TW201324788A - Manufacturing method of embossed structure, thin film transistor, film capacitor, actuator, piezoelectric inkjet head and optical component - Google Patents

Abstract

An object of the present invention is to provide a method for producing a functional element which can be manufactured by a process which is much smaller than the conventional materials and manufacturing energy, and which is shorter than the prior art. The solution of the present invention is a method for manufacturing an embossed structure, comprising the following process: preparing a first process for forming a liquid material of metal oxide or metal by heat treatment; by coating on a substrate The liquid material forms a second process of the precursor composition layer composed of the metal oxide or metal precursor composition; the precursor composition layer is formed by embossing the precursor composition layer using a concave-convex mold a third process of embossing the structure comprising a residual film; a fourth process for treating the residual film by applying a ashing treatment of atmospheric piezoelectric slurry or low-pressure plasma to the precursor composition layer formed with the embossed structure; The fifth process of forming an embossed structure composed of a metal oxide or a metal from the precursor composition by heat-treating the precursor composition layer.

Description

Manufacturing method of embossed structure, thin film transistor, film capacitor, actuator, piezoelectric inkjet head and optical component

The present invention relates to a method of manufacturing an embossed structure, a thin film transistor, a film capacitor, an actuator, a piezoelectric inkjet head, and an optical element.

FIG. 27 is a view for explaining a conventional thin film transistor 900.
A conventional thin film transistor 900 includes a source electrode 950 and a drain electrode 960 as shown in FIG. 27; a channel layer 940 between the source electrode 950 and the germanium electrode 960; A gate electrode 920 of an on state of the channel layer 940; a gate insulating layer 930 formed of a ferroelectric material formed between the gate electrode 920 and the channel layer 940. Further, reference numeral 910 in Fig. 27 denotes an insulating substrate.
In the conventional thin film transistor 900, a material constituting the gate insulating layer 930 is made of a ferroelectric material (for example, BLT ((Bi _4-x La _x Ti ₃ O ₁₂ ), PZT (Pb(Zr _x , Ti _1-x )) O ₃ )), the material constituting the channel layer 940 is an oxide conductor material (for example, Indium Tin Oxide (ITO).
According to the conventional thin film transistor 900, since the oxide conductor material is used as the material constituting the channel layer, the carrier concentration can be increased, and the material constituting the gate insulating layer is made of a ferroelectric material, so that it can be driven at a low level. The drive voltage is switched at a high speed, and as a result, a large current can be controlled at a high speed with a low drive voltage.
A conventional thin film transistor can be manufactured by a conventional method for manufacturing a thin film transistor shown in FIG. Fig. 28 is a view for explaining a method of manufacturing a conventional thin film transistor. 28(a) to 28(e) are plan views, and Fig. 28(f) is a plan view of the film transistor 900.
First, as shown in FIG. 28(a), Ti (10 nm) and Pt are formed by an electron beam evaporation method on an insulating substrate 910 composed of a Si substrate having an SiO ₂ layer formed on the surface thereof. A gate electrode 920 composed of a laminated film of (40 nm).
Next, as shown in Fig. 28(b), BLT (Bi _3.25 La _0.75 Ti ₃ O ₁₂ ) or PZT (Pb (Zr _0.4 Ti) is formed by the sol-gel method from above the gate electrode 920. A gate insulating layer 930 (200 nm) composed of _0.6 )O ₃ ).
Next, as shown in FIG. 28(c), a channel layer 940 (5 nm to 15 nm) made of ITO is formed on the gate insulating layer 930 by a radio frequency sputtering method (Radio Frequency sputtering method).
Next, as shown in FIG. 28(d), a source electrode 950 and a germanium electrode 960 are formed by vacuum-depositing Ti (30 nm) and Pt (30 nm) on the channel layer 940 by electron beam evaporation.
Next, the element region is separated from the other element regions by the RIE method (Reactive Ion Etching method) and the wet etching method (HF: HCl mixed solution).
According to this, the thin film transistor 900 shown in Figs. 28(e) and 28(f) can be manufactured.
Fig. 29 is a view for explaining the electrical characteristics of a conventional thin film transistor 900. Further, reference numeral 940a in Fig. 29 denotes a channel, and symbol 940b denotes a depletion layer.
In the conventional thin film transistor 900, when the gate voltage is 3V (V _G = 3V) as shown in FIG. 29, the ON-state current is about 10 ^-4 A, and the switching ratio ( On/off ratio) obtained 1×10 ⁴ , field-effect mobility μ _FE obtained 10 cm ² /Vs, and memory window (m e m o r y window ) obtained about 2V Value.
[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-121029

