TW201716626A - 配線圖案之製造方法、導電膜之製造方法、及電晶體之製造方法 - Google Patents

配線圖案之製造方法、導電膜之製造方法、及電晶體之製造方法 Download PDF

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TW201716626A
TW201716626A TW105125601A TW105125601A TW201716626A TW 201716626 A TW201716626 A TW 201716626A TW 105125601 A TW105125601 A TW 105125601A TW 105125601 A TW105125601 A TW 105125601A TW 201716626 A TW201716626 A TW 201716626A
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wiring pattern
layer
plating
manufacturing
substrate
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TW105125601A
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TWI702309B (zh
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小泉翔平
川上雄介
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尼康股份有限公司
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    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
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    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
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    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1841—Multistep pretreatment with use of metal first
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
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    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
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    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
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    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
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    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
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    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H10K10/486—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions the channel region comprising two or more active layers, e.g. forming pn heterojunctions

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  • Organic Chemistry (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Chemically Coating (AREA)
  • Thin Film Transistor (AREA)
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Abstract

本發明之課題在於提供一種不使用剝離製程並藉由無電解鍍敷獲得配線圖案之技術。本發明係一種配線圖案之製造方法，其特徵在於具有：基底層形成步驟，其形成包含無電解鍍敷用觸媒與樹脂之基底層；表層去除步驟，其將上述基底層之表層之至少一部分去除；及鍍敷層形成步驟，其進行無電解鍍敷而於上述進行了表層去除步驟之基底層形成鍍敷層。

Description

配線圖案之製造方法、導電膜之製造方法、及電晶體之製造方法
本發明係關於一種配線圖案之製造方法、導電膜之製造方法、及電晶體之製造方法。
已知有於製造配線圖案時使用無電解鍍敷之方法(例如專利文獻1)。
[先前技術文獻] [專利文獻]
[專利文獻1]日本特開2009-224705號公報
然而，由於在習知之方法中係使用抗蝕劑材料，並藉由剝離製程形成配線圖案，故而形成於經去除之抗蝕劑上之配線材料會與抗蝕劑一同被廢棄。
本發明之課題在於提供一種不使用剝離製程並藉由無電解鍍敷獲得配線圖案之技術。
本發明之態樣係一種配線圖案之製造方法，其具有：基底層形成步驟，其形成包含無電解鍍敷用觸媒與樹脂之基底層；表層去除步驟，其將上述基底層之表層之至少一部分去除；及鍍敷層形成步驟，其進行無電解鍍敷，而於進行了上述表層去除步驟之基底層形成鍍敷層。
又，本發明之另一態樣係一種導電膜之製造方法，其中，該導電膜係藉由上述配線圖案之製造方法而製造。
又，本發明之另一態樣係一種電晶體之製造方法，該電晶體包含閘極電極、源極電極、汲極電極、半導體層、及閘極絕緣層，該電晶體之製造方法之特徵在於：上述閘極電極、上述源極電極、及上述汲極電極中之至少1個係藉由上述配線圖案之製造方法而製造。
1‧‧‧基板
11A‧‧‧鍍敷基底層溶液
11B‧‧‧鍍敷基底層
12‧‧‧無電解鍍敷層
13A‧‧‧絕緣體層溶液
13B‧‧‧絕緣體層
14A‧‧‧鍍敷基底層溶液
14B‧‧‧鍍敷基底層
15A‧‧‧有機半導體溶液
15B‧‧‧有機半導體層
16‧‧‧源極電極
17‧‧‧汲極電極
21‧‧‧遮罩
22‧‧‧紫外線
23‧‧‧電漿
圖1係用以說明第1實施形態之配線圖案之製造方法之一例之剖視圖。
圖2係用以說明第2實施形態之電晶體之製造方法之一例之剖視圖(其1)。
圖3係用以說明第2實施形態之電晶體之製造方法之一例之剖視圖(其2)。
圖4係表示第3實施形態之電晶體之一例之圖。
圖5係用以說明第4實施形態之電晶體之製造方法之一例之剖視圖(其1)。
圖6係用以說明第4實施形態之電晶體之製造方法之一例之剖視圖(其2)。
圖7係用以說明第4實施形態之電晶體之製造方法之一例之剖視圖(其3)。
圖8係表示實施例1中之鍍敷基底層之光學顯微鏡像之圖。
圖9係表示實施例1中之鍍敷配線部之光學顯微鏡像之圖。
圖10係表示比較例1中之鍍敷配線部之光學顯微鏡像之圖。
圖11係表示實施例2中之鍍敷配線部之光學顯微鏡像之圖。
圖12係表示實施例3中之基板與閘極電極之光學顯微鏡像之圖。
圖13係表示實施例3中之形成絕緣體層後之基板與該基板之光學顯微鏡像之圖。
圖14係表示實施例3中之形成源極、汲極電極後之基板與電極之光學顯微鏡像之圖。
圖15係表示實施例3中之形成有機半導體層後之基板與該基板之光學顯微鏡像之圖。
