylamino group (-NR'2) or an alkoxy group (-OR'). In the above formula, "p" is an integer of 1 to 3, and "m" is an integer of 1 to 4.

[0024] The molecular weight of such an organic hydroxyoxotin precursor is usually 200-900, preferably 240-700, and particularly preferably 280-500.

[0025] In this embodiment, among the above organic hydroxyoxotin precursors, the use of an organic hydroxyoxotin precursor represented by the following general formula (1) is particularly advantageous in terms of effectiveness. Similarly to "R" in the general formula, R in the following formula is a hydrocarbon group having a beta hydrogen, and among these, those having 1 to 15 carbon atoms, more preferably 1 to 10, and even more preferably 2 to 6 carbon atoms are preferred. Furthermore, X in the following formula is the same as "X" in the general formula, and among these, dialkylamino groups, alkoxy groups, alkylcarbonylamino groups, halogens, and carbonyloxy groups are particularly preferred, and those in which X is a dialkylamino group or an alkoxy group are particularly preferred, and furthermore, a dialkylamino group (-NR'2) or an alkoxy group (-OR'). [5] RSnX3…(1) [R represents a hydrocarbon group having 1 to 30 carbon atoms, and X represents a hydrolyzable substituent.]

[0026] Examples of such organic hydroxyoxotin precursors include t-butyltris(dimethylamino)tin, n-butyltris(dimethylamino)tin, t-butyltris(diethylamino)tin, di(t-butyl)di(dimethylamino)tin, sec-butyltris(dimethylamino)tin, n-pentyltris(dimethylamino)tin, isobutyltris(dimethylamino)tin, isopropyltris(dimethylamino)tin, t-butyltris(t-butoxy)tin, n-butyltris(t-butoxy)tin, and isopropyltris(t-butoxy)tin.

[0027] The organic hydroxyoxotin precursors may be used alone or in combination of two or more. The method for forming a layer using the organic hydroxyoxotin precursor is not particularly limited and can be appropriately selected from various conventional film-forming methods such as spin coating, CVD, physical vapor deposition, and atomic layer deposition.

[0028] In this embodiment, it is particularly preferable to use a CVD method. When using the CVD method, the organic hydroxyoxotin precursor and an oxygen-containing counter reactant for imparting a hydroxy group are introduced into the deposition chamber of a CVD apparatus via separate inlets, and the two are mixed and reacted in the gas phase to form an organic hydroxyoxotin layer 13 on the substrate 10.

[0029] The oxygen-containing counter reactant is used in combination with an organic hydroxyoxotin precursor not only in CVD but also in other deposition methods, and serves to oxidize the organic hydroxyoxotin precursor to generate a large number of hydroxy groups. Examples of the oxygen-containing counter reactant include water, hydrogen peroxide, formic acid, alcohol, oxygen, and ozone, and these may be used alone or in combination of two or more.

[0030] When the organic hydroxyoxotin layer 13 is formed by the CVD method, the pressure conditions during film formation are generally 10 to 1500 Pa, and preferably 65 to 270 Pa. The temperature of the substrate 10 during film formation is generally 0 to 250°C, and preferably 20 to 150°C.

[0031] The thickness of the organic hydroxyoxotin layer 13 is not particularly limited, but it is preferable to set the thickness t1 of the first patterned layer 13a obtained by patterning the organic hydroxyoxotin layer 13 to be slightly thinner than the thickness t2 of the insulating layer 11 to be formed subsequently (see FIG. 1[c]). Incidentally, it is more effective to set the ratio t1 / t2 to 0.7 to 1.

[0032] <2: Patterning and development of organic hydroxyoxotin layer> Next, a first patterning layer 13a is formed by irradiating and curing only specific regions of the organic hydroxyoxotin layer 13. Then, the non-EUV irradiated portions (uncured portions) of the first patterning layer 13a are removed to develop the first patterning layer 13a, as shown in FIG. 1(b).