However, since the conventional thin film transistor 900 is manufactured by the above method, there is a problem that a high vacuum is required in the process of forming the gate electrode 920, the channel layer 940, the source electrode 950, and the drain electrode 960. Process and/or photolithography processes, the use of raw materials or manufacturing energy is inefficient, and manufacturing takes a long time.
Further, such a problem is not only a problem found in the method of manufacturing the above-described thin film transistor, but also a method of manufacturing a functional device such as a film capacitor, an actuator, a piezoelectric ink jet head, an optical element, or the like. problem.
Accordingly, the present invention has been made to solve the above problems, and an object thereof is to provide a thin film transistor which is excellent in the process of manufacturing a raw material and a manufacturing energy which are much smaller than the conventional ones, and which is shorter than the prior art. A method of manufacturing an embossed structure of various functional elements.
[1] The method for producing an embossed structure according to the present invention, characterized by the process of preparing a first process for preparing a liquid material containing a metal-containing compound and forming a metal oxide or a metal by heat treatment; a second process for forming a precursor composition layer composed of the foregoing metal oxide or a precursor composition of the foregoing metal by coating the liquid material on a substrate; by forming the precursor The object layer is embossed using a embossing mold to form a third process of embossing the precursor composition layer including the residual film; by forming the precursor composition layer having the embossed structure described above Applying a fourth process of treating the residual film by an ashing treatment using atmospheric pressure plasma or low pressure plasma; heat treatment of the precursor composition layer A fifth process of forming the embossed structure composed of the metal oxide or the metal from the precursor composition layer in which the embossed structure is formed.
According to the method of manufacturing an embossed structure according to the present invention, the precursor composition layer can be formed by applying a liquid material on the substrate, and the precursor composition layer is embossed to form an embossed structure, thereby borrowing The embossed structure is formed by heat-treating the precursor composition layer at a high temperature, and is formed by embossing by using a mold having a submicron order of fine patterns. Since the micron-sized fine embossed structure is used, it is possible to use various materials and manufacturing energy which are much smaller than the conventional ones, and to manufacture various functional elements including the above-mentioned excellent thin film transistors, which are shorter than the conventional ones.
Further, according to the method for producing an embossed structure of the present invention, since the fourth process of treating the residual film by subjecting the precursor composition layer to ashing treatment is further included, the embossing without the influence of the residual film can be formed. Construct. Here, the embossed structure having no influence on the residual film means an embossed structure having a structure in which a portion where the residual film is present is split. It is included in the case where the residual film is not left at all in the portion where the residual film exists, and in the case where the island-shaped residual film remains in the portion where the residual film exists.
Moreover, according to the method for manufacturing an embossed structure according to the present invention, since the precursor composition layer is subjected to ashing treatment using atmospheric piezoelectric slurry or low-pressure plasma, an environment requiring no high vacuum is required in the fourth process. This eliminates the need for expensive high vacuum equipment and reduces the time required to implement the fourth process.
Further, techniques for forming an embossed structure without requiring a high vacuum environment include various printing techniques (letterpress, gravure printing, offset printing, screen printing method, Printing by inkjet (ink-jet), etc.). However, according to these printing techniques, since an embossed structure having a pattern of several tens of micron orders can be formed at most, an embossed structure having a fine pattern of a submicron order cannot be formed. On the other hand, according to the method for producing an embossed structure of the present invention, an embossed structure having a fine pattern of a submicron order can be formed without requiring a high vacuum environment.
In the method for producing an embossed structure of the present invention, the liquid material may be suitably used [sol-gel solution containing metal alkoxide], [MOD containing organometallic compound ( Metal Organic Decomposition), [containing metal salts (eg metal chloride, metal oxychloride (m e t a l o x y c h l o r i d e), metal nitrate, metal acetate (m e t a l a c e t a liquid material such as a metal salt solution of a t e ) or the like, [a solution in which at least two of the above sol-gel solution, the MOD solution and the metal salt solution are mixed].
In the method for producing an embossed structure according to the present invention, the residual film refers to a convex surface and a base which are most prominent in the concave-convex mold when the embossing process is applied to the precursor composition layer in the third process. A precursor composition layer between the surface of the material. Further, in the method for producing an embossed structure of the present invention, the residual film includes [a film which is discontinuous in each residual film formation region] in addition to [a film continuous in each residual film formation region] ( For example, take the membrane of the island structure).
In addition, [embossing] is sometimes referred to as [nanoimprint].
[2] In the method for producing an embossed structure according to the present invention, it is preferred that the residual film is completely removed in the fourth process.
By this method, an embossed structure free from the influence of the residual film can be formed. That is, in the fifth process, the precursor composition layer is split into a plurality of regions, and the precursor composition layer can be contracted in the in-plane direction without being reluctantly formed, so that it can be formed with high precision. The required embossed construction.
The method of completely removing the residual film can be suitably used [method of applying the first time calculated by ashing only by the relationship between the etching rate of the precursor composition layer and the thickness of the residual film by ashing treatment ( The ashing method by time management)], [the method of applying ashing time exceeding the first time (the ashing method by over etching), in which case the substrate is sometimes etched a substrate made of a material that is an etching stopper or a substrate having a layer made of a material that is an etching stopper at least on the surface is used as a substrate, and is subjected to ashing more than the above. The method of the first time (by the ashing method by using the etching stop layer together)] and the like.
[3] In the method of manufacturing an embossed structure according to the present invention, in the fourth process, the residual film is thinned until the residual film is formed by performing the fifth process subsequent to the fourth process. The thinness of the island structure is better.
By this method, an embossed structure free from the influence of the residual film can be formed. That is, in the fifth process, the precursor composition layer is split into a plurality of regions, and the precursor composition layer can be contracted in the in-plane direction without being reluctantly formed, so that the desired embossed structure can be formed with high precision. .
[4] In the method for producing an embossed structure according to the present invention, in the fourth process, it is preferred that the precursor composition layer having the embossed structure is subjected to ashing treatment using an atmospheric piezoelectric slurry. .
According to this method, since the embossed structure can be produced without using a vacuum process, it is possible to manufacture an embossed structure having no influence of the residual film by using a manufacturing process which is much smaller than the conventional production and which is shorter than the conventional one.
[5] In the method for producing an embossed structure according to the present invention, in the fourth process, the precursor composition layer having the embossed structure is subjected to ashing treatment using low-pressure plasma. good.
According to this method, since the embossed structure can be produced without using a high-vacuum process, it is possible to use an embossed structure which is much smaller than the conventional manufacturing process and which has no residual film effect. .
[6] In the method for producing an embossed structure according to the present invention, it is preferable to carry out the fourth process under a pressure of 0.1 Pa or more.
It is intended to carry out the fourth process under a pressure of 0.1 Pa or more because when the fourth process is carried out under a pressure of less than 0.1 Pa, it is time consuming and productive to form a pressure environment, or a large-scale pressure reducing device is required. There are cases where the manufacturing cost is increased. From this point of view, in the method for producing an embossed structure of the present invention, it is preferable to carry out the fourth process under a pressure of 1 Pa or more, and it is more preferable to carry out the fourth process under a pressure of 10 Pa or more.
On the other hand, in the method for producing an embossed structure of the present invention, it is preferable to carry out the fourth process under a pressure of about 1000 Pa to 100,000 Pa. However, if this pressure range is used, the pressure environment can be formed in a short time. Moreover, if it is such a pressure range, it can be continuously put into a pressure environment while transporting a work in an atmospheric pressure environment. Further, in the method for producing an embossed structure of the present invention, it is also preferable to carry out the fourth process under a pressure of 1000 Pa or less. When the fourth process is performed under a pressure of 1000 Pa or less, as will be described later, the fourth process can be stably performed in a state where a bias voltage is applied. From this point of view, in the method of manufacturing an embossed structure of the present invention, it is more preferable to carry out the fourth process under a pressure of 100 Pa or less.
[7] In the method of manufacturing an embossed structure of the present invention, it is preferable to carry out the fourth process in a state where a bias voltage is applied.
Under reduced pressure conditions, a stable glow discharge can be caused even in a state where a bias voltage is applied. Therefore, by performing the fourth process in a state where the bias voltage is applied as described above, the ashing process can be performed at a high etching rate, and the embossed structure can be manufactured with high productivity.
Moreover, since the mean free path of the gas (ashing gas) used for ashing under reduced pressure is longer than that under atmospheric pressure, and the flying direction of the ashing gas is uniform in one direction, as described above By performing the fourth process in a state where a bias voltage is applied, the ratio of etching (side etching) to the side portion of the embossed structure can be reduced, and an embossed structure having high shape accuracy can be manufactured. body.
[8] In the method of producing an embossed structure of the present invention, it is preferred to carry out the fourth process using a reactive gas.
By this method, the ashing process can be performed at a high etching rate, and the embossed structure can be produced with high productivity. In this case, the reactive gas is preferably a reactive gas which can cause a chemical reaction with a component constituting the precursor composition layer and can etch the precursor composition layer.
[9] In the method for producing an embossed structure according to the present invention, it is preferred that the fourth process is carried out by using the halogen-containing element gas as the reactive gas.
Thus, the fourth process can be carried out by using a highly reactive halogen-containing element gas for a wide variety of metals, and embossing without residual film effects can be produced from various types of precursor composition layers. Construct.
[10] In the method for producing an embossed structure according to the present invention, it is preferred that the fourth process is carried out by using the halogen-containing gas and the mixed gas containing the Ar gas as the reactive gas.
In this manner, the fourth process can be carried out by using a highly reactive halogen-containing element gas and an Ar gas having high grinding characteristics for each type of metal, and can be composed of various types of precursors. The material layer forms an embossed structure without the influence of a residual film with high productivity.
In the method of producing an embossed structure according to any one of the above [9] or [10], the halogen-containing gas can be suitably used as a fluorine-containing gas. Chlorine-containing gas, bromine-containing gas, etc. Specifically, in the case where the precursor composition layer is composed of a substance containing Si, for example, CF ₄ , CF ₄ /O ₂ , CF ₄ /H ₂ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ , SF ₆ /O ₂ , NF ₃ , SiF ₄ /O ₂ , Cl ₂ , BCl ₃ , CCl ₄ , CF ₃ Br, HBr, HBr/NF ₃ , HBr/O ₂ , BCl ₃ /CCl ₄ , BCl ₃ /CF ₄ or the like, in the case where the precursor composition layer is composed of a substance containing Al, for example, Cl ₂ , BCl ₃ , CCl ₄ , SiCl ₄ , BCl ₃ /Cl ₂ /Ar, etc. may be suitably used in the precursor When the composition layer is composed of a substance containing at least one of W, Mo, Ta, and Ti, it is suitable to use, for example, CF ₄ , CF ₄ /O ₂ , NF ₃ , CCl ₄ /O _{2 ,} etc., in the precursor composition. In the case where the layer is composed of a substance containing Cr, for example, Cl ₂ , Cl ₂ /O ₂ , CCl ₄ /O ₂ or the like can be suitably used, and the precursor composition layer is composed of a substance containing at least one of Au and Pt. In the case of, for example, Cl ₂ , Cl ₂ /Ar or the like can be suitably used.
In the method for producing an embossed structure of the present invention, it is preferred that the carrier gas is He gas or N ₂ gas.
[11] In the method of manufacturing an embossed structure according to the present invention, the method further comprises heating the precursor composition layer to a range of from 80 ° C to 200 ° C between the second process and the third process. a preheating process for lowering the fluidity of the precursor composition layer in advance, in the third process, by heating the precursor composition layer to a temperature in the range of 80 ° C to 300 ° C In the state of the precursor composition layer, embossing is performed on the precursor composition layer by using a mold heated to a temperature in the range of 80 ° C to 300 ° C, and an embossed structure is preferably formed on the precursor composition layer.
By this method, the precursor composition layer is previously lowered by performing a solidification reaction of the precursor composition layer to some extent by heating to a temperature in the range of 80 ° C to 200 ° C. Fluidity, and applying a pressure to a precursor composition layer having a high plastic deformation capacity by reducing the hardness of the precursor composition layer by heating to a temperature in the range of 80 ° C to 300 ° C Since the flower is processed, the desired embossed structure can be formed with high precision, and as a result, an embossed structure having desired properties can be produced.
However, unlike the case of a normal embossing technique using embossing using a polymer material, there is a case where an embossing process using embossing of a liquid material which is a metal oxide or a metal by heat treatment is used. A report example of embossing at room temperature. However, in order to provide a predetermined plastic deformation ability, it is necessary to contain an organic component, a solvent, or the like. Therefore, the shape deterioration at the time of firing is severed.
However, as a result of research by the inventors of the present invention, if the precursor composition layer is heated to a temperature in the range of 80 ° C to 300 ° C, the plastic deformation ability of the precursor composition layer becomes high. Moreover, it is obvious that the main solvent can be removed. Therefore, in the method for producing an embossed structure of the present invention, it is intended to obtain a high plastic deformation ability by heating to a temperature in the range of 80 ° C to 300 ° C, and a precursor having less shape deterioration at the time of firing. The composition layer is subjected to embossing.
Here, the heating temperature of the precursor composition layer is in the range of [80 ° C to 300 ° C] because when the above heating temperature is less than 80 ° C, the precursor composition layer is not sufficiently softened, so that the precursor cannot be sufficiently improved. When the heating temperature exceeds 300 ° C, the curing reaction of the precursor composition layer is excessively performed and the plastic deformation ability of the precursor composition layer is again lowered.
From the above point of view, it is more preferable to apply the embossing process to the precursor composition layer while heating the precursor composition layer to a temperature in the range of 100 ° C to 200 ° C.
Further, as described above, since the precursor composition layer is subjected to embossing using a mold heated to a temperature in the range of 80 ° C to 300 ° C, the precursor composition layer is applied while the embossing process is being performed. The plastic deformation ability is not lowered, so that the desired embossed structure can be formed with higher precision.
Here, it is assumed that the heating temperature of the above-mentioned mold is in the range of [80 ° C to 300 ° C] because when the above heating temperature is less than 80 ° C, the temperature of the precursor composition layer is lowered, so that the precursor composition When the plastic deformation ability of the layer is lowered, when the above heating temperature exceeds 300 ° C, the dehydration condensation reaction due to the precursor composition layer (d e h y d r a t i o The n-c o n d e n s a t i o n reaction is excessively performed to lower the plastic deformation ability of the precursor composition layer.
From the above point of view, in the above-described third process, embossing is preferably performed using a mold which is heated to a temperature in the range of 100 ° C to 200 ° C.
In the method for producing an embossed structure according to the present invention, in the third process described above, embossing is preferably performed at a pressure in the range of 1 MPa to 20 MPa.
According to the method for producing an embossed structure according to the present invention, as described above, the embossing process is applied to the precursor composition layer which is capable of obtaining high plastic deformation ability, even if the pressure applied during the embossing process is lowered to 1 MPa. At 20 MPa, the precursor composition layer is also deformed in accordance with the surface shape of the mold, and the desired embossed structure can be formed with high precision. Further, by reducing the pressure applied during the embossing to 1 MPa to 20 MPa, the mold is hardly damaged during the embossing.
Here, in the range where the pressure is in the range of [1 MPa to 20 MPa], when the pressure is less than 1 MPa, the pressure is too low to emboss the precursor composition, and if the pressure is 20 MPa, The precursor composition can be sufficiently embossed, so that it is not necessary to apply a pressure of 20 MPa or more.
From the above point of view, it is more preferable to apply embossing at a pressure in the range of 2 MPa to 10 MPa in the third process.
[12] In the method for producing an embossed structure according to the present invention, in the fifth process, it is preferable to form an embossed structure made of a metal oxide by heat treatment in an oxygen-containing atmosphere.
By this method, an embossed structure can be manufactured as [a gate electrode layer, a gate insulating layer, a source layer, a drain layer, a channel layer or a wiring layer in a thin film transistor], [film capacitor] as described later. First electrode layer, dielectric layer, second electrode layer or wiring layer], [piezoelectric layer in the actuator, electrode layer or wiring layer], [piezoelectric Various functional elements provided in the piezoelectric layer or the cavity member in the ink jet head, and the [lattice layer (lattice layer) in the optical element].
In this case, the metal oxide that can be produced can be exemplified by various paraelectric materials (for example, BZN (Bi _1.5 Zn _1.0 Nb _1.5 O ₇ ) or BST (Ba _x Sr _1-x ) Ti ₃ O ₁₂ ), SiO ₂ , SrTiO ₃ , LaAlO ₃ , HfO ₂ ), various ferroelectric materials (for example, PZT(Pb(Zr _x , Ti _1-x )O ₃ ), BLT(Bi _4-x La _x Ti ₃ O ₁₂ ), Nb Doped PZT (Nb doped PZT), La-doped PZT, barium titanate (BaTiO ₃ ), lead titanate (PbTiO ₃ ), BTO (Bi ₄ Ti ₃ O ₁₂ ), SBT ( SrBi ₂ Ta ₂ O ₉ ), BZN (Bi _1.5 Zn _1.0 Nb _1.5 O ₇ ), bismuth ferrite (BiFeO ₃ ), various semiconductor materials or various conductor materials (eg indium tin oxide (ITO), Indium oxide (In ₂ O ₃ ), antimony doped tin oxide (Sb-SnO ₂ ), zinc oxide (ZnO), aluminum doped zinc oxide (aluminium doped zinc) Oxide (Al-ZnO), gallium doped zinc oxide (Ga-ZnO), ruthenium oxide (RuO ₂ ), iridium oxide (IrO ₂ ), tin oxide ( Tin oxide) (SnO ₂ ), tin monoxide (SnO), antimony doped titanium dioxide (ni) Oxide doped titanium dioxide) (Nb-TiO ₂ ) oxide conductor material, indium gallium zinc complex oxide (IGZO), gallium doped indium oxide (In-Ga) -O(IGO)), an amorphous conducting oxide such as indium doped zinc oxide (In-Zn-O (IZO)), or strontium titanate ( SrTiO ₃ ), niobium doped strontium titanate (Nb-SrTiO ₃ ), strontium barium complex oxide (SrBaO ₃ ), strontium calcium complex oxide (SrCaO ₃ ), strontium ruthenate (SrRuO ₃ ), lanthanum nickelate (LaNiO ₃ ), lanthanum titanate (LaTiO ₃ ), lanthanum copper oxide ( LaCuO ₃ ), neodymium nickelate (NdNiO ₃ ), yttrium nickelate (YNiO ₃ ), Lanthanum Calcium Manganese complex oxide (LCMO), barium lead (barium) Plumbate) (BaPbO ₃ ), LSCO (La _x Sr _1-x CuO ₃ ), LSMO (La _1-x Sr _x MnO ₃ ), YBCO (YBa ₂ C u ₃ O _7-x ), LNTO(La(NI _1-x Ti _x )O ₃ ), LSTO((La _1-x , Sr _x )TiO ₃ ), STRO(Sr(Ti _1-x Ru _x )O ₃ ) and other perovskite type conducting oxides or pyrochlore type conducting oxides, other materials (such as High-k materials (HfO ₂ , Ta ₂ O ₅ , ZrO ₂ , HfSi _x O _y , ZrSi _x O _y , LaAlO ₃ , La ₂ O ₃ , (Ba _1-x , Sr _x )TiO ₃ , Al ₂ O ₃ , (Bi _2-x , Zn _x )(Zn _y , Nb _2-y ), Y ₂ O ₃ , GeO ₂ , Gd ₂ O _{3 ,} etc., Heusler alloy (Co, Co-Pt, Co-Fe, Mn-Pt, Ni-Fe) , alloys such as CoFeB, Co-Cr-Fe-Al, Co ₂ MnAl, etc.), barrier materials for MRAM (Magnetoresistance Random Access Memory) ((La _1-x , An electrode material for MRAM such as an oxide-based semimetal such as Sr _x ) MnO ₃ , AlAs, MgO, or Al ₂ O _{3 ,} or a multiferroic material (perovskite BiMnO ₃ , BiFeO ₃ , YbMnO _{3 ,} etc., garnet type R ₃ FeO ₁₂ (R=Dy, Ho, Er, Tm, Tb, Lu), Y ₃ Al ₅ O ₁₂ , Gd ₃ Ga ₅ O ₁₂ , SGGG (Gd _2.7 Ca _0.3 ) (Ga _4.0 Mg _0.32 Zr _0.65 Ca _0.03 )O _{12 ,} etc.), PRAM (Parameter Random Access Memory) material (Ge _x Te _1-x , Ge ₂ Sb ₂ Te _5th chalcogenide system (c h a l c o g e n i d e system), Sb-X alloy (X=Ge, Ga, In, Se, Te Etc. Photocatalyst uses rutile type titanium dioxide (TiO ₂ ).
[13] In the method for producing an embossed structure according to the present invention, in the fifth process, it is preferable to form an embossed structure made of a metal by heat treatment in a reducing atmosphere.
By this method, as described later, the functional solid material layer can be regarded as [the gate electrode layer or wiring layer in the thin film transistor], [the first electrode layer, the second electrode layer or the wiring layer in the film capacitor] [The electrode layer in the actuator], [the lattice layer in the optical element (metal lattice layer)], etc., can manufacture various functional elements.
In this case, the metal which can be manufactured can exemplify, for example, Au, Pt, Ag, Cu, Ti, Ge, In, Sn, or the like.
[14] The thin film transistor of the present invention, comprising a gate electrode layer, a gate insulating layer, a source layer, a drain layer, a channel layer, and a wiring layer, wherein the gate electrode layer, the gate insulating layer, and the source are At least one of the electrode layer, the above-described drain layer, the channel layer, and the wiring layer is formed by the method of producing the embossed structure of the present invention.
By this method, for at least one layer of the thin film transistor, the embossed structure without the influence of the residual film can be produced by using a process which is shorter than the prior art by using a very small amount of raw materials and manufacturing energy.
[15] The thin film transistor of the present invention, comprising: an oxide conductor layer including a source region, a drain region, and a channel region; and controlling conduction of the channel region a gate electrode of the state; a gate insulating layer formed of a ferroelectric material or a paraelectric material between the gate electrode and the channel region, wherein a thickness of the channel region is greater than a thickness of the source region and the drain region The oxide conductor layer having a thickness of the channel region which is thinner than the layer thickness of the source region and the layer thickness of the drain region is formed by the method for producing an embossed structure of the present invention.
According to the thin film transistor of the present invention, since the oxide conductive material is used as the material constituting the channel region, the carrier concentration can be increased, and since the material constituting the gate insulating layer is made of a ferroelectric material or a paraelectric material, it can be low. The driving voltage is switched at a high speed, and as a result, as in the case of the conventional thin film transistor, a large current can be controlled at a high speed with a low driving voltage.
Further, according to the thin film transistor of the present invention, the layer thickness of the channel region is thinner than the layer thickness of the source region and the layer thickness of the drain region, and the effect of the residual film is formed only by the manufacturing method of the embossed structure of the present invention. The oxide conductor layer can be used to manufacture a thin film transistor. Therefore, in the case of a conventional thin film transistor, it is also possible to form a channel region, a source region, and a drain region without using different materials, and it is possible to use far less raw materials and Energy is produced, and a thin film transistor as described above is produced in a process shorter than the prior art.
[16] In the thin film transistor of the present invention, the carrier concentration and the layer thickness of the channel region are set such that when the thin film transistor is in an OFF state, the entire channel region is depleted. The value is better.
According to this configuration, even if the carrier concentration of the oxide conductor layer is increased, the amount of current flowing when the thin film transistor is turned off can be sufficiently reduced, so that the necessary switching ratio can be maintained while being low. The drive voltage controls a large current.
In this case, when the thin film transistor is an enhancement type transistor, since the thin film transistor is turned off when a control voltage of 0 V is applied to the gate electrode, it is set as in In this case, when the total value of the channel region is depleted, when the thin film transistor is a depletion type transistor, the thin film transistor is turned off when a negative control voltage is applied to the gate electrode. It is also possible to set the value of the channel area as a whole at this time.
[17] The film capacitor of the present invention, comprising: a first electrode layer, a dielectric layer, a second electrode layer, and a wiring layer, wherein the first electrode layer, the dielectric layer, and the second electrode layer At least one of the wiring layers described above is formed by the method of producing the embossed structure of the present invention.
By this method, at least one layer of the film capacitor, the embossed structure without the influence of the residual film can be produced by using a process which is shorter than the prior art by using a very small amount of raw materials and manufacturing energy.
[18] The actuator of the present invention includes a piezoelectric layer, an electrode layer, and a wiring layer, wherein at least one of the piezoelectric layer, the electrode layer, and the wiring layer is an embossed structure of the present invention. The manufacturing method of the body is formed.
By this method, at least the piezoelectric layer, the embossed structure without the influence of the residual film can be produced by a process which is shorter than the conventional one, using a very small amount of raw materials and manufacturing energy.
In this case, the liquid material may be suitably used as a liquid material which becomes a ferroelectric material by heat treatment.
[19] The piezoelectric ink jet head according to the present invention, comprising: a cavity member; a vibrating plate formed on one side of the cavity member and having a piezoelectric layer; and being mounted on the other side of the cavity member a nozzle plate having a nozzle hole; an ink chamber defined by the cavity member, the vibrating plate, and the nozzle plate, the piezoelectric layer and/or the empty The cavity member is formed by the method of manufacturing the embossed structure of the present invention.
According to the piezoelectric ink jet head of the present invention, since the piezoelectric layer and/or the cavity member are formed by the method for producing the embossed structure of the present invention, the embossed structure can be formed without the influence of the residual film. A piezoelectric ink jet head is manufactured by using a process which is much smaller than the conventional materials and manufacturing energy, and which is shorter than the prior art.
[20] The optical element of the present invention comprising a lattice layer on a substrate, wherein the lattice layer is formed by the method for producing an embossed structure of the present invention.
By this method, the embossed structure having no influence of the residual film on the lattice layer can be produced by a process which is shorter than the prior art by using a very small amount of raw materials and manufacturing energy.
Further, when the lattice layer is composed of an insulator, the liquid material may be a liquid material which becomes an insulator material by heat treatment. Further, when the lattice layer is made of a metal, a liquid material which becomes a metal material by heat treatment can be used.

