WO2013069448A1 - Procédé de production de corps structural pressé par matrice, transistor en couches minces, condensateur en couches minces, actionneur, tête à jet d'encre piézoélectrique et dispositif optique - Google Patents

Procédé de production de corps structural pressé par matrice, transistor en couches minces, condensateur en couches minces, actionneur, tête à jet d'encre piézoélectrique et dispositif optique Download PDF

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WO2013069448A1
WO2013069448A1 PCT/JP2012/077323 JP2012077323W WO2013069448A1 WO 2013069448 A1 WO2013069448 A1 WO 2013069448A1 JP 2012077323 W JP2012077323 W JP 2012077323W WO 2013069448 A1 WO2013069448 A1 WO 2013069448A1
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layer
precursor composition
manufacturing
composition layer
embossed structure
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PCT/JP2012/077323
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English (en)
Japanese (ja)
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下田　達也
敏彦 金田
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独立行政法人科学技術振興機構
セイコーエプソン株式会社
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Publication of WO2013069448A1 publication Critical patent/WO2013069448A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1607—Production of print heads with piezoelectric elements
    • B41J2/161—Production of print heads with piezoelectric elements of film type, deformed by bending and disposed on a diaphragm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1623—Manufacturing processes bonding and adhesion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1626—Manufacturing processes etching
    • B41J2/1628—Manufacturing processes etching dry etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/164—Manufacturing processes thin film formation
    • B41J2/1645—Manufacturing processes thin film formation thin film formation by spincoating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/06—Coating on selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/28008—Making conductor-insulator-semiconductor electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/1292—Multistep manufacturing methods using liquid deposition, e.g. printing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
    • H10N30/078—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition by sol-gel deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/08—Shaping or machining of piezoelectric or electrostrictive bodies
    • H10N30/081—Shaping or machining of piezoelectric or electrostrictive bodies by coating or depositing using masks, e.g. lift-off
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
    • H10N30/204—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators using bending displacement, e.g. unimorph, bimorph or multimorph cantilever or membrane benders
    • H10N30/2047—Membrane type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/401—Multistep manufacturing processes
    • H01L29/4011—Multistep manufacturing processes for data storage electrodes
    • H01L29/40111—Multistep manufacturing processes for data storage electrodes the electrodes comprising a layer which is used for its ferroelectric properties

Definitions

  • the present invention relates to a method for manufacturing an embossed structure, a thin film transistor, a thin film capacitor, an actuator, a piezoelectric inkjet head, and an optical device.
  • FIG. 27 is a view for explaining a conventional thin film transistor 900.
  • the conventional thin film transistor 900 controls the source electrode 950 and the drain electrode 960, the channel layer 940 located between the source electrode 950 and the drain electrode 960, and the conduction state of the channel layer 940. It includes a gate electrode 920 and a gate insulating layer 930 formed between the gate electrode 920 and the channel layer 940 and made of a ferroelectric material.
  • reference numeral 910 denotes an insulating substrate.
  • a ferroelectric material for example, BLT (Bi 4-x La x Ti 3 O 12 ), PZT (Pb (Zr x , Ti 1-x )) is used. ) O 3 ) is used, and an oxide conductive material (for example, indium tin oxide (ITO)) is used as a material constituting the channel layer 940.
  • the conventional thin film transistor 900 since an oxide conductive material is used as a material constituting the channel layer, the carrier concentration can be increased, and a ferroelectric material is used as the material constituting the gate insulating layer. Since it is used, switching can be performed at a high speed with a low driving voltage, and as a result, a large current can be controlled at a high speed with a low driving voltage.
  • FIG. 28 is a view for explaining a conventional method of manufacturing a thin film transistor.
  • FIG. 28A to FIG. 28E are process diagrams, and
  • FIG. 28F is a plan view of the thin film transistor 900.
  • a laminated film of Ti (10 nm) and Pt (40 nm) is formed on an insulating substrate 910 made of a Si substrate having a SiO 2 layer formed on the surface by electron beam evaporation.
  • a gate electrode 920 is formed.
  • BLT Bi 3.25 La 0.75 Ti 3 O 12
  • PZT Pb (Zr 0.4 Ti 0 ) is formed by a sol-gel method. .6 )
  • a gate insulating layer 930 (200 nm) made of O 3 ) is formed.
  • a channel layer 940 (5 nm to 15 nm) made of ITO is formed on the gate insulating layer 930 by RF sputtering.
  • Ti (30 nm) and Pt (30 nm) are vacuum-deposited on the channel layer 940 by electron beam evaporation to form a source electrode 950 and a drain electrode 960.
  • the element region is separated from other element regions by the RIE method and the wet etching method (HF: HCl mixed solution). Thereby, a thin film transistor 900 as shown in FIGS. 28E and 28F can be manufactured.
  • FIG. 29 is a diagram for explaining the electrical characteristics of a conventional thin film transistor 900.
  • reference numeral 940a indicates a channel
  • reference numeral 940b indicates a depletion layer.
  • the conventional thin film transistor 900 is manufactured by the above method, a high vacuum process or photolithography is performed in the process of forming the gate electrode 920, the channel layer 940, the source electrode 950, and the drain electrode 960. There is a problem that a process must be used, the use efficiency of raw materials and production energy is low, and a long time is required for production.
  • Such a problem is not a problem that can be seen only in the above-described method for manufacturing a thin film transistor, but a problem that can be found in general methods for manufacturing a functional device such as a thin film capacitor, an actuator, a piezoelectric inkjet head, or an optical device. It is.
  • the present invention has been made to solve the above-described problems.
  • Various functional devices including the above-described excellent thin film transistors are used by using significantly less raw materials and manufacturing energy than conventional ones. And it aims at providing the manufacturing method of the embossing structure which can be manufactured in a shorter process than before.
  • a method for producing an embossed structure includes a first step of preparing a liquid material that contains a metal-containing compound and heat-treats to become a metal oxide or a metal, and the liquid material on a substrate.
  • a third step of forming a stamped structure including a residual film in the precursor composition layer, and an ashing process using atmospheric pressure plasma or reduced pressure plasma on the precursor composition layer formed with the stamped structure From the precursor composition layer in which the embossing structure is formed by heat-treating the precursor composition layer, the fourth step of treating the residual film by applying the metal oxide or the metal Embossed Characterized in that it comprises a fifth step of forming a granulated body in this order.
  • a liquid material is applied onto a substrate to form a precursor composition layer, and the precursor composition layer is embossed to perform an embossing process.
  • the precursor composition layer is embossed to perform an embossing process.
  • the manufacturing method of the stamping structure of this invention since it further includes the 4th process of processing a remaining film by performing an ashing process with respect to a precursor composition layer, there is no influence of a remaining film.
  • An embossed structure can be formed.
  • the “embossed structure without the influence of the remaining film” refers to an embossed structure having a structure divided at the portion where the remaining film was present, and the portion where the remaining film was present Both the case where no residual film remains and the case where the sea-island-like residual film remains in the portion where the residual film existed are included.
  • the precursor composition layer is subjected to the ashing treatment by the atmospheric pressure plasma or the reduced pressure plasma. Since a vacuum environment is not required, expensive high-vacuum equipment can be eliminated, and the time required for performing the fourth step can be shortened.
  • various printing techniques letterpress printing, gravure printing, offset printing, screen printing, ink jet printing, etc.
  • a stamped structure having a pattern on the order of several tens of microns can be formed at most, so that a stamped structure having a fine pattern on the order of submicrons cannot be formed.
  • the method for manufacturing an embossed structure of the present invention it is possible to form an embossed structure having a fine pattern on the order of submicrons without requiring a high vacuum environment. is there.
  • a sol-gel solution containing a metal alkoxide containing a metal alkoxide
  • the remaining film is a convex surface that protrudes most in the concavo-convex mold when the precursor composition layer is embossed using the concavo-convex mold in the third step. It refers to the precursor composition layer remaining between the substrate surface. Further, in the method for producing an embossed structure of the present invention, the remaining film is not “continuous in each remaining film forming region” in addition to “continuous film in each remaining film forming region”. “Membrane” (for example, a membrane having a sea-island structure) is also included.
  • the precursor composition layer By adopting such a method, it is possible to form an embossed structure that is not affected by the remaining film. That is, in the fifth step, as a result of the precursor composition layer being divided into a plurality of regions, the precursor composition layer can be reasonably contracted in the in-plane direction, so that a desired embossed structure can be obtained with high accuracy. It becomes possible to form.
  • a method of performing ashing only for the first time calculated from the relationship between the etching rate of the precursor composition layer by the ashing process and the thickness of the remaining film ashing method by time management
  • a method of performing ashing for a time exceeding the first time an ashing method by over-etching, in which case the base material may be etched
  • a base material made of a material that serves as an etching stopper Preferably, a base material or a base material provided with a layer made of a material to be an etching stopper is prepared on the surface, and a method of ashing for a time exceeding the first time (ashing method in combination with an etching stopper) is used. Can do.
  • the fifth step following the fourth step is performed, so that the remaining film has a sea-island structure.
  • the remaining film is preferably thinned.
  • the precursor composition layer can be reasonably contracted in the in-plane direction, so that a desired embossed structure can be obtained with high accuracy. It becomes possible to form.
  • the fourth step it is preferable to perform an ashing process using atmospheric pressure plasma on the precursor composition layer on which the embossed structure is formed.