[0033] The EUV refers to electromagnetic waves (Extreme Ultra-Violet) with a wavelength of approximately 10 to 15 nm. The EUV irradiation crosslinks the many terminal hydroxy groups in the organic hydroxyoxotin layer 13 to form -O- bonds, curing the EUV-irradiated portions. Since the non-irradiated portions do not cure, the organic hydroxyoxotin layer 13 can be patterned by irradiating only the portions to be patterned with EUV.

[0034] A high-temperature plasma, particularly laser-excited plasma, is used as a light source for the EUV irradiation. The irradiation dose is usually 15 to 80 mJ / cm 2 , depending on the thickness of the first patterning layer 13a, etc. 2 It is preferable that:

[0035] The development of the first patterning layer 13a is carried out by removing the non-EUV irradiated portions (uncured portions) from the first patterning layer 13a, and the development is carried out using a wet etching process or a dry etching process (vapor phase treatment) using acid, which is typically carried out in an etching process.

[0036] When the development is performed using the wet etching process, the solvent for dissolving and removing the uncured portion of the first patterning layer 13a can be, for example, isopropyl alcohol, n-butyl alcohol, n-butyl acetate, 2-heptanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), butyl acetate, etc. These can be used alone or in combination of two or more.

[0037] Furthermore, when development is performed using the dry etching process (gas phase treatment), acidic substances such as hydrogen halides, halogens, diborane, boron trichloride, other Lewis acids, and argon, or O2 or H2 to improve selectivity with silicon, are mixed appropriately and flowed in gaseous form so as to come into contact with the surface of the first patterning layer 13a, while performing a mild plasma treatment (high pressure, low power) or heat treatment. The acidic substances may be used alone or in combination of two or more.

[0038] In this embodiment, it is particularly preferable to use a dry etching process using plasma. When using the plasma etching process, the plasma process includes conventionally known processes such as transformer coupled plasma (TCP), inductively coupled plasma (ICP), capacitively coupled plasma (CCP), and electron cyclotron resonance plasma (ECP). However, since the ion flux and ion energy cannot be independently controlled in CCP plasma, a high-density plasma other than CCP plasma is usually used to increase the electron density to approximately 10 10 From 10 13 / cm 3The pressure is controlled to about 0.6 Pa or higher, more preferably 2 Pa or higher, and the power level is preferably 1 kW or lower, more preferably 500 W or lower. The flow rate is preferably 40 to 1000 standard cubic centimeters per minute (sccm), and more specifically, can be set to about 500 sccm for a period of preferably 1 to 3000 seconds, more preferably 10 to 600 seconds. The temperature can be set to preferably 0 to 300°C, more preferably 30 to 120°C.

[0039] <3: Formation of insulating layer> Next, an insulating layer 11 is formed on the substrate 10 having the developed first patterning layer 13a so as to cover the first patterning layer 13a, as shown in Fig. 1(c). As already mentioned, the thickness t2 of the insulating layer 11 is preferably set so that its relationship with the thickness t1 of the first patterning layer 13a satisfies t1 / t2 = 0.7 to 1, in order to efficiently etch the insulating layer 11.

[0040] The insulating layer 11 may be formed using silicon oxide (SiO2) or the like, which has conventionally been widely used for gate insulating layers and the like. However, in the present invention, it is preferable to use an insulating material made of a difficult-to-etch material, which has a high relative dielectric constant but is difficult to etch, and therefore its use in semiconductor devices has been limited, because the insulating material has the advantage of being able to be etched efficiently.

[0041] Such a hard-to-etch material having a high dielectric constant can be, for example, a high-κ material having a dielectric constant κ of 9 or more. Specific examples include hafnium oxide, hafnium silicate oxinide, hafnium aluminate, zirconium oxide, tantalum oxide, aluminum zirconium oxide, aluminum oxide, lanthanum oxide, and compounds of these with silica aluminum. These can be used alone or in combination of two or more.