圖16係表示實施例3中之電晶體之特性評價之圖。
<第1實施形態>
以下，一面參照圖式，一面對本發明之實施形態之一例進行說明。
圖1係用以說明第1實施形態之配線圖案之製造方法之一例之剖視圖。
(第1步驟)
首先，準備基板1。基板1可使用通常使用之基板材料。例如，可使用玻璃、聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚醚碸(PES)、聚醚醯亞胺、聚醚醚酮、聚苯硫醚、聚芳酯、聚醯亞胺、聚碳酸 酯(PC)、三乙酸纖維素(TAC)、乙酸丙酸纖維素(CAP)等。
又，準備鍍敷基底層溶液11A。鍍敷基底層溶液11A係使感光性樹脂之前驅物與作為無電解鍍敷用觸媒之金屬粒子分散於溶劑中而成之溶液。無電解鍍敷用觸媒例如包含鈀、銅、鎳、鐵、鉑、銀、釕或銠等之至少1種。無電解鍍敷用觸媒之平均粒徑例如可設為10nm以下。再者，所謂平均粒徑，係可將動態光散射法等公知之方法作為測定原理，並採用體積平均粒徑、面積平均粒徑、累積中位直徑(Median直徑)等求出之值。
再者，使用於鍍敷基底層溶液11A之樹脂只要為於特定條件下硬化者即可，並不限定於感光性樹脂。例如亦可為熱硬化性樹脂。以下，對使用感光性樹脂之情形進行說明。
對基板1塗佈鍍敷基底層溶液11A。作為塗佈方法，可使用旋轉塗佈、浸漬塗佈、噴塗、輥塗、模嘴塗佈、毛刷塗裝、柔版印刷或網版印刷等印刷法等通常所知之方法。再者，於塗佈鍍敷基底層溶液11A之前，亦可於大氣壓下對基板1照射將氧氣用作反應氣體之電漿。
其後，視需要進行熱處理而使鍍敷基底層溶液11A中之溶劑揮發。
(第2步驟)
繼而，經由以使鍍敷基底層溶液11A硬化成所需配線圖案之形狀之方式形成之遮罩21而對鍍敷基底層溶液11A照射紫外線22。由於鍍敷基底層溶液11A包含感光性樹脂，故而經紫外線22照射之部分藉由曝光而硬化。再者，使用於鍍敷基底層溶液11A之感光性樹脂不論是負型及正型均可，於使用正型之情形時，曝光部對顯影液之溶解性增大。
(第3步驟)
繼而，使一部分硬化後之鍍敷基底層溶液11A接觸於顯影液，藉此將未硬化部去除，獲得鍍敷基底層11B。作為顯影液，可使用水或有機溶劑等。再者，經去除之基底層溶液可藉由使用蒸發器(evaporator)等適當地調整溶液之濃度而再次用作基底層溶液。
(第4步驟)
繼而，將鍍敷基底層11B中之表層之至少一部分去除。所謂表層，係包含鍍敷基底層11B之表面之區域。作為表層之去除之手段，例如係對鍍敷基底層11B之表面照射將氧氣用作反應氣體之電漿23。又，例如亦可藉由使鹼溶液接觸於鍍敷基底層11B表面而將鍍敷基底層11B之表層之一部分去除。藉由該步驟，而去除鍍敷基底層11B之表面附近之一部分之樹脂。其後，視需要藉由水洗等手段而將鍍敷基底層11B之表面洗淨。
(第5步驟)
繼而，藉由針對鍍敷基底層11B形成無電解鍍敷層12而形成配線。作為無電解鍍敷層12之形成方法，例如藉由使基板1浸漬於鎳磷、銅、錫等無電解鍍敷液中，而使鍍敷金屬於鍍敷基底層11B中之無電解鍍敷用觸媒之表面析出。
藉由以上方法，可獲得適合導電膜或電晶體之配線圖案。於第4步驟中將鍍敷基底層11B中之表面附近之樹脂去除，藉此鍍敷之析出性提高。又，由於該步驟亦具有將鍍敷基底層溶液11A或鍍敷基底層11B之顯影後之殘渣去除之效果，故而鍍敷之選擇性提高，從而可更確實地進行配線圖案化。再者，於第1步驟中，亦可將使基板1之表面之潤濕性變 化之層預先設置於基板1上後塗佈鍍敷基底層溶液11A。例如，於使用包含水溶性樹脂之材料作為鍍敷基底層溶液之情形時，於使樹脂硬化成特定圖案之後，使用水作為用以去除未硬化部分之顯影液。此時，若預先設置親水膜作為使潤濕性變化之層，則殘渣與基板之間之部分對顯影液之浸透性提高而殘渣容易自基板剝離，故而可更有效率地進行殘渣去除。使潤濕性變化之層之材料根據所使用之基板、鍍敷基底層溶液、顯影液等適當決定即可。
於以上步驟中，可不使用剝離製程並利用無電解鍍敷形成配線圖案，從而可減少廢棄之配線材料。又，可藉由濕式製程形成配線圖案，因此無需真空蒸鍍或濺鍍等乾式製程所使用之大型之真空設備。又，無需高溫之製程，故而即便於軟化點較低之樹脂等基板上，亦可較佳地形成配線圖案。再者，可將本實施形態中所形成之配線用作電晶體之閘極電極。以下，使用圖2及圖3對於本實施形態中形成閘極電極後之電晶體之製造方法進行說明。
