Manufacturing method of electronic components

Abstract

To provide an efficient manufacturing method of an electronic component in which a hafnium oxide-containing layer or the like is provided on at least a part of the surface of an underlying layer selected from an electrically insulating layer, a conductive layer, and a semiconductor layer, and provide an efficient manufacturing method of an electronic component in which the hafnium oxide-containing layer is carbon-free.SOLUTION: An electronic component manufacturing method according to the present invention includes a charged particle beam irradiation step of irradiating a precursor gas 5 composed of a hafnium oxide precursor 14 retained on the surface of an underlying layer of a first member 3 having the underlying layer selected from an electrically insulating layer, a conductive layer, and a semiconductor layer with a charged particle beam to form a hafnium oxide-containing layer on at least a portion of the surface of the underlying layer. In order to make the hafnium oxide-containing layer carbon-free, it is preferable to irradiate the precursor gas 5 remaining on the surface of the underlying layer with the charged particle beam in the presence of a plasma gas 7 in the charged particle beam irradiation step.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a method for producing electronic components comprising a layer or film containing hafnium oxide using charged particle beam induced deposition. [Background technology]

[0002] Taking advantage of its high dielectric constant, hafnium oxide is used to form ferroelectric layers and electrically insulating layers (hereinafter sometimes simply referred to as "insulating layers") in capacitor devices, ferroelectric memory devices, semiconductor devices, etc. For example, Patent Document 1 discloses a method for forming a variable capacitor having a ferroelectric / antiferroelectric (FE / AFE) dielectric layer, the method including the steps of: forming a metal electrode layer of platinum or iridium on a substrate, the metal electrode layer having an exposed surface with at least 80% {111} crystal planes; forming an FE / AFE dielectric layer on the exposed surface of the metal electrode layer, the FE / AFE dielectric layer being a group 4 transition metal oxide; forming a second metal electrode layer on the FE / AFE dielectric layer; and patterning the metal electrode layer, the FE / AFE dielectric layer, and the second metal electrode layer to form a variable capacitor having a width ranging from approximately 20 nm to approximately 100 nm. Examples of methods for forming the FE / AFE dielectric layer include chemical solution deposition, PVD (e.g., sputtering), atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), metal-organic chemical vapor deposition (MOCVD), and plasma enhanced metal-organic chemical vapor deposition (PEMOCVD).

[0003] Patent Document 2 discloses a method for manufacturing a semiconductor device, which includes the steps of (a) depositing a metal oxide film containing oxygen and at least one of hafnium and zirconium as its main components on a semiconductor substrate, (b) depositing a conductor film on the metal oxide film, (c) subjecting the metal oxide film to microwave heating treatment, (d) depositing a semiconductor film on the conductor film, and (e) patterning the semiconductor film, conductor film, and metal oxide film to form a gate electrode and a ferroelectric film, the gate electrode and ferroelectric film constituting a ferroelectric memory cell. Patent Document 2 also cites ALD as an example of a method for depositing the metal oxide film.

[0004] Furthermore, Patent Document 3 discloses a method for manufacturing a ferroelectric thin film, which includes a step of preparing a substrate and a step of forming a ferroelectric thin film containing hafnium oxide crystals with an orthorhombic crystal structure on the substrate using a droplet-like material containing a precursor material of an oxide that forms the ferroelectric thin film.Then, as an example of the step of forming the ferroelectric thin film, a method is disclosed in which a precursor material selected from a compound containing hafnium (Hf) and at least one organic compound containing oxygen (O), a hafnium (Hf) halide, a sulfate containing hafnium (Hf), and a nitrate containing hafnium (Hf) is supplied to the surface of the substrate by a mist CVD method. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-503717 [Patent Document 2] Japanese Patent Application Publication No. 2018-195767 [Patent Document 3] Patent Publication No. 2021-61360 Summary of the Invention [Problem to be solved by the invention]

[0006] In the case of chemical vapor deposition methods such as ALD and CVD and physical vapor deposition methods such as PLD and MBE described in Patent Documents 2 and 3, it has been difficult to form, for example, a hafnium oxide film or hafnium oxide layer having a fine pattern. Furthermore, when using the above chemical vapor deposition methods and physical vapor deposition methods, the hafnium oxide layer or the like obtained may contain carbon components (hereinafter referred to as "carbon") as unavoidable impurities, and therefore a method for forming a carbon-free hafnium oxide layer or the like has been desired in order to fully utilize the properties of hafnium oxide.