[0042] In this embodiment, among the above high-κ materials, hafnium oxide (κ is 13 to 18) and zirconium oxide (κ is greater than 13) are particularly suitable because they exhibit an especially high relative dielectric constant.

[0043] The insulating layer 11 can be obtained by depositing an insulating material using any of various conventionally known film-forming methods such as CVD, ALD (Atomic Layer Deposition), and sputtering.

[0044] <4: Formation of electrode layer> 1(d), an electrode layer 12 is formed on the insulating layer 11. The electrode layer 12 can be obtained by depositing a semiconductive material, such as polysilicon, by a conventionally known film deposition method such as a CVD method or a sputtering method.

[0045] The thickness of the electrode layer 12 is not particularly limited, and is set to an appropriate thickness depending on the application and required properties of the resulting patterned substrate.

[0046] <5: Formation of the second organic hydroxyoxotin layer> Next, as shown in Figure 2(a), a second organic hydroxyoxotin layer 14 is formed on the electrode layer 12. The second organic hydroxyoxotin layer 14 is formed using the same organic hydroxyoxotin precursor as that used for the organic hydroxyoxotin layer 13. The second organic hydroxyoxotin layer 14 and the organic hydroxyoxotin layer 13 do not necessarily need to use the same material, and the film formation method does not necessarily need to be the same. However, the types of suitable precursors and the suitable film formation methods are common to both, and therefore a description thereof will be omitted.

[0047] <6: Second patterning and development> Next, a second patterning layer 14a is formed by irradiating and curing only specific regions of the second organic hydroxyoxotin layer 14 with EUV. Then, the non-EUV irradiated portions (uncured portions) of the second patterning layer 14a are removed to develop the second patterning layer 14a, as shown in FIG. 2(b). The patterning and development can be carried out in the same manner as in the method of patterning the organic hydroxyoxotin layer 13 to form the first patterned layer 13a and then developing the resulting layer.

[0048] <7: Patterning of electrode layer> Next, using the second patterning layer 14a as a mask, the exposed portions of the electrode layer 12 are removed by, for example, plasma etching, to pattern the electrode layer 12 as shown in FIG. 2(c).

[0049] <8: Removal of the second patterning layer> Then, the developed second patterning layer 14a on the electrode layer 12 is removed by dry etching (ashing). The dry etching conditions can be the same as those for removing the first patterning layer 13a.

[0050] <9: Removal of insulating layer> Next, the insulating layer 11 exposed in the regions where the second patterning layer 14a and the electrode layer 12 are not present is removed by plasma dry etching. As shown in FIG. 2(c), the insulating layer 11 is significantly thinner in this region because the first patterning layer 13a formed earlier is overlapping the insulating layer 11. Therefore, even if the insulating layer 11 is made of a material that is difficult to etch, this region of the insulating layer 11 can be efficiently etched away. It is effective to perform the plasma dry etching by sequentially changing the reactive gases corresponding to etching and ashing so that both the insulating layer 11 and the second patterning layer 14a (resist layer) can be removed. In this case, for example, the insulating layer 11 can be removed by plasma etching using boron trichloride (BCl3), followed by ashing using hydrogen halide (HX) or chlorine gas (Cl2). Ashing can also be performed using high-concentration BCl3. When etching the insulating layer 11 and ashing the second patterning layer 14a (resist) are performed simultaneously, simultaneous etching and ashing can be performed, for example, by using an ECR plasma device and a mixed gas of BCl3 and Cl2 (with Cl2 being 60% by volume or less).

[0051] Furthermore, if the insulating layer is extremely thin, it is not necessary to carry out etching and ashing in stages while changing the reactive gas, and it is possible to complete the removal of the two layers 11 and 14a in a single-stage process.

[0052] <10: Removal of first patterning layer on substrate> Next, the first patterning layer 13a formed on the substrate 10, which is exposed by removing the insulating layer 11, is removed by dry etching using an acid. The dry etching can be performed in the same manner as in the case of removing the second patterning layer described above.