  • the fourth step it is also preferable to subject the precursor composition layer on which the embossed structure has been formed to an ashing process using reduced-pressure plasma.
  • the fourth step is preferably performed under a pressure of 1 Pa or higher, and the fourth step is performed under a pressure of 10 Pa or higher. More preferably.
  • the fourth step under a pressure of about 1000 Pa to 100,000 Pa. This is because, within such a pressure range, it is possible to form a pressure environment in a short time. In addition, in such a pressure range, it is possible to continuously put the workpiece in the atmospheric pressure environment into the pressure environment while conveying the workpiece. Moreover, in the manufacturing method of the stamping structure of this invention, it is also preferable to implement a 4th process under the pressure of 1000 Pa or less. This is because when the fourth step is performed under a pressure of 1000 Pa or less, the fourth step can be stably performed with a bias voltage applied, as will be described later. From this point of view, it is more preferable to carry out the fourth step under a pressure of 100 Pa or less in the method for manufacturing the embossed structure of the present invention.
  • the ashing process can be performed at a high etching rate by performing the fourth process while the bias voltage is applied, and as a result, the embossed structure is manufactured with high productivity. It becomes possible to do.
  • the mean free path of the gas used for ashing (ashing gas) is longer under reduced pressure conditions than under atmospheric pressure conditions, and the flight direction of the ashing gas is aligned in one direction, the above-mentioned As described above, by performing the fourth step with the bias voltage applied, it is possible to reduce the ratio of etching (side etching) to the side surface portion of the embossing structure, and consequently, embossing with high shape accuracy.
  • a structure can be manufactured.
  • the reactive gas it is preferable to use a reactive gas capable of causing a chemical reaction with components constituting the precursor composition layer and etching the precursor composition layer.
  • the fourth step is performed using a halogen element-containing gas as the reactive gas.
  • the halogen element-containing gas may be a fluorine-based gas or a chlorine-based gas.
  • a gas, a bromine-based gas, or the like can be preferably used.
  • the precursor composition layer is made 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 can be suitably used.
  • the precursor composition layer is made of a substance containing Al, for example, Cl 2 , BCl 3 , CCl 4 , SiCl 4 , BCl 3 / Cl 2 / Ar or the like can be suitably used, and when the precursor composition layer is made of a substance containing at least one of W, Mo, Ta and Ti, for example, CF 4 , CF 4 / O 2 , NF 3 , CCl 4 / O 2 Etc. can be preferably used, if the precursor composition layer is made of a material containing Cr, for example Cl 2, Cl 2 / O 2 , CCl 4 / O 2 , etc. can be preferably used, When the precursor composition layer is made of a substance containing at least one of Au and Pt, for example, Cl 2 , Cl 2 / Ar, etc. can be suitably used.
  • He gas or N2 gas as a carrier gas.
  • the precursor composition layer is heated to a temperature in the range of 80 ° C. to 200 ° C. between the second step and the third step. And further including a preheating step in which the fluidity of the precursor composition layer is previously lowered, and in the third step, the temperature of the precursor composition layer is within a range of 80 ° C. to 300 ° C. Is applied to the precursor composition layer by using a mold heated to a temperature within the range of 80 ° C. to 300 ° C. It is preferable to form an embossed structure.
  • the solidification reaction of the precursor composition layer is advanced to some extent by heating to a temperature within the range of 80 ° C. to 200 ° C., thereby reducing the fluidity of the precursor composition layer in advance.
  • it is embossed with respect to the precursor composition layer that has obtained high plastic deformation ability by reducing the hardness of the precursor composition layer by heating to a temperature within the range of 80 ° C. to 300 ° C. Since the processing is performed, a desired embossed structure can be formed with high accuracy, and as a result, an embossed structure having a desired performance can be manufactured.
  • the embossing technique that performs the embossing process using a liquid material that becomes a metal oxide or metal by heat treatment.
  • embossing at room temperature there is a report example of embossing at room temperature.
  • the heating temperature of the precursor composition layer is set within the range of “80 ° C. to 300 ° C.” when the heating temperature is less than 80 ° C., the precursor composition layer is sufficiently softened. This is because the plastic deformation ability of the precursor composition layer cannot be made sufficiently high, and when the heating temperature exceeds 300 ° C., the solidification reaction of the precursor composition layer proceeds too much and the precursor composition This is because the plastic deformation ability of the material layer is reduced again.
  • the precursor composition layer it is more preferable to subject the precursor composition layer to an embossing process in a state where the precursor composition layer is heated to a temperature within the range of 100 ° C. to 200 ° C.
  • the precursor composition layer is embossed using a mold heated to a temperature within the range of 80 ° C. to 300 ° C., the embossing process is performed. During the process, the plastic deformation ability of the precursor composition layer is not lowered, so that a desired embossed structure can be formed with higher accuracy.
  • the reason why the heating temperature of the mold is within the range of “80 ° C. to 300 ° C.” is that when the heating temperature is less than 80 ° C., the temperature of the precursor composition layer decreases. This is because the plastic deformation ability of the precursor composition layer may be reduced, and when the heating temperature exceeds 300 ° C., the dehydration condensation reaction of the precursor composition layer proceeds excessively. This is because the plastic deformation ability of the precursor composition layer is lowered.
  • the third step it is more preferable to perform an embossing process using a mold heated to a temperature in the range of 100 ° C. to 200 ° C.
  • an embossing process it is preferable to perform an embossing process at a pressure in the range of 1 MPa to 20 MPa in the third step.
  • the stamping process is performed on the precursor composition layer having a high plastic deformation capability, when the stamping process is performed, Even when the pressure applied to the pressure is lowered to 1 MPa to 20 MPa, the precursor composition layer is deformed following the surface shape of the mold, and a desired embossed structure can be formed with high accuracy. . Further, by lowering the pressure applied when performing the stamping process to 1 MPa to 20 MPa, it is difficult to damage the mold when performing the stamping process.
  • the reason why the pressure is within the range of “1 MPa to 20 MPa” is that when the pressure is less than 1 MPa, the pressure is too low to be able to emboss the precursor composition. This is because if the pressure is 20 MPa, the precursor composition can be sufficiently embossed, so that it is not necessary to apply a pressure higher than this.
  • the third step it is more preferable to perform the embossing process at a pressure in the range of 2 MPa to 10 MPa.
  • stamping structure made of a metal oxide by heat treatment in an oxygen-containing atmosphere.
  • the embossed structure material layer is formed into “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”, “in a thin film capacitor “First electrode layer, dielectric layer, second electrode layer or wiring layer”, “piezoelectric layer, electrode layer or wiring layer in actuator”, “piezoelectric layer or cavity member in piezoelectric inkjet head”, “in optical device” It becomes possible to manufacture various functional devices provided as a “lattice layer (metal ceramics lattice layer)”.
  • the manufacturable metal oxides various paraelectric material (e.g., 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, 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 conductive materials (e.g., indium boron x
  • stamping structure of the present invention in the fifth step, it is preferable to form a stamping structure made of metal by heat treatment in a reducing atmosphere.
  • the functional solid material layer is formed into “a gate electrode layer or a wiring layer in a thin film transistor”, “a first electrode layer, a second electrode layer or a wiring layer in a thin film capacitor”.
  • Electrode layer in actuator “lattice layer (metal lattice layer) in optical device”, and the like, so that various functional devices can be manufactured.
  • examples of the metal that can be produced include Au, Pt, Ag, Cu, Ti, Ge, In, and Sn.
  • a thin film transistor of the present invention is a thin film transistor including a gate electrode layer, a gate insulating layer, a source layer, a drain layer, a channel layer, and a wiring layer, and the gate electrode layer, the gate insulating layer, and the source layer At least one of the drain layer, the channel layer, and the wiring layer is formed by the method for manufacturing an embossed structure of the present invention.
  • At least one layer of the thin film transistor is used as an embossed structure free from the influence of the remaining film, using significantly less raw materials and manufacturing energy, and in a shorter process than before. It can be manufactured.
  • the thin film transistor of the present invention includes an oxide conductor layer including a source region, a drain region, and a channel region, a gate electrode that controls a conduction state of the channel region, and between the gate electrode and the channel region.
  • a gate insulating layer made of a ferroelectric material or a paraelectric material, wherein the channel region is thinner than the source region and the drain region.
  • the oxide conductor layer in which the layer thickness of the channel region is thinner than the layer thickness of the source region and the drain region is formed by the method for manufacturing an embossed structure of the present invention.
  • the oxide conductive material is used as the material constituting the channel region, the carrier concentration can be increased, and as the material constituting the gate insulating layer, a ferroelectric material or Since a paraelectric material is used, it is possible to perform high-speed switching with a low driving voltage. As a result, as with conventional thin film transistors, it is possible to control a large current at high speed with a low driving voltage. .
  • an oxide conductor layer in which the layer thickness of the channel region is thinner than the layer thickness of the source region and the drain region and is not affected by the remaining film is formed according to the present invention. Since a thin film transistor can be manufactured only by forming using a manufacturing method of a push structure, a channel region, a source region, and a drain region are not formed from different materials as in the case of a conventional thin film transistor. Therefore, it is possible to manufacture a thin film transistor excellent as described above by using much less raw materials and manufacturing energy than in the past and in a shorter process than in the past.