[0007] An object of the present invention is to provide a method for efficiently manufacturing an electronic component having a hafnium oxide-containing layer containing hafnium oxide and having a desired pattern on the surface of an underlayer by using a charged particle beam induced deposition method. Another object of the present invention is to provide a method for efficiently manufacturing an electronic component having a carbon-free hafnium oxide-containing layer. [Means for solving the problem]

[0008] The present inventors have found that a hafnium oxide film can be efficiently produced on the surface of a substrate by irradiating a charged particle beam onto a precursor gas consisting of a hafnium oxide precursor while the precursor gas is retained on the surface of the substrate.Furthermore, the present inventors have found that a carbon-free hafnium oxide film can be efficiently produced on the surface of the substrate by irradiating a charged particle beam onto the precursor gas retained on the surface of the substrate in the presence of a plasma gas, as described above.

[0009] The present invention is illustrated below. (1) A method for manufacturing an electronic component having a hafnium oxide-containing layer on at least a part of a surface of an underlayer selected from an electrically insulating layer, a conductive layer, and a semiconductor layer, comprising: a charged particle beam irradiation step of irradiating a precursor gas consisting of a hafnium oxide precursor, which is retained on a surface of the underlayer of a first member having the underlayer, with a charged particle beam, to form the hafnium oxide-containing layer on at least a portion of the surface of the underlayer. (2) The method for manufacturing an electronic component according to (1), wherein in the charged particle beam irradiation step, the precursor gas is irradiated with the charged particle beam in the presence of a plasma gas. (3) The method for manufacturing an electronic component according to (2) above, wherein the plasma gas is made of a substance containing oxygen element. (4) The method for manufacturing an electronic component according to any one of (1) to (3) above, wherein the electronic component is at least one selected from a capacitor device, a ferroelectric memory device, and a semiconductor device. [Effects of the Invention]

[0010] In the present invention, when a first member in which the underlying layer is mainly an electrically insulating layer is used, for example, a capacitor device or the like can be efficiently manufactured. In the present invention, when a first member in which the conductive layer is mainly an electrically insulating layer is used, for example, a ferroelectric memory device or the like can be efficiently manufactured. Furthermore, in the present invention, if a first member in which the underlying layer is mainly a semiconductor layer is used, for example, semiconductor devices and the like can be manufactured efficiently. In the charged particle beam irradiation process according to the present invention, a charged particle beam is irradiated onto a stagnant precursor gas in the presence of a plasma gas made of a substance containing an oxygen element, thereby making it possible to reliably manufacture electronic components having a carbon-free hafnium oxide-containing layer. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a schematic diagram showing an example of a manufacturing apparatus used in an electronic component manufacturing method of the present invention. [Figure 2] FIG. 10 is a schematic view showing another example of a manufacturing apparatus used in the electronic component manufacturing method of the present invention. [Figure 3] 1A to 1C are schematic diagrams showing an example of a method for manufacturing a capacitor device. [Figure 4] 1A to 1C are schematic diagrams showing an example of a method for manufacturing a ferroelectric memory device. [Figure 5] 1A to 1C are schematic diagrams illustrating an example of a method for manufacturing a semiconductor device. [Figure 6]10A to 10C are schematic diagrams showing another example of the method for manufacturing a semiconductor device. [Figure 7] 1 shows backscattered electron images of the surfaces of the hafnium oxide deposits (I) to (VI) obtained in Example 1, taken by a scanning electron microscope (SEM). [Figure 8] 1 shows a cross-section of the hafnium oxide deposit obtained in Example 1, where (a) is a scanning transmission electron microscope (STEM) image, and (b), (c), and (d) are mapping images of silicon atoms, oxygen atoms, and hafnium atoms, respectively, obtained by electron energy loss spectroscopy (EELS). [Figure 9] 1 shows cross sections of each hafnium oxide deposit obtained in Example 2, where (a) is a STEM image, and (b) and (c) are mapping images of carbon atoms and hafnium atoms, respectively, obtained by electron energy loss spectroscopy (EELS). [Figure 10] EELS spectra of the hafnium oxide films of the hafnium oxide deposits obtained in Examples 2 and 3, where (A) is the spectrum in the region where the carbon K absorption edge and oxygen K absorption edge are detected, and (B) is the spectrum in the region where the hafnium M absorption edge is detected. DETAILED DESCRIPTION OF THE INVENTION

[0012] The electronic component manufacturing method of the present invention is a method for manufacturing an electronic component by charged particle beam-induced deposition (CPB-induced deposition) comprising a hafnium oxide-containing layer on at least a portion of a surface of an underlayer selected from an insulating layer, an electrode layer, and a semiconductor layer. The method includes a charged particle beam irradiation step of irradiating a precursor gas consisting of a hafnium oxide precursor, which is retained on the surface of a first member comprising the underlayer, with a charged particle beam to decompose the precursor and form a hafnium oxide-containing layer on the surface of the underlayer. Since the "underlayer" is a layer having electrically insulating, conductive, or semiconducting properties, the "first member" of the present invention may be an object consisting of only the underlayer, or may be a composite consisting of the underlayer and a support having properties different from those of the underlayer. Furthermore, "retaining a precursor gas on the surface of the underlayer" means at least one of bringing the precursor gas into contact with (adsorbs onto) the underlayer and bringing the precursor gas into close proximity to the underlayer without contacting the underlayer. Furthermore, the "electronic component" may be a final product, or a precursor product in which the hafnium oxide-containing layer remains entirely or partially exposed before other layers or portions are laminated thereon to form a final product. The electronic components according to the present invention are preferably capacitor devices, ferroelectric memory devices, and semiconductor devices.