Fig. 1 is a view for explaining a method of manufacturing an embossed structure according to the first embodiment.
Fig. 2 is a view for explaining the method of manufacturing the embossed structure according to the second embodiment.
Fig. 3 is a view for explaining the method of manufacturing the embossed structure according to the third embodiment.
Fig. 4 is a view for explaining the method of manufacturing the embossed structure according to the fourth embodiment.
Fig. 5 is a view for explaining the method of manufacturing the embossed structure according to the fifth embodiment.
Fig. 6 is a view for explaining the display of the ashing apparatus 40 used in the sixth embodiment.
Fig. 7 is a view for explaining the method of manufacturing the embossed structure according to the sixth embodiment.
Fig. 8 is a view for explaining the display of the ashing apparatus 40a used in the seventh embodiment.
Fig. 9 is a view for explaining the method of manufacturing the embossed structure according to the seventh embodiment.
Fig. 10 is a view for explaining the film transistor 100 according to the eighth embodiment.
Fig. 11 is a view for explaining the method of manufacturing a thin film transistor according to the eighth embodiment.
Fig. 12 is a view for explaining the method of manufacturing a thin film transistor according to the eighth embodiment.
Fig. 13 is a view for explaining the method of manufacturing a thin film transistor according to the eighth embodiment.
Fig. 14 is a view for explaining the piezoelectric ink jet head 300 according to the ninth embodiment.
Fig. 15 is a view for explaining the method of manufacturing the piezoelectric ink jet head according to the ninth embodiment.
Fig. 16 is a view for explaining the method of manufacturing the piezoelectric ink jet head according to the ninth embodiment.
Fig. 17 is a view for explaining the method of manufacturing the piezoelectric ink jet head according to the ninth embodiment.
Fig. 18 is a view for explaining the ashing process in the first embodiment.
Fig. 19 is a view showing the result of the ashing treatment in the first embodiment.
Fig. 20 is a view showing the result of the ashing treatment in the first embodiment.
Fig. 21 is a view showing the result of the ashing treatment in the first embodiment.
Fig. 22 is a view showing the result of the ashing treatment in the second embodiment.
Fig. 23 is a view for explaining the evaluation method in the third embodiment.
Fig. 24 is a view showing the result of the ashing treatment in the third embodiment.
Fig. 25 is a view showing the result of the ashing treatment in the third embodiment.
Fig. 26 is a view for explaining a method of manufacturing an embossed structure according to a modification.
Fig. 27 is a view for explaining a conventional thin film transistor 900.
Fig. 28 is a view for explaining a method of manufacturing a conventional thin film transistor.
Fig. 29 is a view for explaining the electrical characteristics of a conventional thin film transistor 900.