[0053] In this way, the insulating layer 11 and the electrode layer 12 are laminated in this order on the substrate 10, and a patterned substrate having a predetermined pattern can be obtained, as shown in FIG. 2(d).

[0054] According to the above-described method for manufacturing a patterned substrate, the organic hydroxyoxotin layer 13 (first patterning layer 13a) is used to pattern the insulating layer 11, so that even if the insulating layer 11 is made of a material that is difficult to etch, it can be patterned efficiently. Furthermore, since only a small amount of the insulating layer 11 needs to be etched away, the cost of materials for forming the insulating layer 11 can be reduced.

[0055] The patterned substrate thus obtained has stable electrical properties because the insulating layer 11 is patterned efficiently and in a short time, and no extra load is placed on the substrate 10 or the electrode layer 12. Furthermore, since a patterned substrate using a material with a high relative dielectric constant κ and which is difficult to etch as the insulating layer 11 can be efficiently manufactured, a patterned substrate with particularly excellent electrical properties can be provided.

[0056] In the above embodiment, the removal of the second patterning layer 14a (the eighth step) and the removal of the insulating layer 11 (the ninth step) are performed sequentially or in a single step. However, depending on the etching conditions, the removal of the second patterning layer 14a in the eighth step, the removal of the insulating layer 11 in the ninth step, and the removal of the first patterning layer 13a on the substrate 10 in the tenth step can be performed simultaneously. In this case, it is preferable to perform plasma treatment using a mixed gas of BCl3 and Cl2 at a high power of, for example, 600 W or more (higher than the aforementioned "gentle plasma treatment") and low pressure. Furthermore, in some plasma processes, O2 or H2 may be mixed to obtain reaction selectivity with silicon.

[0057] Furthermore, in the above embodiment, when patterning the electrode layer 12, a second patterning layer 14a similar to the first patterning layer 13a used for patterning the insulating layer 11 is formed and used as a mask when etching the electrode layer 12. However, it is not necessarily necessary to use the second patterning layer 14a for patterning the electrode layer 12, and a general patterning method may be adopted.

[0058] However, when the first patterning layer 13a and the second patterning layer 14a are used in combination as in the above embodiment, as mentioned above, when the second patterning layer 14a is etched and removed, depending on the conditions, the portion of the insulating layer 11 exposed in the area where the patterned electrode layer 12 is not present, and even the first patterning layer 13a underneath, can be removed at the same time, thereby further improving manufacturing efficiency.

[0059] In the above embodiment, an organic hydroxyoxotin layer is used as the organic resist material layer for forming the first patterning layer 13 a and the second patterning layer 14 a, but the organic resist material layer does not necessarily have to be an organic hydroxyoxotin layer, and any type of organic resist material layer that can be handled in the same manner as in the above embodiment may be used. Examples include organometallic compound resist materials using known metals other than tin, polymer resist materials, and metal oxide resist materials.

[0060] 1(a)-(d) and 2(a)-(d) are performed in a sequential order in the above embodiment, but the sequential steps do not necessarily have to be performed in a sequential order. A separately produced intermediate body may be prepared and processed to obtain a patterned substrate. An example of the intermediate body is a substrate 10 having a first patterning layer 13a formed thereon, and an insulating layer 11 formed on the substrate 10 so as to include the first patterning layer 13a (the stage of FIG. 1[c]).

[0061] Another example of the intermediate product is one in which an electrode layer 12 is formed on the insulating layer 11 (the stage shown in FIG. 1[d]). Another example of the intermediate product is one in which a second patterning layer 14a is formed on the electrode layer 12 (the stage shown in FIG. 2[b]).