[0013] FIG. 1 is a schematic diagram showing a method for manufacturing an electronic component using a manufacturing apparatus 1A including a chamber 11 in which a first member 3 having a base layer is placed and a hafnium oxide-containing layer is formed on the surface of the base layer, a precursor gas supply unit 13 that supplies a precursor gas 5 consisting of a hafnium oxide precursor into the chamber 11, and a radiation source 17 that irradiates a charged particle beam onto the precursor gas 5 remaining on the surface of the base layer. FIG. 2 is a schematic diagram showing a method for manufacturing an electronic component using a manufacturing apparatus 1B including a chamber 11 in which a first member 3 having a base layer is placed and a hafnium oxide-containing layer is formed on the surface of the base layer, a precursor gas supply unit 13 that supplies a precursor gas 5 made of a hafnium oxide precursor into the chamber 11, a plasma gas supply unit 15 that supplies a plasma gas 7 into the chamber 11, and a radiation source 17 that irradiates a charged particle beam onto the precursor gas 5 remaining on the surface of the base layer.

[0014] 1 and 2 show preferred embodiments of the present invention, and manufacturing apparatuses 1A and 1B are equipped with a vacuum pump 19 connected to chamber 11 to create a reduced pressure inside chamber 11. In the method of FIG. 1, when a charged particle beam is irradiated onto precursor gas 5 remaining on the surface of the underlayer, not only hafnium oxide but also by-products derived from precursor gas 5 (precursor 14) may be generated. If precursor 14 is a compound containing carbon atoms, the by-products may contain carbon. Therefore, operating vacuum pump 19 can prevent such by-products from being mixed into the hafnium oxide-containing layer. However, according to the method of FIG. 2 using manufacturing apparatus 1B, the carbon-containing by-products react with plasma gas 7 before being incorporated into the hafnium oxide-containing layer, and the reaction products can be removed (exhausted), thereby ensuring the production of a carbon-free hafnium oxide-containing layer. In the manufacturing apparatuses 1A and 1B, the degree of vacuum in the chamber 11 before the precursor gas 5 or plasma gas 7 is supplied is not particularly limited, but is preferably 1×10 -8 ~10 Pa, more preferably 1 × 10 -6 ~1×10 -1 It is Pa.

[0015] In the manufacturing apparatuses 1A and 1B, a precursor gas supply unit 13 supplies a precursor gas 5 made of precursors 14, which are raw materials for manufacturing hafnium oxide, into the chamber 11. As the precursor 14, tetra-tert-butoxyhafnium, HfCl4, Hf[N(CH3)2], tetrakisdimethylaminohafnium, tetrakisethylmethylaminohafnium, tetrakisethylmethylaminohafnium, or the like can be used.

[0016] 1 and 2 shows a preferred embodiment of the present invention, in which a precursor 14 stored in a precursor storage unit (no reference numeral in the figures) is vaporized, and the resulting precursor gas 5 is supplied through a pipe (no reference numeral in the figures) and from the tip of the pipe into the chamber 11. The tip of the pipe may be nozzle-shaped. The precursor gas supply unit 13 may also be equipped with a flow meter for adjusting or managing the amount of gas, a precursor gas heating means, and the like (not shown). The number of precursor gas supply units 13 in the manufacturing apparatuses 1A and 1B is not particularly limited, and can be one or two or more.

[0017] The manufacturing apparatuses 1A and 1B may be equipped with a first member position adjustment means for changing or adjusting the incident angle or irradiation position of the charged particle beam relative to the first member 3, a temperature adjustment means for adjusting the temperature inside the chamber 11 or the temperature of the surface of the base layer of the first member 3, a laser irradiation means, various gas assist means, etc. (not shown).