In the method for producing an embossed structure of the present invention, a thin film transistor, a film capacitor, an actuator, a piezoelectric ink jet head, and an optical element, the method for producing an embossed structure of the present invention, a thin film transistor The piezoelectric ink jet head will be described based on the embodiment of the drawings. Embodiments 1 to 7 are embodiments of a method for producing an embossed structure of the present invention, and Embodiment 8 relates to an embodiment of a thin film transistor of the present invention, and Embodiment 9 relates to a piezoelectric inkjet head of the present invention. The embodiment.
[Embodiment 1]
Fig. 1 is a view for explaining a method of manufacturing an embossed structure according to the first embodiment. Fig. 1(a) to Fig. 1(g) are diagrams of the respective processes. Further, the symbol P in Fig. 1 denotes plasma.
A method for producing an embossed structure according to the first embodiment includes a process of preparing a liquid material containing a metal compound and forming a metal oxide or a metal by heat treatment as shown in FIG. 1; a second process for forming a precursor composition layer 20 composed of a metal oxide or a metal precursor composition by coating a liquid material on the substrate 10 (refer to FIGS. 1(a) and 1(b)); The preliminary heating process for reducing the fluidity of the precursor composition layer 20 in advance by heating the precursor composition layer 20 to a temperature (for example, 150 ° C) in the range of 80 ° C to 200 ° C (refer to FIG. 1 (c)) By heating the precursor composition layer 20 to a temperature (for example, 150 ° C) in the range of 80 ° C to 300 ° C, and using heating to a temperature in the range of 80 ° C to 300 ° C (for example) The concave-convex mold M1 of 150 ° C) is subjected to embossing to the precursor composition layer 20 to form a third process of the embossed structure including the residual film 22 in the precursor composition layer 20 (refer to FIG. 1( d )); The ashing using the atmospheric piezoelectric slurry is applied to the precursor composition layer 20 formed with the embossed structure The fourth process of processing the residual film 22 (refer to FIG. 1(e) and FIG. 1(f)); by the heat treatment of the precursor composition layer 20, the precursor composition layer 20 formed with the embossed structure A fifth process of forming the embossed structure 30 made of a metal oxide or a metal (see FIG. 1(g)).
In the method for producing an embossed structure according to the first embodiment, a liquid material (for example, a metal alkoxide-containing sol-gel solution containing a metal-containing compound and being heat-treated to form a metal oxide or a metal is used. ], [MOD (Metal Organic Decomposition) solution containing an organometallic compound], [metal salt solution containing a metal salt (for example, metal chloride, metal oxychloride, metal nitrate, metal acetate, etc.) ], [mixing the above sol-gel solution, a solution of at least two of the above MOD solution and the above metal salt solution], and the like as a liquid material.
In the method of manufacturing an embossed structure according to the first embodiment, since the precursor composition layer 20 is embossed by using the concave-convex mold M1 in the third process, the precursor is as shown in Fig. 1(d). The composition layer 20 is formed with an embossed structure including the residual film 22. Therefore, the residual film 22 is treated by subjecting the precursor composition layer 20 to ashing treatment using the atmospheric piezoelectric slurry in the fourth process. Specifically, as shown in FIG. 1(e) and FIG. 1(f), the residual film 22 is completely removed.
In the method for producing an embossed structure according to the first embodiment, the fourth process is carried out using a reactive gas (for example, [halogen-containing gas], [halogen-containing gas and mixed gas containing Ar gas], etc.). In this case, a halogen-containing gas can be suitably used for various fluorine-containing gases, chlorine-containing gases, bromine-containing gases, and the like.
By this method, the residual film can be completely removed, [the embossed structure without the influence of the residual film, that is, the embossed structure having the structure split by the portion where the residual film exists). As a result, in the fifth process, as the precursor composition layer is split into individual small regions, the precursor composition layer can be contracted in the in-plane direction without being reluctantly, so that the desired embossing can be formed with high precision. structure.
The method of completely removing the residual film is a method of applying the first time calculated by the relationship between the etching rate of the precursor composition layer and the thickness of the residual film by ashing by ashing (by time management) Ashing method)].
According to the method of manufacturing an embossed structure according to the first embodiment, the precursor composition layer can be formed by applying a liquid material on the substrate to form an embossed structure by embossing the precursor composition layer. Further, the embossed structure is formed by heat-treating the precursor composition layer at a high temperature, and the embossing process can be performed by using a mold having a fine pattern of a submicron order to form a submicron-sized fine Since the embossed structure of the pattern is used, it is possible to use various materials and manufacturing energy which are much smaller than the conventional ones, and to manufacture various functional elements including the above-mentioned excellent thin film transistors, which are shorter than the conventional ones.
Further, according to the method for producing an embossed structure according to the first embodiment, since the fourth process of treating the residual film by subjecting the precursor composition layer to ashing treatment is further included, the effect of the residual film can be formed. The embossed structure.
Further, according to the method for producing an embossed structure according to the first embodiment, since the ashing treatment using the atmospheric piezoelectric slurry is applied to the precursor composition layer, there is no need for a high vacuum environment in the fourth process, so It requires expensive high vacuum equipment and can reduce the time required to implement the fourth process.
Further, according to the method for producing an embossed structure according to the first embodiment, since the fourth process is to be performed using the reactive gas, the ashing process can be performed at a high etching rate, and the embossing can be performed with high productivity. Construct.
Further, according to the method for producing an embossed structure according to the first embodiment, it is intended to reduce the curing reaction of the precursor composition layer to some extent by heating to a temperature in the range of 80 ° C to 200 ° C. The fluidity of the precursor composition layer, and the precursor composition layer obtained by lowering the hardness of the precursor composition layer by heating to a temperature in the range of 80 ° C to 300 ° C to obtain high plastic deformation ability Since embossing is performed, the desired embossed structure can be formed with high precision, and as a result, an embossed structure having desired properties can be produced.
Further, according to the method for producing an embossed structure according to the first embodiment, the precursor composition layer is subjected to embossing by using a mold heated to a temperature in the range of 80 ° C to 300 ° C. When embossing is performed, the plastic deformation ability of the precursor composition layer is not lowered, so that the desired embossed structure can be formed with higher precision.
[Embodiment 2]
Fig. 2 is a view for explaining the method of manufacturing the embossed structure according to the second embodiment. 2(a) is a cross-sectional view of the precursor composition layer 20 when the precursor composition layer 20 is subjected to ashing treatment in the fourth process, and FIG. 2(b) is a composition of the precursor just after the fourth process. The material layer 20 is subjected to a cross-sectional view of the precursor composition layer 20 after the ashing treatment.
The manufacturing method of the embossed structure according to the second embodiment basically includes the same process as the method of manufacturing the embossed structure according to the first embodiment, but the contents of the fourth process and the embossing structure relating to the first embodiment The manufacturing method of the body is different. That is, in the manufacturing method of the embossed structure relating to the second embodiment, as shown in FIG. 2, in the fourth process, the ashing is performed more than the precursor composition layer by the ashing treatment. The relationship between the etching rate and the thickness of the residual film 22 is calculated as the first time. As a result, in the method of manufacturing the embossed structure according to the second embodiment, the concave portion 24 is formed on the base material 10 as shown in Fig. 2(b).
As described above, in the method of manufacturing the embossed structure according to the second embodiment, the content of the fourth process is different from that of the embossed structure according to the first embodiment, but the pressure is related to the first embodiment. In the same manner as in the production method of the flower structure, the fourth process of treating the residual film by subjecting the precursor composition layer to ashing treatment can form an embossed structure without the influence of the residual film. Moreover, since the ashing treatment using the atmospheric piezoelectric slurry is applied to the precursor composition layer, the high-vacuum environment is not required in the implementation of the fourth process, so that expensive high-vacuum equipment can be eliminated, and the fourth process can be shortened. The time required.
Further, the method of manufacturing the embossed structure according to the second embodiment has the same contents as those of the method of manufacturing the embossed structure according to the first embodiment except for the fourth process, and therefore has the first embodiment. The corresponding effect among the effects of the manufacturing method of the embossed structure.
[Embodiment 3]
Fig. 3 is a view for explaining the method of manufacturing the embossed structure according to the third embodiment. Fig. 3(a) is a cross-sectional view of the precursor composition layer 20 when the precursor composition layer 20 is subjected to ashing treatment in the fourth process, and Fig. 3(b) is a composition of the precursor just after the fourth process. The material layer 20 is subjected to a cross-sectional view of the precursor composition layer 20 after the ashing treatment.
The method for producing an embossed structure according to the third embodiment basically includes the same process as the method for producing the embossed structure according to the first embodiment, but the contents of the fourth process and the embossed structure relating to the first embodiment The manufacturing method of the body is different. That is, in the method of manufacturing the embossed structure according to the third embodiment, as shown in Fig. 3, the substrate 10a is made of a material which is an etch stop layer, and the ashing is exceeded by The ashing process is performed for the first time period in which the relationship between the etching rate of the precursor composition layer and the thickness of the residual film 22 is calculated.
As described above, in the method of manufacturing the embossed structure according to the third embodiment, the content of the fourth process is different from that of the embossed structure according to the first embodiment, but the pressure is related to the first embodiment. In the same manner as in the production method of the flower structure, the fourth process of treating the residual film by subjecting the precursor composition layer to ashing treatment can form an embossed structure without the influence of the residual film. Moreover, since the ashing treatment using the atmospheric piezoelectric slurry is applied to the precursor composition layer, the high-vacuum environment is not required in the implementation of the fourth process, so that expensive high-vacuum equipment can be eliminated, and the fourth process can be shortened. The time required.
Further, according to the method for producing an embossed structure according to the third embodiment, although the ashing is performed under the condition of so-called over-etching, the method of manufacturing the embossed structure according to the second embodiment is different. As shown in FIG. 3(b), a concave portion is not formed in the substrate 10a.
Further, the method of manufacturing the embossed structure according to the third embodiment has the same contents as the method of manufacturing the embossed structure according to the first embodiment except for the fourth process, and therefore has the first embodiment. The corresponding effect among the effects of the manufacturing method of the embossed structure.
[Embodiment 4]
Fig. 4 is a view for explaining the method of manufacturing the embossed structure according to the fourth embodiment. 4(a) is a cross-sectional view of the precursor composition layer 20 when the precursor composition layer 20 is subjected to ashing treatment in the fourth process, and FIG. 4(b) is a composition of the precursor just after the fourth process. The material layer 20 is subjected to a cross-sectional view of the precursor composition layer 20 after the ashing treatment.
The manufacturing method of the embossed structure according to the fourth embodiment basically includes the same process as the method of manufacturing the embossed structure according to the first embodiment, but the contents of the fourth process and the embossing structure relating to the first embodiment are basically the same. The manufacturing method of the body is different. In other words, in the method of manufacturing the embossed structure according to the fourth embodiment, as the substrate shown in Fig. 4, a substrate having the layer 14 made of a material which is an etching stopper layer on the surface of the first substrate 12 is used. 10b, and the ashing time is calculated to be longer than the first time calculated by the relationship between the etching rate of the precursor composition layer by the ashing treatment and the thickness of the residual film 22.
As described above, in the method of manufacturing the embossed structure according to the fourth embodiment, the content of the fourth process is different from that of the embossed structure according to the first embodiment, but the pressure is related to the first embodiment. In the same manner as in the production method of the flower structure, the fourth process of treating the residual film by subjecting the precursor composition layer to ashing treatment can form an embossed structure without the influence of the residual film. Moreover, since the ashing treatment using the atmospheric piezoelectric slurry is applied to the precursor composition layer, the high-vacuum environment is not required in the implementation of the fourth process, so that expensive high-vacuum equipment can be eliminated, and the fourth process can be shortened. The time required.
Further, in the method of manufacturing the embossed structure according to the fourth embodiment, as in the case of the method of manufacturing the embossed structure according to the third embodiment, the ashing is performed under the condition of so-called over-etching. However, as shown in FIG. 4(b), a concave portion is not formed in the base material 10b.
Further, since the method of manufacturing the embossed structure according to the fourth embodiment is the same as the method of manufacturing the embossed structure according to the first embodiment except for the fourth process, it is related to the first embodiment. The corresponding effect among the effects of the manufacturing method of the embossed structure.
[Embodiment 5]
Fig. 5 is a view for explaining the method of manufacturing the embossed structure according to the fifth embodiment. Fig. 5(a) is a cross-sectional view of the precursor composition layer 20 when the precursor composition layer 20 is subjected to ashing treatment in the fourth process, and Fig. 5(b) is a composition of the precursor just after the fourth process. The material layer 20 is subjected to a cross-sectional view of the precursor composition layer 20 after the ashing treatment, and FIG. 5(c) is a cross section of the embossed structure 30 formed by heat-treating the precursor composition layer 20 in the fifth process. Figure. In addition, in FIG. 5, in order to make the sea-island structure 28 mentioned later easy to see, it is enlarged by the figure in FIG.