  • the carrier concentration and the layer thickness of the channel region may be set to such values that the entire channel region is depleted when the thin film transistor is in an off state. preferable.
  • the thin film transistor is an enhancement type transistor
  • the thin film transistor is turned off when a control voltage of 0 V is applied to the gate electrode, and thus the entire channel region is depleted in such a case.
  • 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 only necessary to set the value so that the entire channel region is depleted.
  • a thin film capacitor of the present invention is a thin film capacitor including 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 And at least one of the wiring layers is formed by the method for manufacturing an embossed structure of the present invention.
  • At least one layer of the thin film capacitor is used as an embossed structure free from the influence of the remaining film, using significantly less raw materials and manufacturing energy, and in a shorter process than before. It can be manufactured.
  • An actuator of the present invention is an actuator including a piezoelectric layer, an electrode layer, and a wiring layer, and at least one of the piezoelectric layer, the electrode layer, and the wiring layer is formed by embossing of the present invention. It is formed by the manufacturing method of a structure.
  • At least the piezoelectric layer is manufactured as a stamped structure that is not affected by the residual film, using significantly less raw materials and manufacturing energy, and in a shorter process than before. Is possible.
  • liquid material that becomes a ferroelectric material by heat treatment can be suitably used as the liquid material.
  • a piezoelectric ink jet head is attached to a cavity member, a vibration plate attached to one side of the cavity member and having a piezoelectric layer formed thereon, attached to the other side of the cavity member, and having a nozzle hole.
  • a piezoelectric inkjet head comprising a formed nozzle plate and an ink chamber defined by the cavity member, the vibration plate, and the nozzle plate, wherein the piezoelectric layer and / or the cavity member is the present invention. It is formed by the manufacturing method of this type
  • the piezoelectric ink jet head of the present invention since the piezoelectric layer and / or the cavity member is formed by using the method for manufacturing the embossing structure of the present invention, the piezoelectric ink jet head is made of the remaining film. As an embossed structure having no influence, it is possible to manufacture using a raw material and manufacturing energy which are significantly less than those of the conventional structure and in a shorter process than that of the conventional structure.
  • the optical device of the present invention is an optical device 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. To do.
  • the lattice layer can be manufactured as a stamped structure without the influence of the remaining film, using significantly less raw materials and manufacturing energy, and in a shorter process than before. It becomes.
  • the lattice layer is made of an insulator
  • a liquid material that becomes an insulator material by heat treatment can be used as the liquid material.
  • a liquid material that becomes a metal material by heat treatment can be used.
  • FIG. 1 The figure shown in order to demonstrate the manufacturing method of the embossing structure which concerns on Embodiment 1.
  • FIG. The figure shown in order to demonstrate the manufacturing method of the embossing structure which concerns on Embodiment 2.
  • FIG. The figure shown in order to demonstrate the manufacturing method of the embossing structure which concerns on Embodiment 4.
  • FIG. It is a figure shown in order to demonstrate the ashing apparatus 40 used for Embodiment 6.
  • FIG. The figure shown in order to demonstrate the manufacturing method of the embossing structure which concerns on Embodiment 6.
  • FIG. 10 is a view for explaining a thin film transistor 100 according to an eighth embodiment.
  • FIG. 10 is a view for explaining a manufacturing method of the thin film transistor according to the eighth embodiment.
  • FIG. 10 is a view for explaining a manufacturing method of the thin film transistor according to the eighth embodiment.
  • FIG. 10 is a view for explaining a manufacturing method of the thin film transistor according to the eighth embodiment.
  • FIG. 10 is a view for explaining a manufacturing method of the thin film transistor according to the eighth embodiment.
  • FIG. 10 is a view for explaining a piezoelectric inkjet head 300 according to a ninth embodiment.
  • FIG. 10 is a view for explaining a method for manufacturing a piezoelectric inkjet head according to a ninth embodiment.
  • FIG. 10 is a view for explaining a method for manufacturing a piezoelectric inkjet head according to a ninth embodiment.
  • FIG. 10 is a view for explaining a method for manufacturing a piezoelectric inkjet head according to a ninth embodiment. It is a figure shown in order to demonstrate the ashing process in Example 1.
  • FIG. is a figure which shows the result of the ashing process in Example 1.
  • FIG. It is a figure which shows the result of the ashing process in Example 1.
  • FIG. It is a figure which shows the result of the ashing process in Example 2.
  • FIG. 10 is a view for explaining a method for manufacturing a piezoelectric inkjet head according to a ninth embodiment.
  • It is a figure shown in order to demonstrate the ashing process in Example 1.
  • FIG. It is a figure shown in order to demonstrate the evaluation method in Example 3.
  • FIG. It is a figure which shows the result of the ashing process in Example 3.
  • FIG. It is a figure which shows the result of the ashing process in Example 3.
  • FIG. The figure shown in order to demonstrate the manufacturing method of the embossing structure which concerns on a modification.
  • FIG. It is a figure shown in order to demonstrate the manufacturing method of the conventional thin-film transistor.
  • Embodiments 1 to 7 are embodiments relating to a method for manufacturing an embossing structure of the present invention
  • Embodiment 8 is an embodiment relating to a thin film transistor of the present invention
  • Embodiment 9 is an embodiment relating to a piezoelectric inkjet head of the present invention. It is a form.
  • FIG. 1 is a view for explaining the method for manufacturing the embossed structure according to the first embodiment.
  • FIG. 1A to FIG. 1G are process diagrams.
  • the symbol P indicates plasma.
  • the manufacturing method of the embossed structure according to the first embodiment includes a first step of preparing a liquid material that contains a metal-containing compound and is heat-treated to be a metal oxide or metal, and a base material.
  • a second step (see FIGS. 1A and 1B) of forming a precursor composition layer 20 made of a metal oxide or a metal precursor composition by applying a liquid material onto the substrate 10;
  • a preheating step (FIG. 1) in which the fluidity of the precursor composition layer 20 is previously lowered by heating the precursor composition layer 20 to a temperature (for example, 150 ° C.) within the range of 80 ° C. to 200 ° C. (C)), and the precursor composition layer 20 is heated to a temperature in the range of 80 ° C.
  • a third step for forming a stamped structure including the remaining film 22 on the precursor composition layer 20 by performing a stamping process on the composition layer 20;
  • a fourth step for treating the remaining film 22 by subjecting the formed precursor composition layer 20 to an ashing process using atmospheric pressure plasma, and the precursor.
  • the 5th process (refer FIG.1 (g)) which forms the stamping structure 30 which consists of a metal oxide or a metal from the precursor composition layer 20 in which the stamping structure was formed by heat-processing the composition layer 20.
  • FIG. In this order.
  • a liquid material containing a metal-containing compound and becoming a metal oxide or metal by heat treatment for example, “a sol-gel solution containing a metal alkoxide” as the liquid material.
  • a sol-gel solution containing a metal alkoxide as the liquid material.
  • MOD Metal-Organic-Decomposition
  • Metal salt solution containing metal salt for example, metal chloride, metal acid chloride, metal nitrate, metal acetate, etc.
  • stamping is performed on the precursor composition layer 20 using the concavo-convex mold M1, and therefore, as shown in FIG. As described above, an embossed structure including the remaining film 22 is formed in the precursor composition layer 20. Therefore, in the fourth step, the residual film 22 is processed by subjecting such a precursor composition layer 20 to an ashing process using atmospheric pressure plasma. Specifically, FIG. 1 (e) and FIG. As shown in FIG. 1 (f), the remaining film 22 is completely removed.
  • the fourth step using a reactive gas for example, “halogen element-containing gas”, “mixed gas containing a halogen element-containing gas and Ar gas”, etc.
  • a reactive gas for example, “halogen element-containing gas”, “mixed gas containing a halogen element-containing gas and Ar gas”, etc.
  • halogen element-containing gas various fluorine-based gases, chlorine-based gases, bromine-based gases, and the like can be suitably used.
  • the remaining film is completely removed, and “an embossed structure having no influence of the remaining film, that is, an embossed structure having a structure divided at the portion where the remaining film was present”. Can be formed.
  • the precursor composition layer is divided into individual small regions. As a result, the precursor composition layer can be reasonably contracted in the in-plane direction, so that the desired embossed structure is high. It becomes possible to form with accuracy.
  • a liquid material is applied on a substrate to form a precursor composition layer, and the precursor composition layer is embossed.
  • a stamping structure can be formed by forming a stamping structure and further heat-treating the precursor composition layer at a high temperature, a mold having a submicron order fine pattern is used.
  • a mold having a submicron order fine pattern is used.
  • various functional devices including the above-described excellent thin film transistors can be manufactured.
  • the precursor composition layer is advanced to some extent by heating to a temperature within the range of 80 ° C. to 200 ° C.
  • Precursor having high plastic deformation ability by reducing the fluidity of the layer in advance and by lowering the hardness of the precursor composition layer by heating to a temperature in the range of 80 ° C. to 300 ° C. Since the embossing process is performed on the body composition layer, a desired embossed structure can be formed with high accuracy, and as a result, an embossed structure having desired performance can be manufactured. It becomes possible.
  • a stamping process is performed on the precursor composition layer using a mold heated to a temperature in the range of 80 ° C. to 300 ° C. Therefore, since the plastic deformation ability of the precursor composition layer is not reduced during the embossing process, it becomes possible to form a desired embossed structure with higher accuracy. .