[0018] In the manufacturing apparatuses 1A and 1B, the radiation source 17 is not particularly limited as long as it emits a charged particle beam. Examples of the charged particle beam include an electron beam, ions of B, C, Al, Si, Cu, Ag, Au, Ar, N, O, Ge, H, Cs, P, Ga, As, Er, Eu, Sm, Nd, Sb, Sn, In, Br, Be, Ca, Cl, Cr, Cd, Fe, F, I, K, Li, Na, Mg, Pd, Pt, S, Se, Ti, Te, V, W, Zn, He, Kr, Ne, and Xe elements, and ions of molecules containing at least one of these elements. When the charged particle beam is an electron beam, for example, a field emission electron gun, a Schottky electron gun, a thermionic gun, or the like can be used as the beam source 17. Of these, a field emission electron gun is preferred because hafnium oxide can be easily obtained. In addition, in the case of a charged particle beam consisting of ions of B, C, Al, Si, Cu, Ag, Au, Ar, N, O, Ge, H, Cs, P, Ga, As, Er, Eu, Sm, Nd, Sb, Sn, In, Br, Be, Ca, Cl, Cr, Cd, Fe, F, I, K, Li, Na, Mg, Pd, Pt, S, Se, Ti, Te, V, W, Zn, He, Kr, Ne, or Xe elements or ions of molecules containing at least one of these elements, an ion gun can be used as the radiation source 17.

[0019] In the manufacturing apparatus 1B, the plasma gas supply unit 15 supplies the plasma gas 7 into the chamber 11. Plasma gas supply unit 15 typically supplies plasma gas produced by a plasma generator (not shown) into chamber 11. The means for supplying plasma gas 7 can be, but is not particularly limited to, a nozzle or the like. In precursor gas supply unit 13, the direction of the tip of the piping is adjusted to supply precursor gas 5 so that it remains on the surface of the base layer. However, plasma gas supply unit 15 preferably has a plasma gas supply port configured to supply plasma gas 7 so that it fills the entire interior of chamber 11. The number of plasma gas supply units 15 in the production apparatus 1B is not particularly limited, and can be one or two or more.

[0020] Here, the plasma generator can be a plasma generator that uses, for example, inductively coupled plasma (ICP), capacitively coupled plasma (CCP), electron cyclotron resonance plasma (ECRP), helicon wave plasma (HP), surface wave plasma (SWP), microwave plasma, etc., for a raw material gas supplied from a plasma gas source, i.e., a raw material gas storage unit (not shown). Of these, RF plasma generators that use inductively coupled plasma (ICP), capacitively coupled plasma (CCP), etc., which are RF plasmas in the frequency range of 3 to 100 MHz, are preferred.

[0021] In the present invention, it is preferable to use a plasma gas containing oxygen, specifically a plasma gas containing atomic oxygen radicals, as the plasma gas 7. Atomic oxygen radicals are unstable and tend to bond energetically with other atoms or molecules through an oxidation-reduction reaction to stabilize themselves. Therefore, when a charged particle beam is irradiated onto the precursor gas 5 residing on the surface of the underlayer in the presence of a plasma gas containing oxygen, a substance (by-product) derived from the precursor 14 is formed. This substance can then react with the plasma gas containing oxygen to produce reaction products such as CO and CO. By evacuating these reaction products using a vacuum pump 19, a carbon-free hafnium oxide-containing layer can be efficiently formed. The plasma gas containing oxygen element is preferably formed from at least one selected from water, oxygen, ozone, and air.

[0022] When using the manufacturing apparatus 1B, the precursor gas 5 is retained on the surface of the base layer, but the location of the plasma gas 7 is not particularly limited. That is, the plasma gas 7 may be retained on the surface of the base layer together with the precursor gas 5, or may be present around the region where the precursor gas 5 retained on the surface of the base layer is present. The proportions of the precursor gas 5 and the plasma gas 7 used are not particularly limited, but when the total volume of the two is taken as 100 volume %, the amounts of the precursor gas 5 and the plasma gas 7 used are preferably 0.01 to 50 volume % and 50 to 99.99 volume %, respectively, and more preferably 0.1 to 10 volume % and 90 to 99.9 volume %, respectively.

[0023] As described above, in the manufacturing apparatuses 1A and 1B equipped with the vacuum pump 19, the inside of the chamber 11 is preferably under reduced pressure when irradiating with a charged particle beam. When the manufacturing apparatus 1B is used, the plasma gas and precursor gas are preferably introduced at pressures that are 0.001 to 500,000 times and 0.00001 to 10,000 times, and more preferably 1 to 1,000 times and 1 to 1,000 times higher than the pressure inside the chamber 11 before the plasma gas and precursor gas are supplied, respectively.

[0024] In the charged particle beam irradiation process according to the present invention, the underlayer or the first member 3, or the precursor gas 5 may or may not be heated, but from the viewpoint of the yield of hafnium oxide, the temperature thereof is preferably 30°C to 400°C, more preferably 30°C to 120°C.

[0025] In the present invention, a charged particle beam having a small beam diameter is usually used, so that a fine pattern containing hafnium oxide can be easily formed on the surface of the underlayer. For example, to obtain a pattern having a shape consisting of points, lines, circles, or a combination thereof, a method of irradiating the charged particle beam while scanning, or a method of irradiating the charged particle beam while moving the first member and fixing the optical path, can be applied. When an electron beam is used as the charged particle beam, the irradiation conditions are not particularly limited. The acceleration voltage of the electron beam is preferably 0.1 to 30 kV, more preferably 1 to 10 kV.