The manufacturing method of the embossed structure according to the fifth embodiment basically includes the same process as the method of manufacturing the embossed structure according to the first embodiment, but the content of the fourth process and the embossing structure related to the first embodiment The manufacturing method of the body is different. That is, in the method of manufacturing the embossed structure according to the fifth embodiment, as shown in FIG. 5, in the fourth process, the residual film 22 is intended to be thinned until it becomes the fifth by performing the fourth process. The process allows the residual film to take the thinness of the island structure 28.
As described above, in the method of manufacturing the embossed structure according to the fifth embodiment, the content of the fourth process is different from that of the embossed structure according to the first embodiment, but the pressure is related to the first embodiment. In the same manner as in the production method of the flower structure, the fourth process of treating the residual film by subjecting the precursor composition layer to ashing treatment can form an embossed structure without the influence of the residual film. Moreover, since the ashing treatment using the atmospheric piezoelectric slurry is applied to the precursor composition layer, the high-vacuum environment is not required in the implementation of the fourth process, so that expensive high-vacuum equipment can be eliminated, and the fourth process can be shortened. The time required.
Further, in the method of manufacturing an embossed structure according to the fifth embodiment, since the residual film adopts the sea-island structure 28 after the end of the fifth process, even if the residual film is not completely removed at the end of the fourth process, An embossed structure capable of forming an effect without a residual film.
Further, the method of manufacturing the embossed structure according to the fifth embodiment has the same contents as those of the method of manufacturing the embossed structure according to the first embodiment except for the fourth process, and therefore has the first embodiment. The corresponding effect among the effects of the manufacturing method of the embossed structure.
[Embodiment 6]
Fig. 6 is a view for explaining the display of the ashing apparatus 40 used in the sixth embodiment. Fig. 7 is a view for explaining the method of manufacturing the embossed structure according to the sixth embodiment. Fig. 7(a) is a cross-sectional view of the precursor composition layer 20 immediately before the ashing treatment of the precursor composition layer 20 by the fourth process, and Fig. 7(b) is the composition of the precursor just after the fourth process. The material layer 20 is subjected to a cross-sectional view of the precursor composition layer 20 after the ashing treatment. Further, reference numeral 41 in Fig. 6 denotes one electrode, and reference numeral 43 denotes an electrode on the other side. Further, in Fig. 7, in order to make the side etching look easy, it is displayed more enlarged than in Fig. 5.
The method for producing an embossed structure according to the sixth embodiment basically includes the same process as the method for producing an embossed structure according to the first embodiment. Further, as shown in FIG. 6, it is intended to carry out the fourth process by applying ashing treatment to the precursor composition layer by using the ashing apparatus 40 (atmospheric piezoelectric ashing apparatus).
As described above, the method of manufacturing the embossed structure according to the sixth embodiment includes the ashing treatment of the precursor composition layer as in the case of the method of manufacturing the embossed structure according to the first embodiment. The fourth process of the residual film can form an embossed structure without the influence of the residual film. Moreover, since the ashing treatment using the atmospheric piezoelectric slurry is applied to the precursor composition layer, the high-vacuum environment is not required in the implementation of the fourth process, so that expensive high-vacuum equipment can be eliminated, and the fourth process can be shortened. The time required.
Further, in the method of manufacturing an embossed structure according to the sixth embodiment, the average free path of the ashing gas is shortened and the fourth is applied to the precursor composition layer by the ashing treatment using the atmospheric piezoelectric slurry. Lateral etching occurs in the process (see Fig. 7), so it is preferable to design the pattern of the concave-convex mold in consideration of this factor. This point is also the same as the method of manufacturing the embossed structure according to the first to fifth embodiments.
[Embodiment 7]
Fig. 8 is a view for explaining the display of the ashing apparatus 40a used in the seventh embodiment. Fig. 9 is a view for explaining the method of manufacturing the embossed structure according to the seventh embodiment. Figure 9(a) is a cross-sectional view of the precursor composition layer 20 immediately before the ashing treatment of the precursor composition layer 20 by the fourth process, and Figure 9(b) is the composition of the precursor just after the fourth process. The material layer 20 is subjected to a cross-sectional view of the precursor composition layer 20 after the ashing treatment. Further, reference numeral 42 in Fig. 8 denotes a positive electrode, and reference numeral 44 denotes a negative electrode.
The method for producing an embossed structure according to the seventh embodiment basically includes the same process as the method for producing the embossed structure according to the sixth embodiment, but the content of the fourth process and the embossed structure relating to the sixth embodiment are basically the same. The manufacturing method of the body is different. That is, in the manufacturing method of the embossed structure relating to the seventh embodiment, as shown in FIG. 8, in the fourth process, the precursor is intended to be used by using the ashing device 40a (low-pressure plasma ashing device). The composition layer 20 is subjected to a fourth process by applying ashing treatment using low-pressure plasma. In the method for producing an embossed structure according to the seventh embodiment, for example, ashing treatment using low-pressure plasma is performed under a pressure condition of 1 Pa to 1000 Pa (preferably 10 Pa to 100 Pa). Further, in the method of manufacturing an embossed structure according to the seventh embodiment, the fourth process is carried out under the condition that a bias voltage is applied as shown in FIG.
In the method of manufacturing the embossed structure according to the seventh embodiment, the content of the fourth process is different from that of the embossed structure according to the sixth embodiment, but the pressure is related to the sixth embodiment. In the same manner as in the production method of the flower structure, the fourth process of treating the residual film by subjecting the precursor composition layer to ashing treatment further forms an embossed structure having no residual film influence. Further, since the fourth process is performed in a state where a bias voltage is applied, the collision energy of the ashing gas becomes high, so that the ashing process can be performed at a high etching rate, and the ashing process can be manufactured with high productivity. Embossed structure.
Further, according to the method for producing an embossed structure according to the seventh embodiment, the following effects can be obtained. That is, according to the manufacturing method of the embossed structure relating to the seventh embodiment, the average free path of the gas (ashing gas) used for ashing is longer than that under atmospheric pressure, and the flying direction of the ashing gas is in one direction. Consistently, as shown in FIG. 9, the ratio of etching (lateral etching) to the side portion of the embossed structure can be reduced, and an embossed structure having high shape accuracy can be manufactured. Further, since a stable glow discharge can be generated even in a state where a bias voltage is applied, the ashing process can be stably performed at a high etching rate, and the embossed structure can be stably produced with high productivity. Further, since the reaction product generated by the reaction between the precursor composition layer and the reactive gas is volatilized and easily removed, the ashing process can be stably performed at a high etching rate from this viewpoint, and further The embossed structure can be stably produced with high productivity.
In addition, the method of manufacturing the embossed structure according to the seventh embodiment is the same as the case of the method of manufacturing the embossed structure according to the sixth embodiment except for the fourth process. The corresponding effect among the effects of the manufacturing method of the embossed structure.
[Embodiment 8]
1. Thin film transistor 100 related to embodiment VIII
Fig. 10 is a view for explaining the film transistor 100 according to the eighth embodiment. Fig. 10(a) is a plan view of the thin film transistor 100, Fig. 10(b) is a cross-sectional view taken along line A1-A1 of Fig. 10(a), and Fig. 10(c) is a cross-sectional view taken along line A2-A2 of Fig. 10(a).
The thin film transistor 100 according to the eighth embodiment includes, as shown in FIGS. 10(a) and 10(b), an oxide conductor layer 140 including a source region 144 and a drain region 146 and a channel region 142; and a control channel region. a gate electrode 120 of an on state of 142; a gate insulating layer 130 formed of a ferroelectric material formed between the gate electrode 120 and the channel region 142. The layer thickness of the channel region 142 is thinner than the layer thickness of the source region 144 and the layer thickness of the drain region 146. The layer thickness of the channel region 142 is preferably 1/2 or less of the layer thickness of the source region 144 and the layer thickness of the drain region 146. As shown in FIGS. 10(a) and 10(c), the gate electrode 120 is connected to a gate pad 122 exposed to the outside through a through hole 150.
In the thin film transistor 100 according to the eighth embodiment, the oxide conductor layer 140 is formed using an embossing technique.
In the thin film transistor 100 according to the eighth embodiment, the carrier concentration and the layer thickness of the channel region 142 are set to a value at which the channel region 142 is depleted when a control voltage of OFF is applied to the gate electrode 120. . Specifically, the carrier concentration of the channel region 142 is located at 1×10. ¹⁵ Cm ^-3 ~1×10 ^{twenty one} Cm ^-3 Within the range of the channel region 142, the layer thickness is in the range of 5 nm to 100 nm.
Further, in the thin film transistor 100 according to the eighth embodiment, the layer thickness of the source region 144 and the drain region 146 is in the range of 50 nm to 1000 nm.
The oxide conductor layer 140 is composed of, for example, indium tin oxide (ITO), and the gate insulating layer 130 is, for example, PZT (Pb (Zr) _x , Ti _1-x )O ₃ The gate electrode 120 is composed of, for example, lanthanum nickelate (LNO(LaNiO) ₃ )) The insulating substrate 110 which is a solid substrate is interposed, for example, by SiO on the surface of the Si substrate. ₂ The layer and the Ti layer form an insulating substrate of an STO (SrTiO) layer.
2. A method of manufacturing a thin film transistor related to the eighth embodiment
The thin film transistor 100 according to the eighth embodiment can be produced by the method for producing a thin film transistor described below. The following is described in the order of the process.
11 to 13 are views for explaining the method of manufacturing the thin film transistor according to the eighth embodiment. 11(a) to 11(f), 12(a) to 12(f), and Figs. 13(a) to 13(e) are diagrams of the respective processes. Further, the map shown on the left side in each of the process maps is a map corresponding to FIG. 10(b), and the graph shown on the right side is a map corresponding to FIG. 10(c).
(1) Formation of gate electrode 120
First, the preparation is made of a metal oxide ceramic by heat treatment (m e t a l o x i d e c e r a m i c a functional liquid material of a functional solid material composed of s) (barium strontium) (first process). Specifically, a solution containing a metal inorganic salt (lanthanum nitrate (hexahydrate) and nickel acetate (tetrahydrate)) was prepared (solvent: 2) 2-methoxyethanol).
Next, as shown in FIGS. 11( a ) and 11 ( b ), a functional liquid material (for example, 500 rpm, 25 seconds) is applied to one surface of the insulating substrate 110 by a spin coating method. Then, the insulating substrate 110 was placed on a hot plate and dried at 60 ° C for 1 minute to form a precursor composition layer 120' of strontium nickelate (layer thickness: 300 nm) (second process).
Next, as shown in FIGS. 11(c) and 11(d), the concave-convex mold M2 (having a height difference of 300 nm) formed by using the region corresponding to the gate electrode layer 120 and the gate pad 122 is used, and the precursor is 150 ° C. The composition layer 120' is subjected to embossing, and an embossed structure is formed in the precursor composition layer 120' (the layer thickness of the convex portion is 300 nm, and the layer thickness of the concave portion is 50 nm) (third process). The pressure applied to the embossing process was 5 MPa. According to this, since the embossing process is performed on the precursor composition layer which is obtained by heating to the second temperature in the range of 80 ° C to 300 ° C to obtain high plastic deformation ability, the formation can be performed with high precision. The embossed structure required.
Next, by performing the overall ashing treatment on the precursor composition layer 120', as shown in FIG. 11(e), the residual film 120'z existing in the region other than the region corresponding to the gate electrode layer 120 is completely removed (fourth Process). The fourth process is performed using a wet etching apparatus.
Finally, the precursor composition layer 120' is heat-treated at a high temperature (650 ° C, 10 minutes) by using an RTA (Rapid Thermal Annealing) apparatus, as shown in FIG. 11(f), composed of a precursor. The object layer 120' forms a gate electrode 120 and a gate pad 122 composed of a functional solid material layer (barium nickelate) (fifth process).
(2) Formation of the gate insulating layer 130
First, a functional liquid material which becomes a functional solid material composed of a metal oxide ceramic (PZT) by heat treatment is prepared. Specifically, a solution containing a metal alkoxide (PZT sol-gel solution manufactured by Mitsubishi Materials Corporation) was prepared as a functional liquid material (first process).
Next, the above functional liquid material (for example, 2000 rpm, 25 seconds) is applied on one surface of the insulating substrate 110 by spin coating three times, and then the insulating substrate 110 is placed on a hot plate. The operation was carried out by drying at 250 ° C for 5 minutes to form a precursor composition layer 130' (layer thickness 300 nm) of a functional solid material (PZT) (second process, see Fig. 12 (a)).
Next, as shown in FIGS. 12(b) and 12(c), the precursor composition layer 130 is formed at 150 ° C by using the concave-convex mold M3 (having a height difference of 300 nm) formed by the region corresponding to the through-hole 150. The embossing process is performed, and the embossing structure corresponding to the through hole 150 is formed in the precursor composition layer 130' (third process). The pressure applied to the embossing process was 5 MPa. According to this, since the embossing process is performed on the precursor composition layer which is obtained by heating to the second temperature in the range of 80 ° C to 300 ° C to obtain high plastic deformation ability, the formation can be performed with high precision. The embossed structure required.
Next, by performing the overall ashing treatment on the precursor composition layer 130', as shown in Fig. 12 (d), the residual film 130'z (fourth process) existing in the region which becomes the channel region 142 later is completely removed. The fourth process uses a low-pressure plasma etching apparatus to introduce a reactive gas (for example, CF) under a pressure of 10 Pa. ₄ Gas and Ar gas) are carried out at the same time.
Finally, by using the RTA apparatus and heat-treating the precursor composition layer 130' at a high temperature (650 ° C, 10 minutes), as shown in FIG. 12(e), the precursor composition layer 130' is formed of a functional solid. A gate insulating layer 130 (the fifth process) composed of a material layer (PZT).
(3) Formation of oxide conductor layer 140
First, a functional liquid material (first process) which becomes a functional solid material composed of a metal oxide ceramic (ITO) by heat treatment is prepared. Specifically, a solution containing a metal carboxylate (a functional liquid material (trade name: ITO-05C) manufactured by High Purity Chemical Research Co., Ltd., a stock solution: a diluent) is prepared. =1: 1.5) as a functional liquid material. Further, when the functional liquid material is added, the carrier concentration of the channel region 142 is 1 × 10 when completed. ¹⁵ Cm ^-3 ~1×10 ^{twenty one} Cm ^-3 The concentration of impurities within the range.