<第2實施形態>
圖2係用以說明第2實施形態之電晶體之製造方法之一例之剖視圖(其1)。圖3係用以說明第2實施形態之電晶體之製造方法之一例之剖視圖(其2)。該等圖用以說明於圖1所示之第1實施形態之配線圖案之製造方法中獲得閘極電極後之電晶體之製造步驟。
(第6步驟)
繼而，於基板1上塗佈絕緣體層溶液13A。絕緣體層溶液13A例如可使用紫外線硬化型丙烯酸樹脂、紫外線硬化型環氧樹脂、紫外線硬化型烯- 硫醇樹脂、及紫外線硬化型聚矽氧樹脂等之溶液。再者，使用於絕緣體層之材料只要成為於固定條件下硬化且具有絕緣性之材料即可，並不限定於紫外線硬化型樹脂材料。例如，亦可使用熱硬化型樹脂材料代替紫外線硬化型樹脂材料，但於本實施形態中對使用紫外線硬化型樹脂材料之情形進行說明。
(第7步驟)
繼而，經由遮罩21對絕緣體層溶液13A照射紫外線22，而使絕緣體層溶液13A硬化成所需形狀。此時，亦可視需要進行用以促進紫外線22之照射部之化學反應之熱處理。
(第8步驟)
繼而，將未硬化部分之絕緣體層去除。例如，藉由使基板1浸漬於溶解液中而將未硬化之絕緣體層溶液13A去除，獲得形成為所需圖案之絕緣體層13B。再者，於使用熱硬化型樹脂等材料作為絕緣體層溶液13A之情形時，藉由對特定部位加熱，亦可獲得形成為所需圖案之絕緣體層13B。
(第9步驟)~(第12步驟)
繼而，重疊於絕緣體層13B塗佈鍍敷基底層溶液14A。於(第9步驟)~(第12步驟)中，以與(第1步驟)~(第4步驟)相同之方式形成經圖案化之鍍敷基底層14B。
第12步驟之結果為，將圖案化為所需形狀之鍍敷基底層14B之表層之至少一部分去除。
(第13步驟)
繼而，重疊於鍍敷基底層14B形成配線。與第5步驟同樣地，使鍍敷 金屬於鍍敷基底層11B中之無電解鍍敷用觸媒之表面析出，獲得金屬配線。繼而，使金屬配線浸漬於置換鍍金浴中，而使金於金屬配線之表面置換析出。繼而，藉由使金屬配線浸漬於還原鍍金浴中，而以所需厚度之金被覆金屬配線之表面。於該步驟中獲得之金屬配線可用作源極電極16及汲極電極17。
再者，覆蓋金屬配線之材料並不限定於金，使用用作半導體之材料之具有適合HOMO/LUMO能階之功函數之金屬材料。於使用稠五苯等HOMO能階較高之半導體材料之情形時，較理想為利用金被覆金屬配線。作為使金屬積層獲得金屬配線之技術，由於記載於本申請人提出之申請即國際公開WO2013/024734號公報，故而省略說明。
(第14步驟)
繼而，於源極電極16與汲極電極17之間塗佈包含半導體材料之溶液15A。半導體材料例如可使用TIPS稠五苯(6,13-雙(三異丙基甲矽烷基乙炔基)稠五苯)所代表之可溶性稠五苯或P3HT(聚(3-己基噻吩-2,5-二基))等有機半導體、氧化鋅(ZnO)、IGZO或奈米碳管等無機半導體等，此處，作為使用有機半導體者進行說明。將包含使有機半導體溶解於可溶解有機半導體之有機溶劑中而獲得之半導體材料的溶液15A塗佈於源極電極16與汲極電極17之間。
(第15步驟)
繼而，使包含半導體材料之溶液15A中之溶劑蒸發，獲得有機半導體層15B。於該步驟中，既可將基板於常溫下設置特定時間並藉由自然乾燥而獲得有機半導體層15B，亦可藉由加熱使有機溶劑蒸發而獲得有機半導體層 15B。
再者，於該步驟中，係藉由濕式法而形成有機半導體層15B，但有機半導體層15B之形成方法並不限定於此，例如亦可使用昇華法或轉印法。
又，於對基板1進行加熱之情形時，基板1被加熱至軟化點以下之溫度。較理想為於120℃以下之溫度下進行加熱。此處，所謂軟化點，係指於對基板1進行了加熱之情形時基板1軟化而開始產生變形之溫度，例如可藉由依據JIS K7207(A法)之試驗方法而求出。
再者，於上述任一步驟中進行加熱之情形時，均較佳為加熱溫度之上限為基板1之軟化點。
根據本實施形態，可不使用剝離製程並利用無電解鍍敷形成電晶體之電極，從而可減少廢棄之配線材料。又，可利用於形成為輥狀之基板1上連續地製造配線圖案之所謂之輥對輥(Roll to Roll)方式進行配線圖案之製造，從而可期待製造步驟之簡化。