[0026] The following describes methods for manufacturing electronic components such as capacitor devices, ferroelectric memory devices, and semiconductor devices. The first member used in manufacturing these devices depends on the type of device, but the base layer is preferably made of a material that will not be altered, decomposed, or damaged by exposure to charged particle beams, selected from metals, alloys, oxides, nitrides, oxynitrides, carbides, carbonitrides, etc.

[0027] [1] Manufacturing method of capacitor device As a non-limiting example, a method for manufacturing a capacitor device represented by (V) will be described with reference to Fig. 3. Fig. 3 is a partial cross-sectional view of the capacitor device. Both (II) and (IV) are precursor products and are included in the electronic component according to the present invention.

[0028] FIG. 3(I) shows a composite formed by sequentially laminating a patterned first electrode layer 22A and an insulating layer 24A on the surface of a previously prepared auxiliary plate 20A. This composite, with the insulating layer 24A as the base layer, is used as the first member according to the present invention. Here, the auxiliary plate 20A can be made of, for example, glass, metal, etc. The first electrode layer 22A can be made of, for example, Ni, Cu, Al, W, Ti, Ag, Au, Pt, Zn, Sn, Pb, Fe, Cr, Mo, Ru, Pd, Ta, or alloys thereof (e.g., CuNi, AuNi, AuSn), or metal nitrides or metal oxynitrides such as TiN, TiAlN, TiON, TiAlON, TaN, etc. The insulating layer 24A can be made of, for example, a metal oxide (AlO x , SiO x , AlTiO x , SiTiO x , TaO x , ZrO x , HfSiO x , ZrSiO x , TiZrO x , TiZrWO x , TiO x , SrTiO x , PbTiO x , BaTiO x , BaSrTiO x , BaCaTiO x , SiAlO x etc.), metal nitrides (AlN x , SiN x , AlScN x etc.), metal oxynitrides (AlO x N y , SiO x N y , HfSiO x N y , SiC x O y N z It should be noted that the above chemical formulas including x, y, or z simply represent the constitution of the material and do not limit the composition.

[0029] The composite is placed at a predetermined position inside the chamber 11 of FIG. 1 or FIG. 2, and the precursor gas 5 is allowed to remain on the surface of the insulating layer 24A, which is the base layer, and a charged particle beam is irradiated to form a hafnium oxide-containing layer 26 on the surface of the insulating layer 24A (see (II) of FIG. 3). 3(III) and 3(IV), a composite insulating layer 24B formed by sequentially laminating a patterned second electrode layer 22B and an insulating layer 24B is placed on the surface of a separately prepared auxiliary plate 20B so as to face the hafnium oxide-containing layer 26, and these are integrated by pressure treatment or the like. The configurations of auxiliary plate 20B, second electrode layer 22B, and insulating layer 24B may be the same as or different from the configurations of auxiliary plate 20A, second electrode layer 22A, and insulating layer 24A, respectively. Thereafter, the auxiliary plates 20A and 20B are removed, and the capacitor device shown in FIG. 3(V) can be obtained by processing the capacitor device into a desired shape as required.

[0030] [2] Manufacturing method of ferroelectric memory device As a non-limiting example, a method for manufacturing a ferroelectric memory device represented by (V) is described using FIG. 4. The device is formed by sequentially stacking a hafnium oxide layer 34, a paraelectric layer 36, and a patterned second electrode layer 32B (upper electrode) on a patterned first electrode layer (conductive layer, lower electrode) 32A. FIG. 4 is a partial cross-sectional view of the ferroelectric memory device. (II) and (IV) are both precursor products and are included in the electronic component of the present invention. The hafnium oxide layer 34 is a ferroelectric layer that exhibits spontaneous polarization even without the application of an external electric field, and whose polarization is reversed when an external electric field is applied. The paraelectric layer 36 is a layer that exhibits polarization when an electric field is applied, and whose polarization disappears when the electric field is removed.

[0031] FIG. 4(I) shows a composite in which a first electrode layer 32A is laminated on the surface of a previously prepared auxiliary plate 30A. This composite with the first electrode layer 32A as the base layer is used as the first member according to the present invention. Here, the auxiliary plate 30A can be made of an electrically insulating material such as a metal oxide, a metal nitride, or a metal carbide. The first electrode layer 32A can be made of lanthanum strontium manganese oxide or titanium nitride, or can be made of a titanium nitride layer and an iridium (Ir) layer.