Next, as shown in FIG. 12(f), the above-described functional liquid material (for example, 2000 rpm, 25 seconds) is applied by spin coating on one surface of the insulating substrate 110, and then the insulating substrate 110 is placed. It was dried on a hot plate at 150 ° C for 3 minutes to form a precursor composition layer 140' (layer thickness 300 nm) of a functional solid material (ITO) (second process).
Next, as shown in FIGS. 13(a) to 13(c), the concave-convex mold M4 formed by using the region corresponding to the channel region 142 and the region corresponding to the source region 144 and the region corresponding to the gate region 146 is convex. (a height difference of 350 nm), the precursor composition layer 140' is subjected to embossing, and an embossed structure is formed in the precursor composition layer 140' (the layer thickness of the convex portion is 350 nm, and the layer thickness of the concave portion is 100 nm) (third process) ). Accordingly, the layer thickness of the portion of the precursor composition layer 140' that becomes the channel region 142 is thinner than the other portions.
At this time, in the above-described process, it is intended to emboss processing by heating the precursor composition layer 140' to 150 ° C and using a mold heated to 150 ° C. In this case, the pressure at the time of embossing is about 4 MPa.
Further, the concave-convex mold M4 has a structure in which a region corresponding to the element isolation region 160 and the through-hole 150 is more convex than a region corresponding to the channel region 142, and is formed in a region corresponding to the element isolation region 160 and the through-hole 150. There is a residual film 140'z of the precursor composition layer 140' (see Fig. 13(c)).
Next, by performing the overall ashing treatment on the precursor composition layer 140', as shown in FIG. 13(d), the residual film 140'z existing in the region corresponding to the element isolation region 160 and the through hole 150 is completely removed (No. Four processes). The fourth process uses a low-pressure plasma etching apparatus to introduce a reactive gas (for example, CF) under a pressure of 10 Pa. ₄ Gas and Ar gas) are carried out at the same time.
Finally, heat treatment was performed on the precursor composition layer 140' (the precursor composition layer 140' was fired on a hot plate at 400 ° C for 10 minutes, and then 650 ° C, 30 minutes using an RTA apparatus. The condition of the first half of the 15 minute oxygen atmosphere and the second half of the 15 minute nitrogen atmosphere heats the precursor composition layer 140' to form the oxide conductor layer 140 including the source region 144, the drain region 146, and the channel region 142 (the first) In the five-process, a thin film transistor 100 according to the eighth embodiment having a bottom gate structure as shown in Fig. 13(e) can be manufactured.
3. The efficacy of the thin film transistor 100 related to the eighth embodiment
According to the thin film transistor 100 according to the eighth embodiment, since the oxide conductive material is used as the material constituting the channel region 142, the carrier concentration can be increased, and since the ferroelectric material is used as the material constituting the gate insulating layer 130, it is possible to The low driving voltage is switched at a high speed, and as a result, as in the case of the conventional thin film transistor 900, a large current can be controlled at a high speed with a low driving voltage.
Further, according to the thin film transistor 100 according to the eighth embodiment, the layer thickness of the channel region 142 is thinner than the layer thickness of the source region 144 and the layer thickness of the drain region 146, and only by using the embossed structure described above. The manufacturing method forms the oxide conductor layer 140 without the influence of the residual film, and the thin film transistor can be manufactured. Therefore, the channel region and the source region can be formed from different materials unlike the conventional thin film transistor 900. In the polar region, a thin film transistor excellent in the above-described manner can be produced by using a material which is much smaller than the conventional materials and manufacturing energy, and which is shorter than the prior art.
Further, according to the thin film transistor 100 according to the eighth embodiment, since the oxide conductor layer 140, the gate electrode 120, and the gate insulating layer 130 are formed without using a high vacuum process, the thin film transistor can be manufactured without using a vacuum process. A film transistor having excellent properties as described above can be produced by using a process much smaller than the conventional production energy and having a process shorter than the prior art.
Further, according to the thin film transistor 100 according to the eighth embodiment, the carrier concentration and the layer thickness of the channel region 142 are set to a value at which the channel region 142 is depleted when a closed control voltage is applied to the gate electrode 120. Therefore, even if the carrier concentration of the oxide conductor layer is increased, the amount of current flowing during shutdown can be sufficiently reduced, and a large current can be controlled with a low driving voltage while maintaining a necessary switching ratio.
[Embodiment 9]
Fig. 14 is a view for explaining the piezoelectric ink jet head 300 according to the ninth embodiment. Fig. 14 (a) is a cross-sectional view of the piezoelectric ink jet head 300, and Figs. 14 (b) and 14 (c) are views showing a state in which the piezoelectric ink jet head 300 discharges ink.
1. The constitution of a piezoelectric inkjet head 300 according to the ninth embodiment
The piezoelectric ink jet head 300 according to the ninth embodiment includes a cavity member 340 as shown in Fig. 14 (a), and a vibration of a piezoelectric element 320 formed on one side of the cavity member 340. The plate 350 is mounted on the other side of the cavity member 340, the nozzle plate 330 having the nozzle hole 332, and the ink chamber 360 defined by the cavity member 340, the vibration plate 350, and the nozzle plate 330. The vibrating plate 350 is provided with an ink supply port 352 that communicates with the ink chamber 360 for supplying ink to the ink chamber 360.
According to the piezoelectric ink jet head 300 according to the ninth embodiment, as shown in Figs. 14(b) and 14(c), the vibrating plate 350 is scratched by applying an appropriate voltage to the piezoelectric element 320. After the ink is supplied to the ink chamber 360 by an ink reservoir (not shown), the diaphragm 350 is deflected downward, and the ink droplets are ejected from the ink chamber 360 through the nozzle holes 332. According to this, it is possible to perform vivid printing on the printed matter.
2. A method of manufacturing a piezoelectric inkjet head according to Embodiment 9
The piezoelectric ink jet head 300 having such a configuration is that the piezoelectric element 320 (the first electrode layer 322, the piezoelectric layer 324, and the second electrode layer 326) and the cavity member 340 are both embossed structures using the present invention. The manufacturing method is formed. Hereinafter, a method of manufacturing the piezoelectric ink jet head 300 according to the ninth embodiment will be described in accordance with a process sequence.
15 to 17 are views for explaining the method of manufacturing the piezoelectric ink jet head according to the ninth embodiment. 15(a) to 15(f), Figs. 16(a) to 16(d), and Figs. 17(a) to 17(e) are diagrams of the respective processes.
(1) Formation of Piezoelectric Element 320
(1-1) Formation of the first electrode layer 322
First, a functional liquid material (first process) which becomes a functional solid material composed of a metal oxide ceramic (barium nickel hydride) by heat treatment is prepared. Specifically, a solution containing a metal inorganic salt (cerium nitrate (hexahydrate) and nickel acetate (tetrahydrate)) (solvent: 2-methoxyethanol) was prepared.
Next, as shown in FIG. 15(a), a functional liquid material (for example, 500 rpm, 25 seconds) is applied to one surface of a dummy substrate 310 by spin coating, and then the dummy substrate 310 is placed. It was dried on a hot plate at 60 ° C for 1 minute to form a precursor composition layer 322' (layer thickness 300 nm) of a functional solid material (barium strontium) (second process).
Next, as shown in Fig. 15 (b), the precursor composition layer 322' is pressed at 150 ° C by using the concave-convex mold M8 (having a height difference of 300 nm) which is formed by recessing the region corresponding to the first electrode layer 322. In the flower processing, an embossed structure was formed in the precursor composition layer 322' (the layer thickness of the convex portion was 300 nm, and the layer thickness of the concave portion was 50 nm) (third process). The pressure applied to the embossing process was 5 MPa.
Next, by performing the overall ashing treatment on the precursor composition layer 322', as shown in FIG. 15(c), the residual film existing in the region other than the region corresponding to the first electrode layer 322 is completely removed (fourth process) . The fourth process is performed using a wet etching apparatus.
Finally, by using the RTA apparatus and heat-treating the precursor composition layer 322' at a high temperature (650 ° C, 10 minutes), as shown in FIG. 15(d), the precursor composition layer 322' is formed of a functional solid. A first electrode layer 322 composed of a material layer (barium nickelate) (fifth process).
(1-2) Formation of piezoelectric layer 324
First, a functional liquid material (first process) which becomes a functional solid material composed of a metal oxide ceramic (PZT) by heat treatment is prepared. Specifically, a solution containing a metal alkoxide (PZT sol-gel solution manufactured by Mitsubishi Materials Corporation) was prepared as a functional liquid material (first process).
Next, as shown in FIG. 15(e), the above-described functional liquid material is applied by spin coating on one surface of the dummy substrate 310, and then the dummy substrate 310 is placed on a hot plate at 250 ° C. It is dried for 5 minutes to form a precursor composition layer 324' of a functional solid material (PZT) (for example, a layer thickness of 1 μm to 10 μm) (second process).
Next, as shown in Fig. 15 (f), the precursor composition layer 324' is embossed by using the concave-convex mold M9 (having a height difference of 500 nm) formed by the concave portion corresponding to the region of the piezoelectric layer 324. The precursor composition layer 324' forms an embossed structure (for example, a layer thickness of the convex portion is 1 μm to 10 μm, and a layer thickness of the concave portion is 50 nm) (third process).
At this time, in the above-described process, the precursor composition layer 324' was heated to 150 ° C, and embossing was performed using a mold heated to 150 ° C. The pressure at the time of embossing is about 4 MPa.
Next, by performing overall ashing treatment on the precursor composition layer 324', as shown in Fig. 15(g), the residual film existing in the region other than the region corresponding to the piezoelectric layer 324 is completely removed (fourth process). The fourth process uses a low-pressure plasma etching apparatus to introduce a reactive gas (for example, CF) under a pressure of 10 Pa. ₄ Gas and Ar gas) are carried out at the same time.
Finally, by using the RTA apparatus and heat-treating the precursor composition layer 324' at a high temperature (650 ° C, 10 minutes), as shown in FIG. 15 (h), the precursor composition layer 324' is formed of a functional solid. Piezoelectric layer 324 composed of a material layer (PZT) (fifth process).
(1-3), formation of the second electrode layer 326
First, a functional liquid material (first process) which becomes a functional solid material composed of a metal oxide ceramic (barium nickel hydride) by heat treatment is prepared. Specifically, a solution containing a metal inorganic salt (cerium nitrate (hexahydrate) and nickel acetate (tetrahydrate)) (solvent: 2-methoxyethanol) was prepared.
Next, as shown in FIG. 16(a), a functional liquid material (for example, 500 rpm, 25 seconds) is applied on one surface of the dummy substrate 310 by spin coating, and then the dummy substrate 310 is placed on the hot plate. The film was dried at 60 ° C for 1 minute to form a precursor composition layer 326' (layer thickness 300 nm) of a functional solid material (barium nickelate) (second process).
Next, as shown in Fig. 16 (b), the precursor composition layer 326' is pressed at 150 ° C by using the concave-convex mold M10 (having a height difference of 300 nm) which is formed by recessing the region corresponding to the second electrode layer 326. In the flower processing, an embossed structure was formed in the precursor composition layer 326' (the layer thickness of the convex portion was 300 nm, and the layer thickness of the concave portion was 50 nm) (third process). The pressure applied to the embossing process was 5 MPa.
Next, by performing overall ashing treatment on the precursor composition layer 326', as shown in FIG. 16(c), the residual film existing in the region other than the region corresponding to the second electrode layer 326 is completely removed (fourth process) . The fourth process is performed using a wet etching apparatus.
Finally, by using an RTA apparatus and heat-treating the precursor composition layer 326' at a high temperature (650 ° C, 10 minutes), as shown in FIG. 16(d), the precursor composition layer 326' is formed of a functional solid. A second electrode layer 326 of a material layer (barium nickelate) (fifth process). Accordingly, the piezoelectric element 320 composed of the first electrode layer 322, the piezoelectric layer 324, and the second electrode layer 326 is completed.
(2) The bonding of the vibration plate 350 and the piezoelectric element 320
As shown in FIG. 16(e), the vibrating plate 350 having the ink supply port 352 is bonded to the piezoelectric element 320 by using an adhesive.
(3) Formation of the cavity member 340
First, a functional liquid material (first process) which becomes a metal oxide ceramic (quartz glass) by heat treatment is prepared. Specifically, the preparation contains a metal alkoxide (isopropyl silicate (Si (OC) ₃ H ₇ ) ₄ The solution is treated as a functional liquid material.
Next, as shown in Fig. 17 (a), the above-described functional liquid material is applied by spin coating on one surface of the vibrating plate 350, and then placed at 150 ° C by placing the dummy substrate 310 on a hot plate. It is dried for 5 minutes to form a precursor composition layer 340' of a functional solid material (quartz glass) (for example, a layer thickness of 10 μm to 20 μm) (second process).
Next, as shown in Fig. 17 (b), the precursor composition layer 340' is subjected to embossing by using the concave-convex mold M11 having a shape corresponding to the ink chamber 360 or the like, and is formed in the precursor composition layer 340'. The embossed structure (for example, the layer thickness of the convex portion is 10 μm to 20 μm, and the layer thickness of the concave portion is 50 nm) (third process).
At this time, in the above-described process, the precursor composition layer 340' was heated to 150 ° C, and embossing was performed using a mold heated to 150 ° C. The pressure at the time of embossing is about 4 MPa.
Next, by performing the overall ashing treatment on the precursor composition layer 340', as shown in Fig. 17 (c), the residual film existing in the region other than the region where the cavity member 340 is formed is completely removed (fourth process). The fourth process uses an atmospheric piezoelectric slurry etching apparatus to introduce a reactive gas (for example, CF) under atmospheric pressure. ₄ Gas and Ar gas) are carried out at the same time.
Finally, by using the RTA apparatus and heat-treating the precursor composition layer 340' at a high temperature (650 ° C, 10 minutes), as shown in FIG. 17(d), the precursor composition layer 340' is formed of a functional solid. A cavity member 340 of a material layer (quartz glass).
(4) The fitting of the cavity member 340 and the nozzle plate 330
As shown in Fig. 17 (e), the cavity member 340 is attached to the nozzle plate 330 having the nozzle holes 332 using an adhesive.
(5), the removal of the virtual substrate 310
As shown in FIG. 17(f), the dummy substrate 310 is removed by the piezoelectric element 320. According to this, the piezoelectric ink jet head 300 according to the ninth embodiment is completed.
3. The efficacy of the piezoelectric inkjet head 300 related to the ninth embodiment
