TWI648795B - Method of producing metal oxide film - Google Patents

Method of producing metal oxide film Download PDF

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TWI648795B
TWI648795B TW103143397A TW103143397A TWI648795B TW I648795 B TWI648795 B TW I648795B TW 103143397 A TW103143397 A TW 103143397A TW 103143397 A TW103143397 A TW 103143397A TW I648795 B TWI648795 B TW I648795B
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metal oxide
oxide film
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高田真宏
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富士軟片股份有限公司
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Abstract

本發明提供一種金屬氧化物膜的製造方法及其應用，所述金屬氧化物膜的製造方法包括：前驅物膜形成步驟，將含有溶劑及至少含有銦作為金屬成分的溶液塗佈於基板上而形成金屬氧化物前驅物膜；轉化步驟，於將所述金屬氧化物前驅物膜加熱的狀態下，在氧濃度為80000ppm以下的氣體環境下進行紫外線照射，藉此使所述金屬氧化物前驅物膜轉化為金屬氧化物膜。 The present invention provides a method for producing a metal oxide film, comprising: a precursor film forming step of applying a solvent and a solution containing at least indium as a metal component to a substrate; Forming a metal oxide precursor film; and performing a conversion step of irradiating the metal oxide precursor film in a gas atmosphere having an oxygen concentration of 80,000 ppm or less, thereby causing the metal oxide precursor The membrane is converted to a metal oxide film.

Description

金屬氧化物膜的製造方法 Method for producing metal oxide film

本發明是有關於一種金屬氧化物膜的製造方法、金屬氧化物膜、薄膜電晶體及電子元件。 The present invention relates to a method for producing a metal oxide film, a metal oxide film, a thin film transistor, and an electronic device.

作為氧化物半導體膜或氧化物導體膜的金屬氧化物膜已於利用真空成膜法的製造中加以實用，現在正受到關注。 A metal oxide film which is an oxide semiconductor film or an oxide conductor film has been put into practical use in the production by a vacuum film formation method, and is now attracting attention.

另一方面，為了簡便地於低溫且大氣壓下形成具有高的半導體特性的氧化物半導體膜，與利用液相製程製作氧化物半導體膜有關的研究開發正盛行。最近，報告有以下方法：將溶液塗佈於基板上，使用紫外線，藉此於150℃以下的低溫下製造具有高的傳輸特性的薄膜電晶體(Thin Film Transistor，TFT)(參照「自然(Nature)」，489(2012)128.)。 On the other hand, in order to easily form an oxide semiconductor film having high semiconductor characteristics at a low temperature and an atmospheric pressure, research and development related to the production of an oxide semiconductor film by a liquid phase process are prevailing. Recently, there has been reported a method of applying a solution to a substrate and using ultraviolet rays to produce a thin film transistor (TFT) having high transmission characteristics at a low temperature of 150 ° C or lower (refer to "Nature (Nature ), 489 (2012) 128.).

又，揭示有以下方法：將含有硝酸鹽等的溶液塗佈於基材上後，於150℃左右進行加熱而使溶劑揮發，藉此形成含有金屬氧化物半導體的前驅物的薄膜，其後，於氧的存在下照射紫外光(Ultraviolet，UV)，藉此製造金屬氧化物半導體(參照專利文獻1：國際公開第2009/011224號)。 Further, a method in which a solution containing a nitrate or the like is applied onto a substrate, and then heated at about 150 ° C to volatilize the solvent to form a film containing a precursor of the metal oxide semiconductor, and thereafter, A metal oxide semiconductor is produced by irradiating ultraviolet light (Ultraviolet, UV) in the presence of oxygen (see Patent Document 1: International Publication No. 2009/011224).

另一方面，揭示有以下方法：使用廉價的硝酸鹽或乙酸 鹽等的溶液形成氧化物半導體前驅物膜，並藉由對氧化物半導體前驅物膜進行熱處理、微波照射、或UV臭氧法而轉換為半導體膜(參照專利文獻2：國際公開第2009/081862號)。 On the other hand, the following methods are disclosed: using inexpensive nitrate or acetic acid The oxide semiconductor precursor film is formed into a semiconductor film by heat treatment, microwave irradiation, or UV ozone method (see Patent Document 2: International Publication No. 2009/081862). ).