  • FIG. 2 is a view for explaining the method for manufacturing the embossed structure according to the second embodiment.
  • FIG. 2A is a cross-sectional view of the precursor composition layer 20 being subjected to the ashing process on the precursor composition layer 20 in the fourth step
  • FIG. 2B is the fourth step.
  • 3 is a cross-sectional view of the precursor composition layer 20 immediately after the ashing process is performed on the precursor composition layer 20.
  • the manufacturing method of the embossing structure according to the second embodiment basically includes the same steps as the manufacturing method of the embossing structure according to the first embodiment, but the contents of the fourth step are the molds according to the first embodiment. Different from the manufacturing method of the push structure. That is, in the manufacturing method of the embossed structure according to the second embodiment, as shown in FIG. 2, the relationship between the etching rate of the precursor composition layer by the ashing process and the thickness of the remaining film 22 in the fourth step. Ashing is performed for a time exceeding the first time calculated from the above. As a result, in the method for manufacturing the embossed structure according to the second embodiment, the recess 24 is formed in the base material 10 as shown in FIG.
  • the method for manufacturing the embossed structure according to the second embodiment differs from the method for manufacturing the embossed structure according to the first embodiment in the content of the fourth step, but the embossed structure according to the first embodiment.
  • the fourth step of treating the remaining film by subjecting the precursor composition layer to ashing treatment is included, so that a stamped structure without the influence of the remaining film is formed. It becomes possible.
  • the precursor composition layer is subjected to an ashing process using atmospheric pressure plasma, a high-vacuum environment is not required when performing the fourth step, and thus expensive high-vacuum equipment is not required.
  • the method for manufacturing the embossed structure according to the second embodiment is the same as the method for manufacturing the embossed structure according to the first embodiment except for the fourth step. It has the effect applicable among the effects which the manufacturing method of a structure has.
  • FIG. 3 is a view for explaining the manufacturing method of the embossing structure according to the third embodiment.
  • FIG. 3A is a cross-sectional view of the precursor composition layer 20 during the ashing process for the precursor composition layer 20 in the fourth step
  • FIG. 3B is the fourth step.
  • 3 is a cross-sectional view of the precursor composition layer 20 immediately after the ashing process is performed on the precursor composition layer 20.
  • the manufacturing method of the stamping structure according to the third embodiment basically includes the same steps as the manufacturing method of the stamping structure according to the first embodiment, but the contents of the fourth step are the molds according to the first embodiment. Different from the manufacturing method of the push structure. That is, in the method for manufacturing the embossed structure according to the third embodiment, as shown in FIG. 3, the base material 10a made of a material that serves as an etching stopper is used as the base material, and the precursor composition layer by ashing treatment is used. Ashing is performed for a time exceeding the first time calculated from the relationship between the etching rate and the thickness of the remaining film 22.
  • the method for manufacturing the embossed structure according to the third embodiment differs from the method for manufacturing the embossed structure according to the first embodiment in the content of the fourth step, but the embossed structure according to the first embodiment.
  • the fourth step of treating the remaining film by subjecting the precursor composition layer to ashing treatment is included, so that a stamped structure without the influence of the remaining film is formed. It becomes possible.
  • the precursor composition layer is subjected to an ashing process using atmospheric pressure plasma, a high-vacuum environment is not required when performing the fourth step, and thus expensive high-vacuum equipment is not required.
  • the method for manufacturing the embossed structure according to the second embodiment is performed despite the ashing under the so-called over-etching conditions. In contrast, as shown in FIG. 3B, no recess is formed in the substrate 10a.
  • the method for manufacturing the embossed structure according to the third embodiment is the same as the method for manufacturing the embossed structure according to the first embodiment except for the fourth step. It has the effect applicable among the effects which the manufacturing method of a structure has.
  • FIG. 4 is a view for explaining the method for manufacturing the embossed structure according to the fourth embodiment.
  • FIG. 4A is a cross-sectional view of the precursor composition layer 20 being subjected to the ashing process on the precursor composition layer 20 in the fourth step
  • FIG. 4B is the fourth step.
  • 3 is a cross-sectional view of the precursor composition layer 20 immediately after the ashing process is performed on the precursor composition layer 20.
  • the manufacturing method of the embossing structure according to the fourth embodiment basically includes the same steps as the manufacturing method of the embossing structure according to the first embodiment, but the contents of the fourth step are the molds according to the first embodiment. Different from the manufacturing method of the push structure. That is, in the method for manufacturing an embossed structure according to the fourth embodiment, as shown in FIG. 4, a base material 10 b provided with a layer 14 made of a material serving as an etching stopper on the surface of the first base material 12 as a base material. And ashing is performed for a time exceeding the first time calculated from the relationship between the etching rate of the precursor composition layer by the ashing process and the thickness of the remaining film 22.
  • the manufacturing method of the embossing structure according to the fourth embodiment differs from the manufacturing method of the embossing structure according to the first embodiment in the content of the fourth step, but the embossing structure according to the first embodiment.
  • the fourth step of treating the remaining film by subjecting the precursor composition layer to ashing treatment is included, so that a stamped structure without the influence of the remaining film is formed. It becomes possible.
  • the precursor composition layer is subjected to an ashing process using atmospheric pressure plasma, a high-vacuum environment is not required when performing the fourth step, and thus expensive high-vacuum equipment is not required.
  • ashing is performed under so-called overetching conditions. As shown in FIG. 4B, no recess is formed in the base material 10b.
  • the method for manufacturing the embossed structure according to the fourth embodiment is the same as the method for manufacturing the embossed structure according to the first embodiment except for the fourth step. It has the effect applicable among the effects which the manufacturing method of a structure has.
  • FIG. 5 is a view for explaining the method for manufacturing the embossed structure according to the fifth embodiment.
  • FIG. 5A is a cross-sectional view of the precursor composition layer 20 during the ashing process for the precursor composition layer 20 in the fourth step
  • FIG. 5B is the fourth step.
  • FIG. 5C is a cross-sectional view of the precursor composition layer 20 immediately after the ashing process is performed on the precursor composition layer 20, and
  • FIG. 5C is formed by heat-treating the precursor composition layer 20 in the fifth step.
  • FIG. 5 is an enlarged view of FIG. 1 to FIG. 4 to make it easier to see the sea-island structure 24 described later.
  • the manufacturing method of the stamping structure according to the fifth embodiment basically includes the same steps as the manufacturing method of the stamping structure according to the first embodiment, but the contents of the fourth step are the molds according to the first embodiment. Different from the manufacturing method of the push structure. That is, in the method for manufacturing the embossed structure according to the fifth embodiment, as shown in FIG. 5, in the fourth step, the remaining film forms the sea-island structure 26 by performing the fifth step following the fourth step. The remaining film 22 is thinned to the thinness that can be obtained.
  • the method for manufacturing the stamping structure according to the fifth embodiment is different from the method for manufacturing the stamping structure according to the first embodiment in the content of the fourth step, but the stamping structure according to the first embodiment.
  • the fourth step of treating the remaining film by subjecting the precursor composition layer to ashing treatment is included, so that a stamped structure without the influence of the remaining film is formed. It becomes possible.
  • the precursor composition layer is subjected to an ashing process using atmospheric pressure plasma, a high-vacuum environment is not required when performing the fourth step, and thus expensive high-vacuum equipment is not required.
  • the remaining film comes to have the sea-island structure 26 after the fifth process is finished, and therefore the remaining film is not completely removed at the end of the fourth process. Even if it exists, it becomes possible to form the embossing structure without the influence of the remaining film.
  • the method for manufacturing the embossed structure according to the fifth embodiment is the same as the method for manufacturing the embossed structure according to the first embodiment except for the fourth step. It has the effect applicable among the effects which the manufacturing method of a structure has.
  • FIG. 6 is a diagram for explaining an ashing device 40 used in the sixth embodiment.
  • FIG. 7 is a view for explaining the manufacturing method of the embossing structure according to the sixth embodiment.
  • FIG. 7A is a cross-sectional view of the precursor composition layer 20 just before the ashing treatment is performed on the precursor composition layer 20 in the fourth step
  • FIG. 7B is a precursor composition in the fourth step.
  • 3 is a cross-sectional view of the precursor composition layer 20 immediately after the ashing process is performed on the physical layer 20.
  • reference numeral 41 denotes one electrode
  • reference numeral 43 denotes the other electrode.
  • FIG. 7 in order to make it easier to see the side etching, the drawing is further enlarged than in FIG.
  • the manufacturing method of the stamping structure according to the sixth embodiment basically includes the same steps as the manufacturing method of the stamping structure according to the first embodiment. Then, as shown in FIG. 6, the fourth step is performed by performing an ashing process on the precursor composition layer using an ashing device 40 (atmospheric pressure plasma ashing device).
  • ashing device 40 atmospheric pressure plasma ashing device
  • the manufacturing method of the embossed structure according to the sixth embodiment performs the ashing process on the precursor composition layer in the same manner as the manufacturing method of the embossed structure according to the first embodiment. Since the fourth step of processing the remaining film is included, it is possible to form the embossed structure without the influence of the remaining film. In addition, since the precursor composition layer is subjected to an ashing process using atmospheric pressure plasma, a high-vacuum environment is not required when performing the fourth step, and thus expensive high-vacuum equipment is not required. In addition, it is possible to reduce the time required to perform the fourth step.