[0032] The composite is placed at a predetermined position inside the chamber 11 of FIG. 1 or FIG. 2, and the precursor gas 5 is allowed to remain on the surface of the first electrode layer 32A, which is the base layer, and a charged particle beam is irradiated to form a hafnium oxide-containing layer 34 on the surface of the first electrode layer 32A (see (II) of FIG. 4). Next, as shown in (III) and (IV) of Fig. 4, a separately prepared auxiliary plate 20B is provided on its surface with a composite paraelectric layer 36, which is formed by sequentially laminating a second electrode layer 32B and a paraelectric layer 36, and the composite is placed facing the hafnium oxide-containing layer 26, and these are integrated by pressure treatment or the like. The configurations of the auxiliary plate 30B and the second electrode layer 32B may be the same as or different from the configurations of the auxiliary plate 30A and the second electrode layer 32A, respectively. The paraelectric layer 36 is made of, for example, SiO x , SiN x , SrTiO x It should be noted that the above chemical formula including x simply expresses the constitution of the material and does not limit the composition. Thereafter, the auxiliary plates 30A and 30B are removed, and the capacitor device shown in FIG. 4(V) can be obtained by processing the capacitor device into a desired shape as required.

[0033] [3] Manufacturing method of semiconductor device A method for manufacturing a semiconductor device will be described with reference to Figures 5 and 6. In the present invention, the term "semiconductor device" refers to an element (transistor, diode, etc.) that functions by utilizing semiconductor properties, a circuit including the element, and a device including the circuit.

[0034] As an example that is not limited by the present invention, a method for manufacturing a semiconductor device represented by (III) will be described with reference to Fig. 5. Fig. 5 is a partial cross-sectional view of the semiconductor device. Also, (II) is a precursor product, which is included in the electronic component according to the present invention.

[0035] 5(I) shows a composite prepared in advance, in which a gate electrode 41 is laminated on the surface of a substrate 40. This composite with the gate electrode 41 as the base layer is used as the first member according to the present invention. Here, the substrate 40 is made of glass or glass with SiO 2 on the surface. x The gate electrode 41 may be made of Mo, Cr, Al, Ti, or Cu, or an alloy containing two or more of these metal elements.

[0036] The composite is placed at a predetermined position inside the chamber 11 of FIG. 1 or FIG. 2, and the precursor gas 5 is allowed to remain on the surface of the gate electrode 41, which is the base layer, and a charged particle beam is irradiated to form a hafnium oxide-containing layer 43 (gate insulating layer) on the surface of the gate electrode 41 (see (II) of FIG. 5). Next, a semiconductor layer 45 is formed on the surface of the hafnium oxide-containing layer 43, and then a source electrode 46 and a drain electrode 47 are formed on the surface of the hafnium oxide-containing layer 43 while covering the periphery of the semiconductor layer 45. Furthermore, a protective layer 49 is formed to cover the exposed hafnium oxide-containing layer 43, the source electrode 46, and the drain electrode 47, thereby obtaining the semiconductor device shown in FIG. 5 (III). The semiconductor layer 45 can be made of, for example, an oxide containing at least one element selected from indium, zinc, gallium, and tin. The source electrode 46 and the drain electrode 47 can be made of, for example, Mo, Al, Ti, or Cu, or an alloy containing two or more of these metal elements. The protective layer 49 can be made of, for example, SiO x , SiN x , SiO x N y It should be noted that the above chemical formulas including x or y simply represent the constitution of the material and do not limit the composition.

[0037] Next, as another manufacturing example not limited by the present invention, a manufacturing method of a semiconductor device represented by (III) will be described with reference to Fig. 6. Fig. 6 is a partial cross-sectional view of the semiconductor device. Also, (II) is a precursor product, which is included in the electronic component according to the present invention.

[0038] FIG. 6(I) shows a composite prepared in advance, in which a semiconductor layer 51 is laminated on the surface of a substrate 50, and a source region 52 and a drain region 53 are further provided on the surface of the semiconductor layer 51, spaced apart from each other. This composite, with the semiconductor layer 51 as the base layer, is used as the first member according to the present invention. Here, the substrate 50 may be made of, for example, n-type silicon carbide. The semiconductor layer 51 may be made of, for example, p-type silicon carbide or an oxide containing at least one element selected from indium, zinc, gallium, and tin. The source region 52 and the drain region 53 are preferably made of ion-implanted SiO x etc., each consisting of n + type source region and n + The gate electrode is a gate-drain region.