又，提出有以下方法：以硝酸銦等作為起始原料，利用1000℃火焰進行熱分解，藉此製作金屬氧化物半導體粒子，使用分散有金屬氧化物半導體粒子的分散液製造氧化物半導體膜(參照專利文獻3：日本專利特開2012-94841號公報)。 In addition, a method of producing an oxide semiconductor film by dispersing indium nitrate or the like as a starting material by thermal decomposition at a flame of 1000 ° C to prepare metal oxide semiconductor particles and using a dispersion in which metal oxide semiconductor particles are dispersed is proposed ( Reference Patent Document 3: Japanese Patent Laid-Open Publication No. 2012-94841.

又，提出有以下方法：於大氣中對以硝酸銦等作為原料而塗佈形成的金屬氧化物凝膠膜進行UV照射，藉此轉化為金屬氧化物膜(參照專利文獻4：日本專利特開2000-247608號公報)。 Moreover, there has been proposed a method in which a metal oxide gel film formed by coating with indium nitrate or the like as a raw material is subjected to UV irradiation in the atmosphere to be converted into a metal oxide film (refer to Patent Document 4: Japanese Patent Laid-Open) Bulletin 2000-247608).

又，提出有以下方法：對於氧化物半導體前驅物膜，於50℃~200℃的環境下進行UV照射後，進行電漿處理而製成氧化物半導體膜(參照專利文獻5：日本專利特開2013-197539號公報)。 In addition, the oxide semiconductor film is subjected to UV irradiation in an environment of 50 ° C to 200 ° C and then subjected to plasma treatment to form an oxide semiconductor film (refer to Patent Document 5: Japanese Patent Laid-Open) Bulletin 2013-197539).

於所述的專利文獻1~專利文獻5所記載的半導體膜的製造方法中，於大氣環境下進行向半導體膜的轉化處理。本發明的發明者對轉化為氧化物半導體膜時的氣體環境進行了銳意研究，結果發現，藉由將常識上預想為高者為宜的氧濃度調低，可改善半導體膜的電特性。 In the method for producing a semiconductor film described in Patent Document 1 to Patent Document 5, the conversion treatment to the semiconductor film is performed in an atmosphere. The inventors of the present invention conducted intensive studies on the gas atmosphere when converting into an oxide semiconductor film, and as a result, found that the electrical characteristics of the semiconductor film can be improved by lowering the oxygen concentration which is expected to be higher in general knowledge.

本發明的目的在於提供一種可容易地製造具有導體或半導體特性的金屬氧化物膜的金屬氧化物膜的製造方法、以及電 特性優異的金屬氧化物膜、薄膜電晶體及電子元件。 An object of the present invention is to provide a method for producing a metal oxide film which can easily produce a metal oxide film having a conductor or a semiconductor property, and an electric method Metal oxide film, thin film transistor and electronic components with excellent properties.

為了達成所述目的，提供以下的發明。 In order to achieve the object, the following invention is provided.

<1>一種金屬氧化物膜的製造方法，其包括以下步驟：前驅物膜形成步驟，將含有溶劑及至少含有銦作為金屬成分的溶液塗佈於基板上而形成金屬氧化物前驅物膜；轉化步驟，於將金屬氧化物前驅物膜加熱的狀態下，在氧濃度為80000ppm以下的氣體環境下進行紫外線照射，藉此使金屬氧化物前驅物膜轉化為金屬氧化物膜。 <1> A method for producing a metal oxide film, comprising the steps of: a precursor film forming step of applying a solvent and a solution containing at least indium as a metal component on a substrate to form a metal oxide precursor film; In the step of heating the metal oxide precursor film, ultraviolet irradiation is performed in a gas atmosphere having an oxygen concentration of 80,000 ppm or less, thereby converting the metal oxide precursor film into a metal oxide film.

<2>如<1>所記載的金屬氧化物膜的製造方法，其中將紫外線照射中的基板的溫度保持為超過120℃。 <2> The method for producing a metal oxide film according to <1>, wherein the temperature of the substrate during the ultraviolet irradiation is maintained at more than 120 °C.

<3>如<1>或<2>所記載的金屬氧化物膜的製造方法，其中將紫外線照射中的基板的溫度保持為低於200℃。 <3> The method for producing a metal oxide film according to <1>, wherein the temperature of the substrate during ultraviolet irradiation is kept below 200 °C.

<4>如<1>至<3>中任一項所記載的金屬氧化物膜的製造方法，其中所述溶液中所含的銦為銦離子。 The method for producing a metal oxide film according to any one of the above aspects, wherein the indium contained in the solution is indium ions.

<5>如<1>至<4>中任一項所記載的金屬氧化物膜的製造方法，其中溶液含有硝酸根離子。 The method for producing a metal oxide film according to any one of <1> to <4> wherein the solution contains nitrate ions.