  • the ashing treatment using the atmospheric pressure plasma is performed on the precursor composition layer, so that the mean free path of the ashing gas is shortened. Since side etching occurs during the four steps (see FIG. 7), it is preferable to design a concavo-convex pattern in consideration of this. The same applies to the method for manufacturing the embossed structure according to the first to fifth embodiments.
  • FIG. 8 is a diagram for explaining an ashing device 40a used in the seventh embodiment.
  • FIG. 9 is a view for explaining the manufacturing method of the embossing structure according to the seventh embodiment.
  • FIG. 9A is a cross-sectional view of the precursor composition layer 20 just before the ashing treatment is performed on the precursor composition layer 20 in the fourth step
  • FIG. 9B is a precursor composition in the fourth step.
  • 3 is a cross-sectional view of the precursor composition layer 20 immediately after the ashing process is performed on the physical layer 20.
  • reference numeral 42 indicates a positive electrode
  • reference numeral 44 indicates a negative electrode.
  • the manufacturing method of the embossing structure according to the seventh embodiment basically includes the same steps as the manufacturing method of the embossing structure according to the sixth embodiment, but the contents of the fourth step are the molds according to the sixth embodiment. Different from the manufacturing method of the push structure. That is, in the manufacturing method of the embossed structure according to the seventh embodiment, as shown in FIG. 8, the ashing process using the low pressure plasma is performed on the precursor composition layer 20 using the ashing device 40 a (low pressure plasma ashing device). The fourth step is carried out by applying In the method for manufacturing the embossed structure according to the seventh embodiment, for example, an ashing process using reduced-pressure plasma is performed under a pressure condition of 1 Pa to 1000 Pa (preferably 10 Pa to 100 Pa). Moreover, in the manufacturing method of the stamping structure which concerns on Embodiment 7, as shown in FIG. 8, it is supposed that a 4th process is implemented on the conditions which applied the bias voltage.
  • the method for manufacturing the stamping structure according to the seventh embodiment differs from the method for manufacturing the stamping structure according to the sixth embodiment in the content of the fourth step, but the stamping structure according to the sixth embodiment.
  • it further includes a fourth step of treating the remaining film by subjecting the precursor composition layer to an ashing treatment, thereby forming an embossed structure free from the influence of the remaining film. It becomes possible to do.
  • the fourth step is performed with the bias voltage applied, the ashing gas collision energy increases, so that the ashing step can be performed at a high etching rate, and thus high productivity. Thus, it becomes possible to manufacture the embossed structure.
  • the mean free path of the gas used for ashing becomes longer than that under atmospheric pressure conditions.
  • ashing gas etching gas
  • FIG. 9 it is possible to reduce the ratio of etching (side etching) to the side surface portion of the embossing structure, and as a result, the embossing structure having high shape accuracy.
  • a stable glow discharge occurs even when a bias voltage is applied, the ashing process can be carried out stably at a high etching rate, and the mold can be stably produced with high productivity.
  • a push structure can be manufactured.
  • the reaction product generated by the reaction between the precursor composition layer and the reactive gas volatilizes and is easily removed, the ashing process can be stably performed at a high etching rate from this viewpoint. As a result, it is possible to stably manufacture the embossed structure with high productivity.
  • the method for manufacturing the embossed structure according to the seventh embodiment is the same as the method for manufacturing the embossed structure according to the sixth embodiment except for the fourth step. It has the effect applicable among the effects which the manufacturing method of a structure has.
  • FIG. 10 is a view for explaining the thin film transistor 100 according to the eighth embodiment.
  • 10A is a plan view of the thin film transistor 100
  • FIG. 10B is a cross-sectional view along A1-A1 in FIG. 10A
  • FIG. 10C is A2-A2 in FIG. 10A. It is sectional drawing.
  • the thin film transistor 100 includes an oxide conductor layer 140 including a source region 144, a drain region 146, and a channel region 142, and a channel region 142. And a gate insulating layer 130 formed between the gate electrode 120 and the channel region 142 and made of a ferroelectric material.
  • the channel region 142 is thinner than the source region 144 and the drain region 146.
  • the layer thickness of the channel region 142 is preferably less than or equal to 1 ⁇ 2 of the layer thickness of the source region 144 and the layer thickness of the drain region 146.
  • the gate electrode 120 is connected to the gate pad 122 exposed to the outside through the through hole 150.
  • the oxide conductor layer 140 is formed using an embossing technique.
  • the carrier concentration and the layer thickness of the channel region 142 are set to such values that the channel region 142 is depleted when an off control voltage is applied to the gate electrode 120. Yes.
  • the carrier concentration of the channel region 142 is in the range of 1 ⁇ 10 15 cm ⁇ 3 to 1 ⁇ 10 21 cm ⁇ 3
  • the layer thickness of the channel region 142 is in the range of 5 nm to 100 nm. .
  • 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 made of, for example, indium tin oxide (ITO), the gate insulating layer 130 is made of, for example, PZT (Pb (Zr x , Ti 1-x ) O 3 ), and the gate electrode 120 is made of, for example, An insulating substrate 110 made of nickel lanthanum oxide (LNO (LaNiO 3 )), which is a solid substrate, for example, is an insulating substrate in which an STO (SrTiO) layer is formed on the surface of a Si substrate via a SiO 2 layer and a Ti layer. Become.
  • ITO indium tin oxide
  • PZT Pb (Zr x , Ti 1-x ) O 3
  • the gate electrode 120 is made of, for example,
  • the thin film transistor 100 according to Embodiment 8 can be manufactured by the following manufacturing method of a thin film transistor. Hereinafter, it demonstrates in order of a process.
  • FIGS. 11 to 13 are views for explaining the thin film transistor manufacturing method according to the eighth embodiment.
  • FIGS. 11 (a) to 11 (f), FIGS. 12 (a) to 12 (f) and FIGS. 13 (a) to 13 (e) are process diagrams. In each process drawing, the figure shown on the left side is a figure corresponding to FIG. 10B, and the figure shown on the right side is a figure corresponding to FIG.
  • the functional liquid material used as the functional solid material which consists of metal oxide ceramics is prepared by heat-processing (1st process). Specifically, a solution (solvent: 2-methoxyethanol) containing a metal inorganic salt (lanthanum nitrate (hexahydrate) and nickel acetate (tetrahydrate)) is prepared.
  • a functional liquid material is applied to one surface of the insulating substrate 110 using a spin coating method (for example, 500 rpm for 25 seconds). Thereafter, the insulator substrate 110 is placed on a hot plate and dried at 60 ° C. for 1 minute to form a nickel lanthanum precursor composition layer 120 ′ (layer thickness: 300 nm) (second step).
  • a spin coating method for example, 500 rpm for 25 seconds.
  • the insulator substrate 110 is placed on a hot plate and dried at 60 ° C. for 1 minute to form a nickel lanthanum precursor composition layer 120 ′ (layer thickness: 300 nm) (second step).
  • the precursor composition layer 120 ′ is embossed at 150 ° C. to form an embossed structure (a convex layer thickness of 300 nm and a concave layer thickness of 50 nm) on the precursor composition layer 120 ′.
  • the pressure at the time of embossing is 5 MPa.
  • the stamping process is performed on the precursor composition layer that has obtained a high plastic deformation ability by heating to a second temperature in the range of 80 ° C. to 300 ° C.
  • the structure can be formed with high accuracy.
  • the entire surface of the precursor composition layer 120 ′ is ashed to completely remove the remaining film 120′z existing in a region other than the region corresponding to the gate electrode 120 as shown in FIG. (4th process).
  • the fourth step is performed using a wet etching apparatus.
  • the precursor composition layer 120 ′ is heat-treated at a high temperature (650 ° C., 10 minutes) using an RTA apparatus, so that the precursor composition layer 120 ′ has a function as shown in FIG. 11 (f).
  • a gate electrode 120 and a gate pad 122 made of a conductive solid material layer (nickel lanthanum oxide) are formed (fifth step).
  • the functional liquid material used as the functional solid material which consists of metal oxide ceramics (PZT) is prepared by heat-processing. Specifically, a solution containing a metal alkoxide (PZT sol-gel solution, manufactured by Mitsubishi Materials Corporation) is prepared as a functional liquid material (first step).
  • the above-described functional liquid material is applied on one surface of the insulating substrate 110 by using a spin coating method (for example, 2000 rpm for 25 seconds), and then the insulating substrate 110 is placed on a hot plate.
  • a functional solid material (PZT) precursor composition layer 130 ′ (layer thickness 300 nm) is formed by repeating the operation of drying at 250 ° C. for 5 minutes three times (see the second step, FIG. 12A). ).
  • a stamping structure corresponding to the through hole 150 is formed in the precursor composition layer 130 ′ by performing a stamping process on the precursor composition layer 130 ′ (third step).
  • the pressure at the time of embossing is 5 MPa.
  • the stamping process is performed on the precursor composition layer that has obtained a high plastic deformation ability by heating to a second temperature in the range of 80 ° C. to 300 ° C.
  • the structure can be formed with high accuracy.
  • the fourth step is performed using a reduced pressure plasma etching apparatus while introducing a reactive gas (for example, CF 4 gas and Ar gas) under a pressure condition of 10 Pa.