<第3實施形態>
圖4係表示第3實施形態之電晶體之一例之圖。於第2實施形態中，製造於有機半導體層15B之下部形成有源極電極16及汲極電極17之所謂之底部接觸型之電晶體。於第3實施形態中，藉由於有機半導體層15B之上部形成源極電極16及汲極電極17而製造所謂之頂部接觸型之電晶體。
即，於形成絕緣體層13B之後，將有機半導體溶液15A重疊塗佈於絕緣體層13B而獲得有機半導體層15B。繼而，重疊於有機半導體 層15B塗佈鍍敷基底層溶液14A，並使用遮罩21使鍍敷基底層溶液14A選擇性地硬化，而獲得鍍敷基底層11B。再者，為了不對有機半導體層15B施加負載，此處所使用之鍍敷基底層溶液14A較佳為使用利用了水溶性之感光性樹脂之基底層溶液。
繼而，藉由照射電漿23等方法，而將鍍敷基底層11B中之樹脂之至少一部分去除。其後，使鍍敷金屬於鍍敷基底層11B中之無電解鍍敷用觸媒之表面析出而獲得金屬配線。
以上，根據本實施形態，可獲得用於導電膜或電晶體之情形時更佳之配線圖案。
<第4實施形態>
繼而，對第4實施形態進行說明。於第2及第3實施形態中，對於源極電極16及汲極電極17之下部形成有閘極電極之所謂之底部閘極型之電晶體之製造步驟進行了說明。於本實施形態中，使用圖5~圖7對使用與第2及第3實施形態相同之材料於源極電極16及汲極電極17之上部形成有閘極電極之所謂之頂部閘極型之電晶體之製造步驟進行說明。
圖5係用以說明第4實施形態之電晶體之製造方法之一例之剖視圖(其1)，圖6係用以說明第4實施形態之電晶體之製造方法之一例之剖視圖(其2)，圖7係用以說明第4實施形態之電晶體之製造方法之一例之剖視圖(其3)。
(第1步驟)~(第5步驟)
於(第1步驟)至(第5步驟)中，以與第1實施形態中之(第1步驟)至(第5步驟)相同之方式形成配線圖案。再者，於圖5之(第5步驟) 所表示之基板1上形成有2個電極。於本實施形態中，以鍍敷基底層11B成為用以形成源極電極16及汲極電極17之基底膜之方式使鍍敷基底層溶液11A選擇性地硬化。其後，進行無電解鍍敷而於鍍敷基底層11B上形成配線，藉此獲得源極電極16及汲極電極17。再者，與上述實施形態同樣地，源極電極16及汲極電極17亦可為以金被覆金屬配線而成者。
(第6步驟)
繼而，於源極電極16與汲極電極17之間塗佈包含半導體材料之溶液15A。
(第7步驟)
繼而，使包含半導體材料之溶液15A中之溶劑蒸發而獲得有機半導體層15B。
(第8步驟)
繼而，於基板1上塗佈絕緣體層溶液13A。
(第9步驟)
繼而，對於第8步驟中塗佈之絕緣體層溶液13A照射紫外線而使其硬化，獲得絕緣體層13B。此處，對針對經塗佈之絕緣體層溶液13A整面照射紫外線之例進行說明，但亦可與第2實施形態之(第7步驟)及(第8步驟)同樣地，使用遮罩照射紫外線而獲得具有所需圖案之絕緣體層13B。
(第10步驟)~(第14步驟)
繼而，重疊於絕緣體層13B塗佈鍍敷基底層溶液14A。於(第10步驟)至(第14步驟)中，可獲得以與第1實施形態中之(第1步驟)至(第5步驟)相同之方式形成配線圖案且(第14步驟)之結果為於源極電極16 及汲極電極17之上部配置有閘極電極之頂部閘極型之電晶體。
<實施例1>
利用圖1所示之配線圖案之製造方法製造鍍敷配線。首先，準備PET膜(COSMOSHINE A-4100(無塗佈)：東洋紡織股份有限公司)作為基板1。又，分別準備作為使用於鍍敷基底層11B之感光性樹脂之水溶性之感光性樹脂(BIOSURFINE-AWP-MRH(東洋紡織股份有限公司))、分散有作為無電解鍍敷用觸媒之鈀(Pd)之微粒子之奈米Pd分散液(Pd濃度10mM：Renaissance Energy Research股份有限公司製造)。鍍敷基底層溶液11A係以1：1：1之重量比使BIOSURFINE-AWP-MRH、奈米Pd分散液與水混合而製備。
繼而，為了提高基板1與形成於基板1上之鍍敷基底層之密接性，而使用氧氣於大氣壓下對基板1照射電漿23。其後，藉由旋轉塗佈對基板1塗佈鍍敷基底層溶液11A。旋轉塗佈之條件設為2000rpm、30秒。