According to the piezoelectric ink jet head 300 according to the ninth embodiment, the piezoelectric element 320 (the first electrode layer 322, the piezoelectric layer 324, and the second electrode layer 326) and the cavity member 340 are formed using an embossing technique. Since it is formed, it is possible to manufacture a piezoelectric ink jet head using a process which is much smaller than the conventional materials and manufacturing energy, and which is shorter than the conventional one.
Further, the piezoelectric ink jet head 300 according to the ninth embodiment is provided with a precursor composition which is highly heat-resistant by heat treatment at a second temperature in the range of 80 ° C to 300 ° C. The first electrode layer, the piezoelectric layer, the second electrode layer and the cavity member having an embossed structure formed with high precision are formed by embossing, so that it is a piezoelectric type having desired properties. Inkjet head.
Further, according to the piezoelectric ink jet head 300 according to the ninth embodiment, the piezoelectric element 320 (the first electrode layer 322, the piezoelectric layer 324, and the second electrode layer 326) and the cavity member 340 are both made of a liquid material. Since it is formed, a piezoelectric ink jet head can be manufactured by using an embossing forming technique, and a piezoelectric ink jet head excellent in the above-described manner can be manufactured using much less raw materials and manufacturing energy.
Further, according to the piezoelectric ink jet head 300 according to the ninth embodiment, the piezoelectric element 320 (the first electrode layer 322, the piezoelectric layer 324, and the second electrode layer 326) and the cavity member 340 are not used high. Since it is formed by a vacuum process, it is possible to manufacture a piezoelectric ink jet head which is excellent as described above by using a manufacturing process which is much smaller than the conventional one and which is shorter than the prior art.
Further, according to the piezoelectric ink jet head 300 according to the ninth embodiment, the cavity member is manufactured by using an atmospheric piezoelectric device without using a vacuum process, and it is possible to use much less manufacturing energy than conventional ones, and it is shorter than ever. Process manufacturing.
Further, according to the piezoelectric ink jet head 300 according to the ninth embodiment, since the piezoelectric layer and/or the cavity member are formed by using the method for producing the embossed structure of the present invention, it is possible to have no residual film influence. The embossed structure is manufactured using a material that is much smaller than conventional materials and manufacturing energy, and is manufactured in a shorter process than in the past.
[Examples]
[Example 1]
The first embodiment shows an embodiment in which the precursor composition layer can be completely removed by applying a reactive gas to the ashing treatment.
Fig. 18 is a view for explaining the ashing process in the first embodiment. 18(a) to 18(e) are process diagrams of the ashing process. 18(c) to 18(e) are diagrams showing the results of the ashing treatment in the ashing condition 1, and FIG. 18(b) is the ash in the ashing condition 2. FIG. 18(c) is a view showing the result of the ashing treatment in the ashing condition 3. FIG.
Fig. 19 is a view showing the result of the ashing treatment in the first embodiment. The horizontal axis represents the ashing time, and the vertical axis represents the layer thickness of the precursor composition layer after the ashing treatment is applied to the precursor composition layer 520. Further, in FIG. 19, in the region where the layer thickness of the precursor composition layer 520 is negative, the display is etched to the insulating substrate 510.
Fig. 20 is a view showing the result of the ashing treatment in the first embodiment. Fig. 20 (a) is a view showing a SEM (Scanning Electron Microscope) photograph in a boundary portion between a portion subjected to ashing treatment and a portion not subjected to ashing treatment, and Fig. 20 (b) is a view showing A map of the distribution of Ti (titanium) in the boundary portion.
Fig. 21 is a view showing the result of the ashing treatment in the first embodiment. Fig. 21 (a) is a view showing an EDX spectrum (Energy Dispersive X-ray spectrum) in a portion R1 not subjected to ashing treatment, and Fig. 21 (a) is a display showing A plot of the EDX spectrum in the portion R2 treated with ashing.
In the first embodiment, SiO is formed on the surface of the Si substrate. ₂ On the insulating substrate 510 of the layer, TiO is coated by spin coating ₂ The sol-gel solution forms the precursor composition layer 520, and then the insulating substrate on which the precursor composition layer 520 was formed was dried at 200 ° C for 5 minutes on a hot plate as a sample. For the size and shape of the insulating substrate 510, for example, a rectangular parallelepiped having a length of 20 mm, a width of 20 mm, and a height of 0.7 mm is used. The layer thickness of the precursor composition layer 520 after drying at 200 ° C was 75 nm.
Then, as shown in FIG. 18(a), after the heat-resistant insulating tape M20 is partially attached to the surface of the precursor composition layer 520, the precursor composition layer 520 is ashed as shown in FIG. 18(b). deal with. Set one side to make reactive gas (CF ₄ Gas: a flow rate of 0.1 L/min) flows together with a carrier gas (He gas: flow rate: 9 L/min), and the precursor composition layer 520 is subjected to ashing treatment to ashing condition 1, and Ar gas is disposed at the same time. 0.1 L/min) flows along with the carrier gas (He gas: flow rate: 9 L/min), and the precursor composition layer 520 is subjected to ashing treatment to the ashing condition 2, and the reactive gas (CF) is set. ₄ Gas: flow rate: 0.05 L/min) and Ar gas (flow rate: 0.05 L/min) flowed together with a carrier gas (He gas: flow rate: 9 L/min), and the precursor composition layer 520 was subjected to ashing treatment to be ashed. Condition 3.
Then, the sample which was subjected to the ashing treatment by the ashing condition 1 was peeled off from the surface of the precursor composition layer 520 by the heat-resistant insulating tape M20, and a step gauge manufactured by KLA-Tencor Co., Ltd. was used. [Alpha Step-500], the amount of etching (level difference) from the surface of the precursor composition layer 520 was measured. Furthermore, a scanning electron microscope/energy dispersive X-ray analyzer [JSM-5510] manufactured by JEOL Ltd. was used, and the part to be subjected to ashing treatment was obtained. The SEM image and the element mapping image (Ti) in the boundary portion of the portion subjected to the ashing treatment. Furthermore, using a scanning electron microscope/energy dispersive X-ray analyzer [JSM-5510] manufactured by JEOL Ltd., the EDX in the boundary portion between the portion subjected to the ashing treatment and the portion not subjected to the ashing treatment was obtained. Spectra (energy dispersive X-ray spectroscopy).
As a result, as shown in FIG. 18 and FIG. 19, in the case where the precursor composition layer 520 is subjected to ashing treatment by the ashing condition 1, the precursor composition can be completely removed by the ashing time of about 10 minutes. In the layer 520, and even if the ashing time is 10 minutes or more, the insulating substrate 510 is not etched (see FIGS. 18(c) and 19). Further, it is understood that in the case where the precursor composition layer 520 is subjected to ashing treatment by the ashing condition 2, the precursor composition layer 520 can be completely removed by the ashing time of about 30 minutes. However, in this case, when the ashing time is 5 minutes or more, the insulating substrate 510 is also etched (see FIGS. 18(d) and 19). On the other hand, in the case where the precursor composition layer 520 is subjected to ashing treatment by the ashing condition 3, it is difficult to completely remove the precursor composition layer 520 with an ashing time of about 30 minutes (refer to FIG. 18). (e) and Figure 19).
Further, as shown in Fig. 20, a clear boundary line in the SEM image between the portion subjected to the ashing treatment and the portion not subjected to the ashing treatment was observed (refer to Fig. 20 (a)). Further, in the portion to which the ashing treatment was applied, it was confirmed that the amount of Ti (titanium) observed was greatly reduced as compared with the portion to which the ashing treatment was not applied (see FIG. 20(b)).
Further, as shown in Fig. 21, it was not observed in the portion R2 subjected to the ashing treatment: the peak of Ti (4.6 KeV and 4.9 KeV) observed in the portion R1 to which the ashing treatment was not applied ( 21(a) and 21(b)).
[Embodiment 2]
In the second embodiment, in the case where the precursor composition layer before firing is subjected to ashing treatment, the precursor composition layer (metal oxide layer) after the firing can be subjected to ashing treatment. It is also the case that the precursor composition layer or the metal oxide layer is etched at high speed.
Fig. 22 is a view showing the result of the ashing treatment in the second embodiment. Fig. 22 (a) is a view showing the result of ashing treatment in the case where the precursor composition layer before firing is subjected to ashing treatment, and Fig. 22 (b) is a diagram showing the precursor composition after firing. A diagram showing the results of the ashing treatment in the case where the layer (metal oxide layer) is subjected to ashing treatment.
In the second embodiment, as in the case of the first embodiment, SiO is formed on the surface of the Si substrate. ₂ On the insulating substrate 510 of the layer, TiO is coated by spin coating ₂ The sol-gel solution forms the precursor composition layer 520, and then the insulating substrate on which the precursor composition layer 520 is formed is dried at 200 ° C for 5 minutes on the hot plate as a sample (sample 1) )use. Further, the sample fired by heat-treating the sample 1 at 600 ° C by an RTA apparatus was used as a sample (sample 2).
Then, after the heat-resistant insulating tape M20 was partially attached to the surfaces of the sample 1 and the sample 2, the same conditions as those of the ashing condition 3 in the first embodiment (the reactive gas (CF) were made. ₄ Gas: flow rate: 0.05 L/min) and Ar gas (flow rate: 0.05 L/min) flowed together with carrier gas (He gas: flow rate: 9 L/min), and the conditions of ashing treatment were applied to the sample 1 and the sample. 2 Apply ashing treatment.
Then, for both the sample 1 and the sample 2, the heat-resistant insulating tape M20 was peeled off from the surface of the precursor composition layer 520, and a step gauge [Alpha Step-500] manufactured by KLA-Tencor Co., Ltd. was used. The amount of etching from the surface of the precursor composition layer 520 was measured.
As a result, as shown in Fig. 22, in the case where the precursor composition layer before firing is subjected to ashing treatment (see Fig. 22 (a)), the precursor composition after firing can be compared. When the layer (metal oxide layer) is subjected to ashing treatment (refer to FIG. 22(b)), the precursor composition layer or the metal oxide layer is also removed by high-speed etching.
[Embodiment 3]
The third embodiment is an embodiment in which the residual film can be completely removed in the case where a predetermined ashing treatment is applied to the precursor composition layer containing the residual film.
Fig. 23 is a view for explaining the evaluation method in the third embodiment. 23(a) to 23(d) are diagrams showing the procedure. Fig. 24 is a view showing the result of the ashing treatment in the third embodiment (AFM (Atomic Force Microscopy) image or SPM (Scanning Probe Microscope image). Fig. 24(a) shows use. A three-dimensional image of the surface of the sample after the ashing treatment obtained by a scanning probe microscope (AFM or SPM), FIG. 24(b) is a view showing a cross-sectional image thereof, and FIG. 25 is a view showing the ash in the third embodiment. A graph showing the result of the treatment (IV characteristics). In Fig. 25, symbol A is an IV characteristic in Measurement Example 1, and symbol B is an IV characteristic in Measurement Example 2.
In the third embodiment, TiO is coated by spin coating on the substrate 610 on which the Pt layer 614 is formed on the surface of the Si substrate 612. ₂ The MOD solution (0.4 mol) (2000 rpm, 30 seconds) formed the precursor composition layer 620 to dry the substrate 610 on which the precursor composition layer 620 was formed on a hot plate at 150 ° C for 5 minutes. It is used as it is (refer to Fig. 23 (a)). The size and shape of the substrate 610 are, for example, a rectangular parallelepiped of 20 mm in length × 20 mm in width × 0.7 mm in height.
Then, by using a square concave portion having a square shape of 10 mm × 10 mm, nine square concave patterns having a length of 3 μm × a width of 3 μm × a height difference of 200 nm are arranged in a matrix of three rows and three columns at a pitch of 10 μm in the vertical and horizontal directions, and the precursor is formed. The composition layer 620 is subjected to embossing (80 ° C → 200 ° C → 80 ° C, 10 MPa, 5 minutes) to form an embossed structure including the residual film 622 in the precursor composition layer 620 (refer to FIG. 23( b ) ).
Then, the precursor composition layer 620 formed with the embossed structure is subjected to ashing treatment using atmospheric piezoelectric slurry (output 300 W, time 3 minutes, ashing gas: He+Ar+CF ₄ The residual film was treated (see Fig. 23(c)).
Then, using a scanning probe microscope [S-Image] manufactured by SII NanoTechnology Co., Ltd., a three-dimensional image of the surface of the sample and a cross-sectional image thereof were obtained. Further, the IV characteristics were measured in combination with the IV measurement system shown in Fig. 23(d).
As a result, as seen from Fig. 24, a beautiful pattern having a width of 3 μm and a height of 170 nm can be formed. Further, as is clear from Fig. 24, in the measurement example 1 (reference symbol A), since only a very small current flows, the precursor composition layer 620 has high insulation (see Fig. 25). Further, in Measurement Example 2 (reference symbol B), since a very large current flows, it is suggested that the residual film 622 is cleanly removed by the region 630 in which the residual film 622 is present by applying the ashing treatment (refer to FIG. 25). .
The present invention has been described above based on the above-described embodiments, but the present invention is not limited to the embodiments, and may be practiced without departing from the scope of the invention. For example, the following modifications are possible.
(1) In the above-described first to fourth, sixth and seventh embodiments, the residual film is completely removed by subjecting the precursor composition layer including the [residual film continuous in each residual film formation region] to an ashing treatment. Further, in the fifth embodiment, the precursor composition layer including the [residual film continuous in each residual film formation region] is subjected to ashing treatment to thin the residual film until the fifth step is performed. The process makes the residual film take the thinness of the island structure. However, the invention is not limited thereto.
Fig. 26 is a view for explaining a method of manufacturing an embossed structure according to a modification. Figure 26(a) is a cross-sectional view of the precursor composition layer 20 when the precursor composition layer 20 is subjected to ashing treatment in the fourth process, and Figure 26(b) is a composition of the precursor just after the fourth process. The material layer 20 is subjected to a cross-sectional view of the precursor composition layer 20 after the ashing treatment, and FIG. 26(c) is an embossed structure 30 formed by heat-treating the precursor composition layer 20 in the fifth process. Sectional view.
In the method of manufacturing an embossed structure relating to the modification, as shown in FIG. 26(a), a residual film including [discontinued in each residual film formation region (for example, taking an island structure 28) is formed in the third process. The embossed structure of the film)] and (see FIG. 26(a)) may be completely removed by applying the ashing treatment to the precursor composition layer 20 in the fourth process (refer to FIG. 26 (refer to FIG. 26 ( a) ~ Figure 26 (c)).
(2) In the eighth embodiment, the present invention has been described by taking a thin film transistor as an example. In the above-described ninth embodiment, the present invention has been described by taking a piezoelectric ink jet head as an example, but the present invention is not Limited to this. For example, the present invention can also be applied to a film capacitor including a first electrode layer, a dielectric layer, a second electrode layer, and a wiring layer, and an actuator including a piezoelectric layer, an electrode layer, and a wiring layer; An optical element (for example, a reflective polarizing plate, a diffraction grating, or the like) having a lattice layer (a metal oxide layer or a metal layer) on a substrate.