  • a reactive gas for example, CF 4 gas and Ar gas
  • the precursor composition layer 130 ′ is heat-treated at a high temperature (650 ° C., 10 minutes) using an RTA apparatus, so that the precursor composition layer 130 ′ has a function from the precursor composition layer 130 ′ as shown in FIG.
  • a gate insulating layer 130 made of a conductive solid material layer (PZT) is formed (fifth step).
  • the functional liquid material is doped with an impurity having a concentration such that the carrier concentration in the channel region 142 is in the range of 1 ⁇ 10 15 cm ⁇ 3 to 1 ⁇ 10 21 cm ⁇ 3 when completed.
  • the above-described functional liquid material is applied to one surface of the insulating substrate 110 using a spin coating method (for example, 2000 rpm ⁇ 25 seconds), and then The insulator substrate 110 is placed on a hot plate and dried at 150 ° C. for 3 minutes to form a functional solid material (ITO) precursor composition layer 140 ′ (layer thickness 300 nm) (second step).
  • a spin coating method for example, 2000 rpm ⁇ 25 seconds
  • the region corresponding to the channel region 142 is formed to be more convex than the region corresponding to the source region 144 and the region corresponding to the drain region 146.
  • the precursor composition layer 140 ′ is embossed by using a concavo-convex mold M4 (difference in height of 350 nm), so that the precursor composition layer 140 ′ has an embossed structure (a layer thickness of 350 nm of convex portions, (Recess layer thickness 100 nm) is formed (third step). Thereby, the layer thickness of the part which becomes the channel region 142 in the precursor composition layer 140 ′ becomes thinner than the other part.
  • the precursor composition layer 140 ′ is heated to 150 ° C. and is subjected to embossing using a mold heated to 150 ° C.
  • the pressure when embossing is about 4 MPa.
  • the concavo-convex mold M4 has a structure in which the region corresponding to the element isolation region 160 and the through hole 150 is more convex than the region corresponding to the channel region 142.
  • the remaining film 140′z of the precursor composition layer 140 ′ is formed in the region corresponding to (see FIG. 13C).
  • the fourth step is performed using a reduced pressure plasma etching apparatus while introducing a reactive gas (for example, CF 4 gas and Ar gas) under a pressure condition of 10 Pa.
  • a reactive gas for example, CF 4 gas and Ar gas
  • the precursor composition layer 140 ′ is subjected to a heat treatment (precursor composition layer 140 ′ is baked on a hot plate at 400 ° C. for 10 minutes, and then 650 ° C./30 using an RTA apparatus.
  • the precursor composition layer 140 ′ is heated under the conditions of a minute (first 15 minutes oxygen atmosphere, second half 15 minutes nitrogen atmosphere)), whereby an oxide conductor layer including a source region 144, a drain region 146, and a channel region 142 is obtained.
  • 140 (fifth step) and the thin film transistor 100 according to the eighth embodiment having the bottom gate structure as shown in FIG. 13E can be manufactured.
  • the carrier concentration can be increased because the oxide conductive material is used as the material constituting the channel region 142, and Since the ferroelectric material is used as the material constituting the gate insulating layer 130, it is possible to perform high-speed switching with a low driving voltage. It becomes possible to control at high speed with voltage.
  • the oxide conductor having the channel region 142 thinner than the source region 144 and the drain region 146 and having no influence of the remaining film Since the thin film transistor can be manufactured simply by forming the layer 140 using the method for manufacturing the embossed structure described above, the channel region, the source region, the drain region, and the like as in the conventional thin film transistor 900 are obtained. It is possible to manufacture a thin film transistor that is excellent as described above by using significantly less raw materials and manufacturing energy and in a shorter process than the conventional one. Become.
  • the oxide conductor layer 140, the gate electrode 120, and the gate insulating layer 130 are all formed without using a high vacuum process. It is possible to manufacture a thin film transistor without using it, and it is possible to manufacture an excellent thin film transistor as described above, using much less manufacturing energy than in the past, and in a shorter process than in the past. Become.
  • the carrier concentration and the layer thickness of the channel region 142 are values such that the channel region 142 is depleted when an off control voltage is applied to the gate electrode 120. Therefore, even when the carrier concentration of the oxide conductor layer is increased, the amount of current that flows during off-state can be sufficiently reduced, and a large current can be controlled with a low driving voltage while maintaining the required on / off ratio. It becomes.
  • FIG. 14 is a view for explaining the piezoelectric inkjet head 300 according to the ninth embodiment.
  • FIG. 14A is a cross-sectional view of the piezoelectric inkjet head 300
  • FIGS. 14B and 14C are diagrams illustrating a state in which the piezoelectric inkjet head 300 ejects ink.
  • a piezoelectric inkjet head 300 according to Embodiment 9 is attached to a cavity member 340 and one side of the cavity member 340 as shown in FIG.
  • a diaphragm 350 having a body element 320 formed thereon, a nozzle plate 330 attached to the other side of the cavity member 340 and having nozzle holes 332 formed therein, and defined by the cavity member 340, the diaphragm 350 and the nozzle plate 330.
  • the vibration plate 350 is provided with an ink supply port 352 that communicates with the ink chamber 360 and supplies ink to the ink chamber 360.
  • the diaphragm 350 is temporarily moved upward by applying an appropriate voltage to the piezoelectric element 320.
  • the vibration plate 350 is bent downward, whereby the ink droplet i is ejected from the ink chamber 360 through the nozzle hole 332. Thereby, vivid printing can be performed on the substrate.
  • a piezoelectric inkjet head 300 having such a structure includes a piezoelectric element 320 (first electrode layer 322, piezoelectric layer 324, and second electrode layer 326) and a cavity member. Both 340 are formed using the manufacturing method of the stamping structure of the present invention. Hereinafter, the manufacturing method of the piezoelectric inkjet head 300 according to the ninth embodiment will be described in the order of steps.
  • FIGS. 15 to 17 are views for explaining the method of manufacturing the piezoelectric inkjet head according to the eighth embodiment.
  • FIGS. 15 (a) to 15 (f), FIGS. 16 (a) to 16 (d) and FIGS. 17 (a) to 17 (e) are process diagrams.
  • first electrode layer 322 Formation of piezoelectric element 320 (1-1) Formation of first electrode layer 322 First, a functional liquid material that becomes a functional solid material made of metal oxide ceramics (nickel lanthanum oxide) is prepared by heat treatment. (First step). Specifically, a solution (solvent: 2-methoxyethanol) containing a metal inorganic salt (lanthanum nitrate (hexahydrate) and nickel acetate (tetrahydrate)) is prepared.
  • solvent 2-methoxyethanol
  • a functional liquid material is applied to one surface of the dummy substrate 310 by using a spin coating method (for example, 500 rpm for 25 seconds), and then the dummy substrate 310 is mounted.
  • a precursor composition layer 322 ′ (layer thickness: 300 nm) of a functional solid material (nickel lanthanum oxide) is formed by placing on a hot plate and drying at 60 ° C. for 1 minute (second step).
  • a precursor composition is used at 150 ° C. using a concavo-convex mold M8 (height difference of 300 nm) formed so that the region corresponding to the first electrode layer 322 is concave.
  • a concavo-convex mold M8 height difference of 300 nm
  • an embossed structure is formed in the precursor composition layer 322 ′ (third step).
  • the pressure at the time of embossing is 5 MPa.
  • the entire surface of the precursor composition layer 322 ′ is ashed to completely remove the remaining film existing in the region other than the region corresponding to the first electrode layer 322 as shown in FIG. (4th process).
  • the fourth step is performed using a wet etching apparatus.
  • the precursor composition layer 322 ′ is heat-treated at a high temperature (650 ° C., 10 minutes) by using an RTA apparatus, so that the precursor composition layer 326 ′ has a function as shown in FIG.
  • the first electrode layer 322 made of a conductive solid material layer (nickel lanthanum oxide) is formed (fifth step).
  • a functional liquid material to be a functional solid material made of metal oxide ceramics is prepared by heat treatment (first step). Specifically, a solution containing a metal alkoxide (PZT sol-gel solution, manufactured by Mitsubishi Materials Corporation) is prepared as a functional liquid material (first step).
  • a functional solid material (PZT) precursor composition layer 324 ′ (for example, a layer thickness of 1 ⁇ m to 10 ⁇ m) is formed by drying at 250 ° C. for 5 minutes (second step).
  • a concavo-convex mold M 9 (with a height difference of 500 nm) formed so that the region corresponding to the piezoelectric layer 324 is concave is used for the precursor composition layer 324 ′.
  • a stamping structure (for example, a layer thickness of 1 ⁇ m to 10 ⁇ m of convex portions and a layer thickness of 50 nm of concave portions) is formed in the precursor composition layer 324 ′ by performing a stamping process (third step).
  • the precursor composition layer 324 ′ is heated to 150 ° C. and embossed using a mold heated to 150 ° C.
  • the pressure at the time of embossing is about 4 MPa.
  • the entire surface of the precursor composition layer 324 ′ is subjected to ashing to completely remove the remaining film existing in a region other than the region corresponding to the piezoelectric layer 324 as shown in FIG. (4th process).
  • the fourth step is performed using a reduced pressure plasma etching apparatus while introducing a reactive gas (for example, CF 4 gas and Ar gas) under a pressure condition of 10 Pa.
  • a reactive gas for example, CF 4 gas and Ar gas
  • the precursor composition layer 324 ′ is heat-treated at a high temperature (650 ° C., 10 minutes) using an RTA apparatus, so that the precursor composition layer 324 ′ has a function as shown in FIG.