繼而，以60℃將基板1加熱3分鐘。其後，經由遮罩21照射24rmJ/cm2之紫外線22。繼而，使基板1浸漬於純水中，並進行1分鐘28kHz之超音波處理，藉此去除未曝光部。
圖8係表示實施例1中之鍍敷基底層11B之光學顯微鏡像之圖。圖8(A)係表示L/S=30μm/30μm之圖案之圖，圖8(B)係表示L/S=8μm/8μm之圖案之圖。深色部分為鍍敷基底膜，淺色部分為配線部分。確認描繪出L/S=8μm/8μm之微細之圖案。
繼而，使用氧氣於大氣壓下對基板1進行電漿處理，藉此將鍍敷基底層11B之表層之樹脂去除。其後，使基板1浸漬於純水中，並進 行1分鐘28kHz之超音波處理。繼而，使基板1於無電解NiP鍍敷浴(Melplate NI-867：Meltex公司製造)中浸漬40秒。
圖9係表示實施例1中之鍍敷配線部之光學顯微鏡像之圖。圖9(A)係表示L/S=30μm/30μm之圖案之圖，圖9(B)係表示L/S=8μm/8μm之圖案之圖。圖9(A)及圖9(B)均係淺色部分為配線部分。配線部分與配線以外之部分之對比度變得明確，從而得知被適當地圖案化。
<比較例1>
於本比較例中，與實施例1同樣地對鍍敷基底層11B進行圖案化，但其後與實施例1不同，並不對基板1進行利用氧氣而進行之電漿處理。關於其他步驟與實施例1相同。
圖10係表示比較例1中之鍍敷配線部之光學顯微鏡像之圖。圖10(A)係表示L/S=30μm/30μm之圖案之圖，圖10(B)係表示L/S=8μm/8μm之圖案之圖，圖10(A)及圖10(B)均係淺色部分為配線部分。於圖10(B)中尤其顯著，配線以外之部分局部變白。該情況表示於配線以外之部分亦析出鍍敷金屬。結果得知並未適當地圖案化。
<實施例2>
於本實施例中，與實施例1同樣地對鍍敷基底層11B進行圖案化後，與實施例1不同，並不進行利用氧氣而進行之電漿處理，而是使基板1浸漬於0.2mol/L、70℃之氫氧化鉀水溶液中。關於其他步驟與實施例1相同。
圖11係表示實施例2中之鍍敷配線部之光學顯微鏡像之圖。圖11表示L/S=30μm/30μm之圖案，淺色部分為配線部分。配線部 分與配線以外之部分之對比度變得明確，從而得知即便於浸漬於氫氧化鉀溶液中之情形時，與進行電漿處理之情形同樣地，亦被適當地圖案化。
<實施例3>
(閘極電極之形成)
與實施例1同樣地，於基板1上形成NiP鍍敷配線，並將其設為閘極電極。其後，為了將無電解NiP鍍敷浴所產生之水分去除，以105℃將基板1加熱20分鐘。
圖12係表示實施例3中之基板1與閘極電極之光學顯微鏡像之圖。圖12(A)係表示於實施例3中形成閘極電極後之基板1之照片。圖12(B)係閘極電極之光學顯微鏡像。於基板1上適當地形成有閘極電極。
(絕緣體層13B之形成)
繼而，使用氧氣於大氣壓下對基板1進行電漿照射。繼而，利用浸漬塗佈將絕緣膜樹脂溶液塗佈於基板1上。絕緣膜樹脂溶液使用利用環己酮將絕緣性之樹脂材料(SU8 3005：日本化藥公司製造)稀釋成2倍而成者。又，浸漬塗佈之上提速度設為1mm/s。
繼而，以105℃將基板1加熱10分鐘。其後，經由光罩21照射200mJ/cm2之紫外線22，並以105℃加熱60分鐘。繼而，使基板1含浸於PGMEA(丙二醇1-單甲醚2-乙酸酯)中，使絕緣體層13B中之紫外線22之未曝光部分之區域溶解。其後，以105℃將基板1加熱30分鐘，形成厚度為1μm之絕緣體層13B。
圖13係表示實施例3中之形成絕緣體層13B後之基板1與該基板1之光學顯微鏡像之圖。圖13(A)係形成絕緣體層13B後之基板1 之照片，並且由虛線所包圍之區域為形成有絕緣體層13B之區域。再者，虛線係為了使形成有絕緣體層13B之區域與其他區域之交界明確而事後重疊於照片者，並非映入照片之圖像之一部分。圖13(B)係形成絕緣體層13B後之基板1之光學顯微鏡像。
(源極電極16及汲極電極17之形成)
於與實施例1同樣地於絕緣體層13B上形成NiP之鍍敷配線之後，使基板1含浸於置換Au鍍敷浴(Supermex#255：N.E.CHEMCAT製造)中1分鐘。繼而，使基板1含浸於還原Au鍍敷浴(Supermex#880：N.E.CHEMCAT製造)中1分鐘。其後，為了將水分去除，而以105℃使基板1乾燥60分鐘。