<6>如<1>至<5>中任一項所記載的金屬氧化物膜的製造方法，其中於轉化步驟中，進行紫外線照射的氣體環境的氧濃度為30000ppm以下。 The method for producing a metal oxide film according to any one of the above aspects, wherein in the conversion step, the oxygen concentration in the gas atmosphere in which the ultraviolet ray is irradiated is 30,000 ppm or less.

<7>如<1>至<6>中任一項所記載的金屬氧化物膜的製造方法，其中將紫外線照射中的基板升溫或降溫的速度設為 ±0.5℃/min以內。 The method for producing a metal oxide film according to any one of the above aspects, wherein the temperature at which the substrate is heated or lowered during the ultraviolet irradiation is set to a speed Within ±0.5 °C/min.

<8>如<1>至<7>中任一項所記載的金屬氧化物膜的製造方法，其中溶液中所含的金屬成分的50atom%以上為銦。 The method for producing a metal oxide film according to any one of the above aspects, wherein a 50 atom% or more of the metal component contained in the solution is indium.

<9>如<1>至<8>中任一項所記載的金屬氧化物膜的製造方法，其中溶液為至少溶解有硝酸銦的溶液。 The method for producing a metal oxide film according to any one of <1> to <8> wherein the solution is a solution in which at least indium nitrate is dissolved.

<10>如<1>至<9>中任一項所記載的金屬氧化物膜的製造方法，其中溶液更含有選自鋅、錫、鎵及鋁中的至少一種金屬成分。 The method for producing a metal oxide film according to any one of the above aspects, wherein the solution further contains at least one metal component selected from the group consisting of zinc, tin, gallium, and aluminum.

<11>如<1>至<10>中任一項所記載的金屬氧化物膜的製造方法，其中溶劑為甲醇、甲氧基乙醇、或水。 The method for producing a metal oxide film according to any one of <1> to <10> wherein the solvent is methanol, methoxyethanol or water.

<12>如<1>至<11>中任一項所記載的金屬氧化物膜的製造方法，其中溶液中的金屬成分的濃度為0.01mol/L以上且1.0mol/L以下。 The method for producing a metal oxide film according to any one of the above aspects, wherein the concentration of the metal component in the solution is 0.01 mol/L or more and 1.0 mol/L or less.

<13>如<1>至<12>中任一項所記載的金屬氧化物膜的製造方法，其中轉化步驟中的紫外線照射是藉由以10mW/cm2以上的照度對金屬氧化物前驅物膜照射波長為300nm以下的紫外線而進行。 The method for producing a metal oxide film according to any one of <1> to <12> wherein the ultraviolet ray irradiation in the conversion step is performed by illuminating the metal oxide precursor at an illuminance of 10 mW/cm 2 or more. The film is irradiated with ultraviolet rays having a wavelength of 300 nm or less.

<14>如<1>至<13>中任一項所記載的金屬氧化物膜的製造方法，其中用於紫外線照射的光源為低壓水銀燈。 The method for producing a metal oxide film according to any one of the above aspects, wherein the light source for ultraviolet irradiation is a low pressure mercury lamp.

<15>如<1>至<14>中任一項所記載的金屬氧化物膜的製造方法，其中前驅物膜形成步驟是將溶液塗佈於基板上，將基板加熱至35℃以上且100℃以下而將其乾燥，藉此形成金屬 氧化物前驅物膜。 The method for producing a metal oxide film according to any one of the above aspects, wherein the precursor film forming step is to apply a solution onto the substrate, and heat the substrate to 35 ° C or higher and 100. Drying below °C to form a metal Oxide precursor film.

<16>如<1>至<15>中任一項所記載的金屬氧化物膜的製造方法，其中於前驅物膜形成步驟中，藉由選自噴墨法、分配器法、凸版印刷法、及凹版印刷法中的至少一種塗佈法來將溶液塗佈於基板上。 The method for producing a metal oxide film according to any one of the above aspects, wherein the precursor film forming step is selected from the group consisting of an inkjet method, a dispenser method, and a letterpress printing method. And at least one coating method in the gravure printing method to apply the solution onto the substrate.

<17>一種金屬氧化物膜，其是使用如<1>至<16>中任一項所記載的金屬氧化物膜的製造方法而製作。 <17> A metal oxide film produced by the method for producing a metal oxide film according to any one of <1> to <16>.