  • a piezoelectric layer 324 made of a conductive solid material layer (PZT) is formed (fifth step).
  • a functional liquid material to be a functional solid material made of metal oxide ceramics (nickel lanthanum oxide) is prepared by heat treatment (first step). Specifically, a solution (solvent: 2-methoxyethanol) containing a metal inorganic salt (lanthanum nitrate (hexahydrate) and nickel acetate (tetrahydrate)) is prepared.
  • a functional liquid material is applied on one surface of the dummy substrate 310 by using a spin coating method (for example, 500 rpm ⁇ 25 seconds), and then the dummy substrate 310. Is placed on a hot plate and dried at 60 ° C. for 1 minute to form a precursor composition layer 326 ′ (layer thickness 300 nm) of a functional solid material (nickel lanthanum oxide) (second step).
  • a spin coating method for example, 500 rpm ⁇ 25 seconds
  • a precursor composition is used at 150 ° C. using a concavo-convex mold M10 (height difference of 300 nm) formed so that the region corresponding to the second electrode layer 326 is concave.
  • a concavo-convex mold M10 height difference of 300 nm
  • an embossed structure is formed in the precursor composition layer 326 ′ (third step).
  • the pressure at the time of embossing is 5 MPa.
  • the entire surface of the precursor composition layer 326 ′ is subjected to ashing to completely remove the remaining film existing in a region other than the region corresponding to the second electrode layer 326 as shown in FIG. (4th process).
  • the fourth step is performed using a wet etching apparatus.
  • the precursor composition layer 326 ′ is heat-treated at a high temperature (650 ° C., 10 minutes) using an RTA apparatus, so that the precursor composition layer 326 ′ has a function from the precursor composition layer 326 ′ as shown in FIG.
  • a second electrode layer 326 made of a conductive solid material layer (nickel lanthanum oxide) is formed (fifth step).
  • the piezoelectric element 320 including the first electrode layer 322, the piezoelectric layer 324, and the second electrode layer 326 is completed.
  • vibration plate 350 and piezoelectric element 320 are bonded together using an adhesive.
  • a functional liquid material that becomes metal oxide ceramics is prepared by heat treatment (first step). Specifically, a solution containing metal alkoxide (isopropyl silicate (Si (OC 3 H 7 ) 4 )) is prepared as a functional liquid material.
  • the above-described functional liquid material is applied to one surface of the diaphragm 350 by using a spin coating method, and then the dummy substrate 310 is placed on a hot plate.
  • a precursor composition layer 340 ′ for example, a layer thickness of 10 ⁇ m to 20 ⁇ m
  • a functional solid material (quartz glass)
  • the precursor composition layer 340 ′ is embossed using a concavo-convex mold M11 having a shape corresponding to the ink chamber 360 or the like, thereby providing a precursor.
  • An embossing structure (for example, a layer thickness of 10 ⁇ m to 20 ⁇ m of a convex portion and a layer thickness of 50 nm of a concave portion) is formed on the composition layer 340 ′ (third step).
  • the precursor composition layer 340 ′ is heated to 150 ° C. and subjected to a pressing process using a mold heated to 150 ° C.
  • the pressure at the time of embossing is about 4 MPa.
  • the entire surface of the precursor composition layer 340 ′ is subjected to ashing to completely remove the remaining film existing in the region other than the region where the cavity member 340 is formed as shown in FIG. (4th process).
  • the fourth step is performed using an atmospheric pressure plasma etching apparatus while introducing a reactive gas (for example, CF 4 gas and Ar gas) under atmospheric pressure conditions.
  • a reactive gas for example, CF 4 gas and Ar gas
  • the precursor composition layer 340 ′ is heat-treated at a high temperature (650 ° C., 10 minutes) using an RTA apparatus, so that the precursor composition layer 340 ′ has a function as shown in FIG.
  • a cavity member 340 made of a conductive solid material layer (quartz glass) is formed.
  • the piezoelectric element 320 (the first electrode layer 322, the piezoelectric layer 324, and the second electrode layer 326) and the cavity Since the member 340 is formed using an embossing technique, a piezoelectric inkjet head can be manufactured using much less raw materials and manufacturing energy than in the past and in a shorter process than in the past. It becomes possible.
  • the mold is formed on the precursor composition layer that has obtained high plastic deformation ability by heat treatment at the second temperature in the range of 80 ° C. to 300 ° C.
  • a piezoelectric ink jet head having a desired performance because it includes a first electrode layer, a piezoelectric layer, a second electrode layer, and a cavity member that are formed by pressing and have a stamping structure formed with high accuracy. It becomes.
  • 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 all made of a liquid material. Since it is formed, it becomes possible to manufacture a piezoelectric ink jet head using an embossing technique, and the excellent piezoelectric ink jet head as described above is produced with significantly less raw materials and manufacturing energy than conventional ones. It becomes possible to manufacture using.
  • the piezoelectric element 320 (the first electrode layer 322, the piezoelectric layer 324, and the second electrode layer 326) and the cavity member 340 all use a high vacuum process.
  • the piezoelectric ink jet head excellent as described above can be manufactured using much less manufacturing energy than in the past and in a shorter process than in the past.
  • the cavity member is manufactured using an atmospheric pressure plasma apparatus without using a vacuum process, the manufacturing energy is significantly less than that in the past. It is possible to use and manufacture in a shorter process than before.
  • the piezoelectric inkjet head 300 since the piezoelectric layer and / or the cavity member is formed by using the method for manufacturing an embossing structure of the present invention, the piezoelectric inkjet head is used.
  • the head can be manufactured as an embossed structure free from the influence of the remaining film, using raw materials and manufacturing energy that are significantly less than in the past, and in a shorter process than in the past.
  • Example 1 is an example showing that the precursor composition layer can be completely removed by performing an ashing process using a reactive gas.
  • FIG. 18 is a diagram for explaining the ashing process in the first embodiment.
  • FIGS. 18A to 18E are process diagrams of the ashing process.
  • FIG. 18C shows the result of the ashing process under ashing condition 1
  • FIG. 18B shows the result of the ashing process under ashing condition 2.
  • FIG. 18C is a diagram illustrating a result of the ashing process under the ashing condition 3.
  • FIG. 19 is a diagram illustrating a result of the ashing process in the first embodiment.
  • the horizontal axis indicates the ashing time, and the vertical axis indicates the layer thickness of the precursor composition layer after the ashing treatment is performed on the precursor composition layer 520.
  • the region where the thickness of the precursor composition layer 520 is negative indicates that the insulating substrate 510 is etched.
  • FIG. 20 is a diagram illustrating a result of the ashing process in the first embodiment.
  • FIG. 20A is a view showing an SEM photograph at the boundary portion between the portion subjected to ashing and the portion not subjected to ashing
  • FIG. 20B shows the distribution of Ti (titanium) at the boundary portion.
  • FIG. 21 is a diagram illustrating a result of the ashing process in the first embodiment.
  • FIG. 21A is a diagram showing an EDX spectrum (energy dispersive X-ray spectrum) in the portion R1 that has not been subjected to the ashing process, and
  • FIG. 21A shows an EDX spectrum in the portion R2 that has been subjected to the ashing process.
  • FIG. 21A shows an EDX spectrum in the portion R2 that has been subjected to the ashing process.
  • a precursor composition layer 520 is formed by applying a sol-gel solution of TiO 2 by spin coating on an insulating substrate 510 having a SiO 2 layer formed on the surface of a Si substrate.
  • a sample obtained by drying an insulating substrate on which the composition layer 520 was formed at 200 ° C. for 5 minutes on a hot plate was used as a sample.
  • As the size and shape of the insulating substrate 510 for example, a rectangular parallelepiped having a length of 20 mm ⁇ width of 20 mm ⁇ height of 0.7 mm was used.
  • the layer thickness of the precursor composition layer 520 after drying at 200 ° C. is 75 nm.
  • Ashing treatment was applied to 520.
  • Ashing condition 1 is that the precursor composition layer 520 is subjected to an ashing process while flowing a reactive gas (CF 4 gas: flow rate 0.1 L / min) together with a carrier gas (He gas: flow rate 9 L / min),
  • the ashing condition 2 is applied to the precursor composition layer 520 while flowing Ar gas (flow rate 0.1 L / min) together with the carrier gas (He gas: flow rate 9 L / min), and the reactive gas (CF 4 gas: flow rate of 0.05 L / min) and Ar gas (flow rate of 0.05 L / min) together with carrier gas (He gas: flow rate of 9 L / min) are applied to the precursor composition layer 520 to perform ashing treatment.
  • CF 4 gas flow rate 0.1 L / min
  • Ar gas flow rate of 0.05 L / min
  • Ar gas flow rate of 0.05 L / min
  • the heat-resistant insulating tape M20 was peeled off from the surface of the precursor composition layer 320, and then a step meter “Alpha Step-500” manufactured by KLA Tencor Co., Ltd. was used. Then, the etching amount (step) from the surface of the precursor composition layer 320 was measured. Also, using a scanning electron microscope / energy dispersive X-ray analyzer “JSM-5510” manufactured by JEOL Ltd., SEM images and elements at the boundary between the part subjected to ashing and the part not subjected to ashing A mapping image (Ti) was acquired.