圖14係表示實施例3中之形成源極電極16及汲極電極17後之基板1與電極之光學顯微鏡像之圖。圖14(A)係形成源極電極16及汲極電極17後之基板1之照片，圖14(B)係電極之光學顯微鏡像。以成為通道長20μm、通道寬500nm之方式形成源極電極16及汲極電極17。
(有機半導體層15B之形成)
繼而，於通道區域中滴加2wt%TIPS稠五苯-甲苯溶液並使之成膜而製作有機電晶體。
圖15係表示實施例3中之形成有機半導體層15B後之基板1與該基板1之光學顯微鏡像之圖。圖15(A)係形成有機半導體層15B後之基板1之照片，圖15(B)係有機半導體層15B之光學顯微鏡像。得知於通道區域上形成了有機半導體層15B。
圖16係表示實施例3中之電晶體之特性評價之圖。電晶體 特性評價係使用半導體參數分析器(4200-SCS：TFF Keithley Instruments公司製造)而進行。圖16(A)係表示於實施例3中所製作之底部閘極、底部接觸型有機電晶體之傳遞特性之圖，圖16(B)係表示該電晶體之輸出特性之圖。又，該電晶體表示出遷移率1.2×103cm2/Vs、On/Off比1.9×105之相對良好之特性。
(評價)
以上，未使用剝離製程並利用無電解鍍敷成功地製作了配線圖案及電晶體。根據本實施形態，可於大氣壓下實施所有步驟。又，任一製程均可於100℃左右之溫度下進行，故而即便於基板1使用PET之情形時，亦可於基板1之軟化點以下之溫度下製作較佳之電晶體。又，由於係使用光進行圖案化，故而可獲得高精度之配線圖案。
1‧‧‧基板
11A‧‧‧鍍敷基底層溶液
11B‧‧‧鍍敷基底層
12‧‧‧無電解鍍敷層
21‧‧‧遮罩
22‧‧‧紫外線
23‧‧‧電漿

Claims (12)

  1. 一種配線圖案之製造方法，其具有：基底層形成步驟，其形成包含無電解鍍敷用觸媒與樹脂之基底層；表層去除步驟，其將上述基底層之表層之至少一部分去除；及鍍敷層形成步驟，其進行無電解鍍敷而於進行了上述表層去除步驟之基底層形成鍍敷層。
  2. 如申請專利範圍第1項之配線圖案之製造方法，其中，於上述基底層形成步驟中，塗佈包含上述無電解鍍敷用觸媒與上述樹脂之前驅物的溶液，並使上述樹脂之前驅物硬化成特定圖案，藉此形成上述基底層。
  3. 如申請專利範圍第2項之配線圖案之製造方法，其中，上述樹脂之前驅物藉由照射包含特定波長之光的光而硬化。
  4. 如申請專利範圍第3項之配線圖案之製造方法，其中，經由具有與上述特定圖案對應之開口部之遮罩照射上述包含特定波長之光的光，藉此使上述樹脂之前驅物硬化。
  5. 如申請專利範圍第2至4中任一項之配線圖案之製造方法，其中，上述樹脂之前驅物為水溶性。
  6. 如申請專利範圍第1至5中任一項之配線圖案之製造方法，其中，於上述表層去除步驟中，對上述基底層之表面照射電漿。
  7. 如申請專利範圍第1至5中任一項之配線圖案之製造方法，其中，於上述表層去除步驟中，使鹼溶液接觸於上述基底層。
  8. 如申請專利範圍第1至7中任一項之配線圖案之製造方法，其中， 上述無電解鍍敷用觸媒包含鈀、銅、鎳、鐵、鉑、銀之至少1種。
  9. 如申請專利範圍第1至8中任一項之配線圖案之製造方法，其中，上述基底層形成步驟係於包含樹脂材料之基板上形成上述基底層。
  10. 如申請專利範圍第9項之配線圖案之製造方法，其中，上述基底層形成步驟、上述表層去除步驟及上述鍍敷層形成步驟係以低於上述基板之軟化點之溫度進行。
  11. 一種導電膜之製造方法，其中，該導電膜係使用申請專利範圍第1至10中任一項之配線圖案之製造方法進行製造。
  12. 一種電晶體之製造方法，其係包含閘極電極、源極電極、汲極電極、半導體層、及閘極絕緣層的電晶體之製造方法，其特徵在於：藉由申請專利範圍第1至10中任一項之配線圖案之製造方法而製造上述閘極電極、上述源極電極、及上述汲極電極中之至少1個。
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