10, 10a, 10b. . . Substrate

12. . . First substrate

14. . . a layer composed of a material that becomes an etch stop layer

20, 20a. . . Precursor composition layer

22, 22a, 120'z, 130'z, 140'z, 522. . . Residual film

twenty four. . . Concave

26, 28. . . Island structure

30. . . Embossed structure

40, 40a. . . Ashing device

41, 43. . . electrode

42. . . Positive electrode

44. . . Negative electrode

100, 900. . . Thin film transistor

110, 510, 910. . . Insulating substrate

120, 920. . . Gate electrode

120’. . . Precursor composition layer (gate electrode)

122. . . Brake pad

130, 930. . . Brake insulation

130’. . . Precursor composition layer (gate insulating layer)

140. . . Oxide conductor layer

140’. . . Precursor composition layer (oxide conductive layer)

142. . . Channel area

144. . . Source area

146. . . Bungee area

150. . . Through hole

160. . . Component separation area

300. . . Piezoelectric inkjet head

310. . . Virtual substrate

320. . . Piezoelectric element

322. . . First electrode layer

322', 324’. . . Precursor composition layer

324. . . Piezoelectric layer

326. . . Second electrode layer

330. . . Nozzle plate

332. . . Nozzle hole

340. . . Cavity member

350. . . Vibrating plate

352. . . Ink supply port

360. . . Ink room

520, 620. . . Precursor composition layer

610. . . Substrate

612. . . Si substrate

614. . . Pt layer

622. . . Residual film

630. . . Area where residual film 622 is absent

940. . . Channel layer

950. . . Source electrode

960. . . Helium electrode

i. . . Ink drop

M1, M2, M3, M4, M8, M9, M10, M11. . . Concave mode

M20. . . Heat resistant insulation tape

P. . . Plasma

10. . . Substrate

20. . . Precursor composition layer

twenty two. . . Residual film

30. . . Embossed structure

40. . . Ashing device

M1. . . Concave mode

P. . . Plasma

Claims (20)

A method of manufacturing an embossed structure, the method comprising the following sequence of processes:
a first process for preparing a liquid material containing a metal-containing compound and forming a metal oxide or a metal by heat treatment;
Forming a second process of a precursor composition layer composed of the metal oxide or a precursor composition of the metal by coating the liquid material on a substrate;
Forming an embossed structure including a residual film in the precursor composition layer by embossing using the embossing mold on the precursor composition layer;
Forming the fourth process of treating the residual film by applying a ashing treatment using atmospheric piezoelectric or low-pressure plasma to the precursor composition layer having the embossed structure; and by using the precursor composition The layer is subjected to a heat treatment for forming a fifth process of the embossed structure composed of the metal oxide or the metal from the precursor composition layer in which the embossed structure is formed. A method of producing an embossed structure according to claim 1, wherein in the fourth process, the residual film is completely removed. The method of manufacturing an embossed structure according to claim 1, wherein in the fourth process, the residual film is thinned until the residual film is formed by performing the fifth process subsequent to the fourth process. Take the thinness of the island structure. The method for producing an embossed structure according to any one of claims 1 to 3, wherein in the fourth process, the precursor composition layer on which the embossed structure is formed is subjected to atmospheric pressure. Ashing of the plasma. The method for producing an embossed structure according to any one of claims 1 to 3, wherein in the fourth process, the precursor composition layer having the embossed structure is used at a low utilization level. Ashing of the piezoelectric slurry. A method of producing an embossed structure according to claim 5, wherein the fourth process is carried out under a pressure of 0.1 Pa or more. A method of producing an embossed structure according to claim 5 or 6, wherein the fourth process is carried out in a state where a bias voltage is applied. The method for producing an embossed structure according to any one of claims 1 to 7, wherein the fourth process is carried out using a reactive gas. A method of producing an embossed structure according to the eighth aspect of the invention, wherein the fourth process is carried out using a halogen-containing element gas. A method of producing an embossed structure according to the eighth aspect of the invention, wherein the fourth process is carried out using a halogen-containing gas and a mixed gas containing an Ar gas. The method of manufacturing an embossed structure according to any one of the preceding claims, wherein the second process and the third process further comprise heating the precursor composition layer to a preheating process in which the temperature of the precursor composition layer is lowered in advance in a temperature range of 80 ° C to 200 ° C,
In the third process, by heating the precursor composition layer to a temperature in a range of 80 ° C to 300 ° C, and using a temperature heated to a temperature in the range of 80 ° C to 300 ° C The mold applies embossing to the precursor composition layer, and an embossed structure is formed on the precursor composition layer. The method for producing an embossed structure according to any one of the items 1 to 11, wherein in the fifth process, embossing composed of a metal oxide is formed by heat treatment in an oxygen-containing atmosphere. Construct. The method for producing an embossed structure according to any one of claims 1 to 11, wherein in the fifth process, the embossed structure made of a metal is formed by heat treatment in a reducing atmosphere. A thin film transistor comprising a gate electrode layer, a gate insulating layer, a source layer, a drain layer, a channel layer and a wiring layer, and is characterized by:
At least one of the gate electrode layer, the gate insulating layer, the source layer, the drain layer, the channel layer, and the wiring layer is pressed by any one of the first to the thirteenth claims A method of manufacturing a flower structure is formed. A thin film transistor characterized by:
An oxide conductor layer including a source region and a drain region and a channel region;
a gate electrode for controlling an on state of the channel region; and a gate insulating layer formed of a ferroelectric material or a paraelectric material formed between the gate electrode and the channel region,
The layer thickness of the channel region is thinner than the layer thickness of the source region and the layer thickness of the drain region.
The oxide conductor layer having a layer thickness of the channel region which is thinner than the layer thickness of the source region and the layer thickness of the drain region is an embossed structure according to any one of claims 1 to 13. The manufacturing method is formed. The thin film transistor of claim 15, wherein the carrier concentration and the layer thickness of the channel region are set to a value of a total depletion of the channel region when the thin film transistor is in a closed state. A film capacitor comprising a first electrode layer, a dielectric layer, a second electrode layer and a wiring layer, wherein:
At least one of the first electrode layer, the dielectric layer, the second electrode layer, and the wiring layer is a method of manufacturing an embossed structure according to any one of claims 1 to 13. form. An actuator comprising a piezoelectric layer, an electrode layer and a wiring layer, characterized by:
At least one of the piezoelectric layer, the electrode layer, and the wiring layer is formed by the method for producing an embossed structure according to any one of claims 1 to 13. A piezoelectric inkjet head characterized by:
Cavity member
a vibration plate formed on one side of the cavity member and having a piezoelectric layer;
a nozzle plate formed on the other side of the cavity member, the nozzle hole is formed; and an ink chamber defined by the cavity member, the vibration plate, and the nozzle plate,
The piezoelectric layer and/or the cavity member is formed by the method for producing an embossed structure according to any one of the first to thirteenth aspects of the invention. An optical component comprising a lattice layer on a substrate, characterized by:
The lattice layer is formed by the method for producing an embossed structure according to any one of claims 1 to 13.