  • FIG. 20 a clear boundary line in the SEM image was observed between the portion subjected to ashing and the portion not subjected to ashing (see FIG. 20 (a)). Further, it was confirmed that the observed amount of Ti (titanium) was significantly reduced in the portion subjected to the ashing treatment as compared with the portion not subjected to the ashing treatment (FIG. 20B). reference.).
  • Example 2 when the ashing treatment was performed on the precursor composition layer before firing, the ashing treatment was performed on the precursor composition layer (metal oxide layer) after firing. It is an Example which shows that a precursor composition layer or a metal oxide layer can be etched at high speed.
  • FIG. 22 is a diagram illustrating a result of the ashing process in the second embodiment.
  • FIG. 22 (a) is a diagram showing the results of ashing when the precursor composition layer before firing is subjected to ashing
  • FIG. 22 (b) shows the precursor composition layer (metal) after firing. It is a figure which shows the result of the ashing process at the time of performing an ashing process with respect to (oxide layer).
  • Example 2 as in the case of Example 1, a TiO 2 sol-gel solution was applied by spin coating onto an insulating substrate 510 in which a SiO 2 layer was formed on the surface of a Si substrate. A layer (520) was formed, 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, and used as a sample (Sample 1). Sample 1 (heated at 600 ° C. with a RTA apparatus) and fired was used as a sample (sample 2).
  • the precursor composition layer after firing metal oxide
  • the precursor composition layer or the metal oxide layer can be removed by etching faster than when the ashing treatment is performed on the material layer (see FIG. 22B).
  • Example 3 is an example showing that when a predetermined ashing process is performed on a precursor composition layer including a residual film, the residual film can be completely removed.
  • FIG. 23 is a diagram for explaining the evaluation method in the third embodiment.
  • FIG. 23A to FIG. 23D are diagrams showing the procedure.
  • FIG. 24 is a diagram illustrating a result (AFM image or SPM image) of the ashing process according to the third embodiment.
  • FIG. 24A is a diagram showing a three-dimensional image of the sample surface after performing an ashing process using a scanning probe microscope (AFM or SPM), and
  • FIG. 24B is a diagram showing a cross-sectional image thereof. is there.
  • FIG. 25 is a diagram illustrating the results (IV characteristics) of the ashing process according to the third embodiment.
  • symbol A indicates the IV characteristic in Measurement Example 1
  • symbol B indicates the IV characteristic in Measurement Example 2.
  • Example 3 a MOD solution (0.4 mol) of TiO 2 was applied by spin coating (2000 rpm, 30 seconds) on a substrate 610 on which a Pt layer 614 was formed on the surface of a Si substrate 612 (precursor composition). A physical layer 620 was formed, and the substrate 610 on which the precursor composition layer 620 was formed was dried on a hot plate at 150 ° C. for 5 minutes as a sample (see FIG. 23A). As the size and shape of the substrate 610, for example, a rectangular parallelepiped of 20 mm long ⁇ 20 mm wide ⁇ 0.7 mm high was used.
  • a stamping structure including the remaining film 622 was formed on the precursor composition layer 620 by performing a stamping process (80 ° C. ⁇ 200 ° C. ⁇ 80 ° C., 10 MPa, 5 minutes) on the precursor composition layer 620. (See FIG. 23 (b)).
  • the residual film was processed by subjecting the precursor composition layer 620 formed with the embossed structure to an ashing process using an atmospheric pressure plasma (output 300 W, time 3 minutes, ashing gas: He + Ar + CF 4 ) (FIG. 23). (See (c).)
  • the remaining film is formed by subjecting the precursor composition layer including “the remaining film continuous in each remaining film forming region” to ashing treatment. It is completely removed.
  • the ashing process is performed on the precursor composition layer including the “residual film that is continuous in each residual film formation region”, thereby performing the fifth step to perform the residual process.
  • the remaining film is thinned to such a thickness that the film becomes sea-island structure.
  • the present invention is not limited to this.
  • FIG. 26 is a view for explaining the manufacturing method of the embossed structure according to the modification.
  • FIG. 26A is a cross-sectional view of the precursor composition layer 20 during the ashing process for the precursor composition layer 20 in the fourth step
  • FIG. 26B is the fourth step.
  • FIG. 26C is a cross-sectional view of the precursor composition layer 20 immediately after the ashing process is performed on the precursor composition layer 20, and
  • FIG. 26C is formed by heat-treating the precursor composition layer 20 in the fifth step.
  • FIG. 26A is a cross-sectional view of the precursor composition layer 20 during the ashing process for the precursor composition layer 20 in the fourth step
  • FIG. 26B is the fourth step
  • FIG. 26C is a cross-sectional view of the precursor composition layer 20 immediately after the ashing process is performed on the precursor composition layer 20, and
  • FIG. 26C is formed by heat-treating the precursor composition layer 20 in the fifth step.
  • the remaining film that is not continuous in each remaining film forming region for example, the sea-island structure 28
  • an ashing process is performed on the precursor composition layer 20 to form the remaining film. It may be completely removed (see FIGS. 26 (a) to 26 (c)).
  • the present invention has been described by taking a thin film transistor as an example.
  • the present invention has been described by taking a piezoelectric inkjet head as an example.
  • the present invention is not limited to this. Absent.
  • the present invention provides a thin film capacitor including a first electrode layer, a dielectric layer, a second electrode layer, and a wiring layer, an actuator including a piezoelectric layer, an electrode layer, and a wiring layer, and a lattice layer (metal oxide on a substrate).
  • the present invention is also applicable when manufacturing an optical device (for example, a reflective polarizing plate, a diffraction grating, or the like) including a layer or a metal layer.
  • Precursor composition layer (gate) Insulating layer), 140, ... Oxide conductor layer, 140 '... Precursor composition layer (oxide conductive layer), 142 ... Channel region, 144 ... Source region, 146 ... Drain region, 150 ... Through hole, 60 ... Element isolation region, 300 ... Piezoelectric ink jet head, 310 ... Dummy substrate, 320 ... Piezoelectric element, 322 ... First electrode layer, 324 ... Piezoelectric layer, 326 ... Second electrode layer, 330 ... Nozzle plate, 332 ... Nozzle hole, 340 ... Cavity member, 350 ... Vibration plate, 352 ... Ink supply port, 360 ... Ink chamber, 510 ... Insulating substrate, 520 ...
  • Precursor composition layer 522 ... Residual film, 610 ... Substrate, 612 ... Si substrate, 614 ... Pt layer, 622 ... precursor composition layer, 622 ... residual film, 630 ... region where residual film 622 was present, 940 ... channel layer, 950 ... source electrode, 960 ... drain electrode, M1, M2, M3, M4, M8, M9, M10, M11 ... uneven type, M20 ... heat resistant insulating tape, P ... plasma

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Abstract

La présente invention porte sur un procédé pour produire un corps structural pressé par matrice qui comprend, dans l'ordre suivant : une première étape de préparation d'une matière liquide qui devient un oxyde métallique ou un métal en étant soumise à un traitement thermique ; une deuxième étape de formation d'une couche de composition de précurseur faite d'une composition de précurseur dudit oxyde métallique ou dudit métal par application de la matière liquide sur une matière de base ; une troisième étape de formation, sur la couche de composition de précurseur, d'une structure pressée par matrice comprenant un film résiduel en soumettant la couche de composition de précurseur à un processus de pressage par matrice à l'aide d'une matrice ayant des saillies et des renfoncements ; et une quatrième étape de traitement de film résiduel en soumettant la couche de composition de précurseur, qui a la structure pressée par matrice formée sur celle-ci, à un traitement de calcination avec un plasma à pression atmosphérique ou un plasma à pression réduite ; et une cinquième étape de formation d'un corps structural pressé par matrice fait dudit oxyde métallique ou dudit métal à partir de la couche de composition de précurseur en soumettant la couche de composition de précurseur à un traitement thermique. Selon ce procédé de production de corps structural pressé par matrice, il est possible de produire différents dispositifs fonctionnels à l'aide de quantités de matières premières et d'énergie de production significativement plus petites en comparaison avec l'état de la technique classique et avec moins d'étapes en comparaison avec l'état de la technique classique.
PCT/JP2012/077323 2011-11-09 2012-10-23 Procédé de production de corps structural pressé par matrice, transistor en couches minces, condensateur en couches minces, actionneur, tête à jet d'encre piézoélectrique et dispositif optique WO2013069448A1 (fr)

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JP2011-245360 2011-11-09
JP2011245360A JP2013102072A (ja) 2011-11-09 2011-11-09 型押し構造体の製造方法、薄膜トランジスター、薄膜キャパシター、アクチュエーター、圧電式インクジェットヘッド及び光学デバイス

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WO2018066203A1 (fr) * 2016-10-05 2018-04-12 国立大学法人北陸先端科学技術大学院大学 Élément composite et son procédé de production

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JP6260326B2 (ja) * 2014-02-14 2018-01-17 凸版印刷株式会社 薄膜トランジスタ装置及びその製造方法
JP2016021298A (ja) * 2014-07-14 2016-02-04 東芝機械株式会社 導電性基板、導電性基板の製造装置および導電性基板の製造方法
DE102018132904B4 (de) * 2018-12-19 2020-10-29 RF360 Europe GmbH Piezoelektrisches Material und piezoelektrische Vorrichtung

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