[0062] By using these patterned substrate intermediates, the production process of patterned substrates can be divided into separate processes depending on the scale of the factory, the equipment, etc., and patterned substrates can be manufactured efficiently. [Example]

[0063] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[0064] [1. Formation of organic resist material layer] An organic hydroxyoxotin layer is used as the organic resist material layer. A 50 μm thick silicon substrate is prepared as the substrate, and a 15 nm thick organic hydroxyoxotin layer is formed on it by CVD using tris(dimethylamino)isopropyltin, a precursor of the organic hydroxyoxotin layer (see Figure 1[a]). The conditions for the CVD method are as follows: Pressure during film formation: 133 Pa (1 Torr) Temperature during film formation: 120°C (wafer stage temperature)

[0065] [2: Patterning and development of organic resist material layer] The specific region of the organic resist material layer is irradiated with EUV light to harden the specific region of the organic hydroxyoxotin layer. The EUV irradiation conditions are as follows: Light source: Extreme ultraviolet EUV) (wavelength 13.5nm) Irradiation amount: 50mJ / cm 2

[0066] Then, the uncured portion of the patterned layer is removed using a plasma dry etching process to develop the patterned layer (see Figure 1[b]). The etching conditions are as follows: Etching gas: HCl Pressure: 2.6 Pa (20 mTorr) Gas flow rate: 200sccm Temperature: 80℃ Output: 400W

[0067] [3. Formation of insulating layer] Next, an insulating layer made of hafnium oxide (dielectric constant κ=15) is formed on the substrate with the developed patterned layer (referred to as the first patterned layer) by RF plasma (high frequency) (see Figure 1[c]). Note that the thickness (t2) of the insulating layer is 10 μm, and the thickness (t1) of the first patterned layer is 9.5 μm, so t1 / t2=0.95.

[0068] [4: Formation of electrode layer] Next, a 20 μm thick electrode layer made of polysilicon is formed on the insulating layer by CVD (see FIG. 1[d]).

[0069] [5: Formation of second organic resist material layer] An organic hydroxyoxotin layer is used as the second organic resist material layer. Then, a 15 nm thick second organic hydroxyoxotin layer is formed on the electrode layer by CVD using tris(dimethylamino)isopropyltin, a precursor of the organic hydroxyoxotin layer (see Figure 2[a]). The CVD conditions are as follows: Pressure during film formation: 133 Pa (1 Torr) Temperature during film formation: 120°C (wafer stage temperature)

[0070] [6: Patterning and developing the second organic resist material layer] Next, in the same manner as in the above-mentioned step [2: Patterning and developing the organic resist material layer], the second organic hydroxyoxotin layer is patterned and developed so as to mask the non-existent areas of the first patterned layer (see Figure 2[b]), thereby obtaining a second patterned layer.

[0071] [7. Patterning of electrode layer] Next, the portion of the electrode layer exposed from the second patterning layer is removed by plasma dry etching to pattern the electrode layer (see FIG. 2[c]).

[0072] [8.9.10: Removal of second patterning layer, insulating layer, and organic resist material layer on substrate] The three layers, the second patterning layer, the insulating layer, and the first patterning layer on the substrate, are removed in one go by dry etching using an ECR plasma device (see Figure 2[d]). The etching conditions are as follows: Etching gas: BCl3 and Cl2 mixed gas (Cl2 is 60% by volume) Pressure: 0.7 Pa (5 mTorr) Gas flow rate: 40sccm Electron density; approx. 10 10 / cm 3 Processing time: 60 to 90 seconds Temperature: 25~60℃

[0073] According to the above embodiment, even though the insulating layer is made of hafnium oxide, which is difficult to etch, it can be smoothly etched away. Therefore, according to this method, it is possible to efficiently provide patterned substrates using various types of difficult-to-etch materials as the insulating layer, not limited to hafnium oxide. [Industrial Applicability]

[0074] The method for producing a patterned substrate of the present invention is useful in that it allows the production of a patterned substrate having excellent electrical properties using a material that is difficult to etch as an insulating layer. The patterned substrate can be widely used in a wide variety of semiconductor devices, such as transistors. [Explanation of symbols]