[0039] The composite is placed at a predetermined position inside the chamber 11 of FIG. 1 or FIG. 2, and the precursor gas 5 is allowed to remain on the surface of the semiconductor layer 51, which is the base layer, and a charged particle beam is irradiated to form a hafnium oxide-containing layer 54 (gate insulating layer) on the surface of the semiconductor layer 51 (see (II) of FIG. 6). Next, a gate electrode 57 is formed on the surface of the hafnium oxide-containing layer 54, and a source electrode 55 and a drain electrode 56 are formed so as to straddle the surface of the semiconductor layer 51 while covering part of the surfaces of the source region 52 and the drain region 53, thereby obtaining the semiconductor device shown in Fig. 6 (III). The source electrode 55 and the drain electrode 56 can be made of, for example, Mo, Al, Ti, or Cu, or an alloy containing two or more of these metal elements. Although not shown in FIG. 6(III), a protective layer similar to the protective layer 49 in FIG. 5(III) may be formed to cover the gate electrode 57, the source electrode 55, and the drain electrode 56. [Example]

[0040] Hereinafter, an example will be shown in which the base layer is a semiconductor layer, a P-doped n-type silicon substrate (size: 5 mm × 5 mm × 0.5 mm, hereinafter referred to as "Si plate") is used as the first member 3 made of this semiconductor layer, and a hafnium oxide film is formed on the surface while being patterned to produce a composite simulating an electronic component. Note that the present invention is not limited to these examples in any way.

[0041] Example 1 An electronic component manufacturing apparatus 1A was used, which was a tabletop microscope "Miniscope TM4000" (model name) manufactured by Hitachi High-Technologies Corporation, equipped with a precursor gas supply unit 13 that supplies a precursor gas into the chamber, and a vacuum pump (see FIG. 1). The electronic component manufacturing apparatus 1A in FIG. 1 is a schematic diagram of an apparatus for synthesizing and depositing hafnium oxide from a hafnium oxide precursor on the surface of a first member 3 (Si plate). The manufacturing apparatus 1A in FIG. 1 includes a precursor gas supply unit 13 that supplies a precursor gas 5 toward the first member 3 (Si plate), and a vacuum pump 19. Note that, since this tabletop microscope is an electron microscope, the radiation source 17 is an electron gun. The precursor gas 5 was prepared by evaporating a precursor 14 in the precursor gas supply unit 13.

[0042] First, in the electronic component manufacturing apparatus 1A, the degree of vacuum is set to 2×10 -3 A precursor gas 5 consisting of tetra-tert-butoxyhafnium (Hf(O-tert-C4H9)4) volatilized at 35°C was supplied into a chamber 11 at 25 Pa using a nozzle with an inner diameter of 0.25 mm toward the surface of a first member 3 (Si plate) at 25°C. The angle between the nozzle and the first member 3 (Si plate) was 30°, and the distance between the nozzle and the first member 3 (Si plate) was 1.4 mm. The degree of vacuum in the chamber 11 after the precursor gas supply was 2×10 -2 It was Pa. Next, an electron beam was irradiated at an acceleration voltage of 5 kV and a working distance of 7 mm toward the surface of the first member 3 (Si plate) where the precursor gas 5 was retained. The electron beam was scanned at 3.3 to 50 μsec / pixel, and patterned deposition films were formed in six locations on the surface of the first member 3 (Si plate) with different areas: 72 μm × 48 μm (region I), 15 μm × 10 μm (region II), 7.5 μm × 5 μm (region III), 5 μm × 3.3 μm (region IV), 3.7 μm × 2.5 μm (region V), and 3.0 μm × 2.0 μm (region VI), to obtain a composite C1 (see FIG. 7).

[0043] Figure 8 shows a cross-sectional image (a) of the deposited film of the obtained composite C1 taken by a scanning transmission electron microscope, and a mapping image (oxygen atoms (b), oxygen atoms (c), and hafnium atoms (d)) obtained by electron energy loss spectroscopy. Before taking these images, a carbon protective layer was applied to the surface of the deposited film. As shown in Figure 8, signals of hafnium atoms and oxygen atoms were confirmed in the deposited film, and therefore the deposited film was determined to be composed of hafnium oxide (HfO x ) can be seen to consist of

[0044] Example 2 Electronic component manufacturing apparatus 1B was used, which was the same as electronic component manufacturing apparatus 1A used in Example 1 but further provided with plasma gas supply unit 15 for supplying plasma gas into chamber 11 (see FIG. 2).

[0045] In electronic component manufacturing equipment 1B, the vacuum level is 2 x 10 -3 A plasma gas consisting of air generated at 13.56 MHz with an RF output of 40 W was supplied into the chamber 11 at 200 Pa, filling the chamber 11. Then, a precursor gas 5 consisting of tetra-tert-butoxyhafnium (Hf(O-tert-C4H9)4) volatilized at 35°C was supplied to the surface of the first member 3 (Si plate) at 25°C using a nozzle with an inner diameter of 0.25 mm. The angle between the nozzle and the first member 3 (Si plate) was 30°, and the distance between the nozzle and the first member 3 (Si plate) was 1.4 mm. The vacuum level in the chamber after the precursor gas supply was 2×10-2 It was Pa. The degree of vacuum after supplying only the plasma gas and only the precursor gas into the chamber was 7×10 -1 Pa and 2 x 10 -2 It was Pa. Next, an electron beam was irradiated at an acceleration voltage of 5 kV and a working distance of 7 mm toward the surface of the first member 3 (Si plate) where the precursor gas 5 was retained. The electron beam was scanned at 3.3 μsec / pixel for 3 minutes, forming a 150 nm thick deposition film (hereinafter referred to as a "hafnium oxide film") in a 7 μm × 3 μm region on the surface of the first member 3 (Si plate), thereby obtaining a composite C2 (see FIGS. 9 and 10).