[0075] 10 Substrate 11 Insulating layer 12 Electrode layer 13 Organic hydroxyoxotin layer (organic resist material layer) 13a First patterning layer

Claims

1. A method for manufacturing a patterned substrate in which an insulating layer and an electrode layer are laminated in this order on a substrate, comprising: the insulating layer is formed of a high-κ material having a relative dielectric constant of 9 or more, which is difficult to etch; forming an organic resist material layer; patterning the organic resist material layer by EUV irradiation to obtain a first patterned layer; developing the first patterning layer; forming an insulating layer on the substrate having the developed first patterned layer; forming an electrode layer on the insulating layer; forming a second organic resist material layer on the electrode layer; patterning the second organic resist material layer by EUV irradiation to obtain a second patterned layer; developing the second patterning layer; patterning the electrode layer by removing the electrode layer in the areas where the developed second patterning layer is not present; removing the first patterning layer and the insulating layer on the first patterning layer in the areas where the developed second patterning layer does not exist; removing the developed second patterning layer; A method for manufacturing a patterned substrate having the above structure.

2. patterning the electrode layer by removing the electrode layer in the areas where the developed second patterning layer is not present; removing the first patterning layer and the insulating layer on the first patterning layer in the areas where the developed second patterning layer does not exist; 2. The method for producing a patterned substrate according to claim 1, wherein the step of removing the developed second patterning layer is carried out sequentially or simultaneously.

3. 3. The method for producing a patterned substrate according to claim 1, wherein the organic resist material layer and the second organic resist material layer are organic hydroxyoxotin layers.

4. 4. The method for producing a patterned substrate according to claim 3, wherein the organic hydroxyoxotin layer is formed using an organic hydroxyoxotin precursor represented by the following general formula (1): [Chemical formula 1] RS.X 3 …(1) [R represents a hydrocarbon group having 1 to 30 carbon atoms, and X represents a hydrolyzable substituent.]

5. 3. The method for producing a patterned substrate according to claim 1, wherein in the step of developing the first patterning layer, the non-EUV irradiated portion of the first patterning layer is removed with an acid.

6. 6. The method for producing a patterned substrate according to claim 5, wherein the non-EUV irradiated portion is removed by a gas phase treatment using an acidic gas.

7. 3. The method for producing a patterned substrate according to claim 1, wherein the high-κ material having a relative dielectric constant κ of 9 or more is at least one compound selected from the group consisting of hafnium oxide, hafnium oxinide silicate, hafnium aluminate, zirconium oxide, tantalum oxide, aluminum zirconium oxide, aluminum oxide, lanthanum oxide, and compounds of any of these with silica aluminum.

8. 3. The method for producing a patterned substrate according to claim 1, wherein in the step of developing the second patterning layer, the non-EUV irradiated portion of the second patterning layer is removed with an acid.

9. The method for producing a patterned substrate according to claim 8 , wherein the non-EUV irradiated portion is removed by a gas phase treatment using an acidic gas.

10. A method for manufacturing a semiconductor device, comprising the steps of forming a patterned substrate on a substrate, in which an insulating layer and an electrode layer are laminated in this order, and forming a semiconductor element using the patterned substrate thus obtained, The step of forming the patterned substrate includes forming an organic resist material layer; patterning the organic resist material layer by EUV irradiation to obtain a first patterned layer; developing the first patterning layer; forming an insulating layer on the substrate having the developed first patterned layer, using a high-κ material that is difficult to etch and has a dielectric constant of 9 or more; forming an electrode layer on the insulating layer; forming a second organic resist material layer on the electrode layer; patterning the second organic resist material layer by EUV irradiation to obtain a second patterned layer; developing the second patterning layer; patterning the electrode layer by removing the electrode layer in the areas where the developed second patterning layer is not present; removing the first patterning layer and the insulating layer on the first patterning layer in the areas where the developed second patterning layer does not exist; and removing the developed second patterning layer.

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