[0046] Example 3 The same operation as in Example 2 was carried out except that no plasma gas was used, to obtain a composite C3 having a deposition film made of hafnium oxide on part of the surface of the first member 3 (Si plate) (see Figures 9 and 10).

[0047] FIG. 9 shows cross-sectional images (a) of the composites obtained in Examples 2 and 3 taken by a scanning transmission electron microscope, and mapping images (carbon atoms (b) and hafnium atoms (c)) obtained by electron energy loss spectroscopy. When taking these images, a carbon protective layer was applied to the surface of the hafnium oxide film in advance. In the mapping image (b) of Example 2 in FIG. 9, no carbon signal is observed, indicating that the formed hafnium oxide film does not contain impurities. On the other hand, in the mapping image (b) of Example 3 in FIG. 9, a weak carbon signal is observed, indicating that the formed hafnium oxide film contains impurities including carbon.

[0048] Figure 10 shows the HfO x10A shows a spectrum obtained by electron energy loss spectroscopy of the inside of the portion (hafnium oxide film) indicated by "." According to FIG. 10A, in Example 3, the carbon-K absorption edge was detected, which makes it clear that the formed hafnium oxide film contains carbon. On the other hand, in Example 2, the carbon-K absorption edge was not detected, which makes it clear that no carbon is contained. As is clear from FIG. 10B, in both Examples 2 and 3, the Hf-M4 and M5 absorption edges derived from hafnium oxide in the hafnium oxide film were detected. [Industrial Applicability]

[0049] In the method for manufacturing electronic components of the present invention, a charged particle beam is used, and the irradiation method can be modified depending on the structure of the intermediate or final product to manufacture electronic components having a hafnium oxide-containing layer with a fine pattern, a thin film, or the like. In particular, when a precursor gas is irradiated with a charged particle beam in the presence of a plasma gas, a carbon-free high-purity hafnium oxide layer can be formed, making it possible to manufacture electronic components that fully exhibit the chemical and physical properties of hafnium oxide. Therefore, the electronic components obtained by the present invention are suitable as, for example, capacitor devices, ferroelectric memory devices, semiconductor devices, etc. [Explanation of symbols]

[0050] 1A, 1B: Electronic component manufacturing equipment 3: First member having a base layer 5: Precursor gas 7: Plasma gas 9: By-products 11: Chamber 13: Precursor gas supply unit 14: Precursor 15: Plasma gas supply unit 17: Line source 19: Vacuum pump 20A, 20B: Auxiliary board 22A: 1st electrode layer 22B: Second electrode layer 24A, 24B: Electrically insulating layer 26: Hafnium oxide-containing layer (dielectric layer) 30A, 30B: Auxiliary board 32A: 1st electrode layer 32B: Second electrode layer 34: Hafnium oxide-containing layer 36: Paraelectric layer 40: Circuit board 41: Gate electrode 43: Hafnium oxide-containing layer (gate insulating layer) 45: Semiconductor layer 46: Source electrode 47: Drain electrode 49:Protective layer 50: Circuit board 51: Semiconductor layer 52: Source area 53: Drain region 54: Hafnium oxide-containing layer (gate insulating layer) 55: Source electrode 56: Drain electrode 57: Gate electrode

Claims

1. 1. A method for manufacturing an electronic component comprising a hafnium oxide-containing layer on at least a portion of an underlayer selected from an electrically insulating layer, a conductive layer, and a semiconductor layer, the method comprising: a charged particle beam irradiation step of irradiating a precursor gas made of a hafnium oxide precursor, which is retained on a surface of the underlayer of the first member having the underlayer, with a charged particle beam to form the hafnium oxide-containing layer on at least a portion of the surface of the underlayer; the temperature of the underlayer in the charged particle beam irradiation step is 30°C to 120°C; The method for manufacturing electronic components is characterized in that the acceleration voltage of the charged particle beam is 0.1 to 10 kV.

2. 2. The method for manufacturing an electronic component according to claim 1, wherein in the charged particle beam irradiation step, the precursor gas is irradiated with the charged particle beam in the presence of a plasma gas.

3. 3. The method for manufacturing an electronic component according to claim 2, wherein the plasma gas is made of a substance containing oxygen element.

4. 4. The method for manufacturing an electronic component according to claim 1, wherein the electronic component is at least one selected from the group consisting of a capacitor device, a ferroelectric memory device, and a semiconductor device.

Images