<18>如<17>所記載的金屬氧化物膜，其中金屬氧化物膜中所含的金屬成分的50atom%以上為銦。 <18> The metal oxide film according to <17>, wherein 50 atom% or more of the metal component contained in the metal oxide film is indium.

<19>如<17>或<18>所記載的金屬氧化物膜，其是半導體膜。 <19> The metal oxide film according to <17> or <18> which is a semiconductor film.

<20>一種薄膜電晶體，其具有含有如<19>所記載的金屬氧化物膜的活性層、源極電極、汲極電極、閘極絕緣膜及閘極電極。 <20> A thin film transistor comprising an active layer, a source electrode, a gate electrode, a gate insulating film, and a gate electrode containing the metal oxide film according to <19>.

<21>一種電子元件，其具備如<20>所記載的薄膜電晶體。 <21> An electronic component comprising the thin film transistor according to <20>.

根據本發明，提供一種可容易地製造具有導體或半導體特性的金屬氧化物膜的金屬氧化物膜的製造方法、以及電特性優異的金屬氧化物膜、薄膜電晶體及電子元件。 According to the present invention, there is provided a method for producing a metal oxide film which can easily produce a metal oxide film having a conductor or a semiconductor property, and a metal oxide film, a thin film transistor and an electronic component which are excellent in electrical characteristics.

10、30、40、50‧‧‧薄膜電晶體(TFT) 10, 30, 40, 50‧‧‧ Film Transistor (TFT)

10a‧‧‧驅動用薄膜電晶體(TFT) 10a‧‧‧Drive film transistor (TFT)

10b‧‧‧開關用薄膜電晶體(TFT) 10b‧‧‧Transistor Thin Film Transistor (TFT)

12‧‧‧基板 12‧‧‧Substrate

14‧‧‧活性層 14‧‧‧Active layer

16‧‧‧源極電極 16‧‧‧Source electrode

18‧‧‧汲極電極 18‧‧‧汲electrode

20‧‧‧閘極絕緣膜 20‧‧‧gate insulating film

22‧‧‧閘極電極 22‧‧‧gate electrode

100‧‧‧液晶顯示裝置 100‧‧‧Liquid crystal display device

102、202、216‧‧‧鈍化層 102, 202, 216‧‧ ‧ passivation layer

104‧‧‧畫素下部電極 104‧‧‧ pixel lower electrode

106‧‧‧對向上部電極 106‧‧‧for the upper electrode

108‧‧‧液晶層 108‧‧‧Liquid layer

110‧‧‧彩色濾光片 110‧‧‧Color filters

112、220、320‧‧‧閘極配線 112, 220, 320‧‧‧ gate wiring

112a、112b‧‧‧偏光板 112a, 112b‧‧‧ polarizing plate

114、222、322‧‧‧資料配線 114, 222, 322‧‧‧ data wiring

116、318‧‧‧接觸孔 116, 318‧‧‧ contact holes

118、226、310‧‧‧電容器 118, 226, 310‧‧‧ capacitors

200‧‧‧有機EL顯示裝置 200‧‧‧Organic EL display device

208‧‧‧下部電極 208‧‧‧lower electrode

210、306‧‧‧上部電極 210, 306‧‧‧ upper electrode

212‧‧‧有機發光層 212‧‧‧Organic light-emitting layer

214‧‧‧有機EL發光元件 214‧‧‧Organic EL light-emitting elements

224‧‧‧驅動配線 224‧‧‧Drive wiring

300‧‧‧X射線感測器 300‧‧‧X-ray sensor

302‧‧‧電荷收集用電極 302‧‧‧Electrical electrodes for charge collection

304‧‧‧X射線轉換層 304‧‧‧X-ray conversion layer

308‧‧‧鈍化膜 308‧‧‧passivation film

312‧‧‧電容器用下部電極 312‧‧‧The lower electrode for capacitors

314‧‧‧電容器用上部電極 314‧‧‧Upper electrode for capacitor

316‧‧‧絕緣膜 316‧‧‧Insulation film

圖1為表示藉由本發明所製造的薄膜電晶體的一例(頂部閘 極-頂部接觸型)的構成的概略圖。 1 is a view showing an example of a thin film transistor manufactured by the present invention (top gate) Schematic diagram of the configuration of the pole-top contact type.

圖2為表示藉由本發明所製造的薄膜電晶體的一例(頂部閘極-底部接觸型)的構成的概略圖。 2 is a schematic view showing a configuration of an example of a thin film transistor (top gate-bottom contact type) manufactured by the present invention.

圖3為表示藉由本發明所製造的薄膜電晶體的一例(底部閘極-頂部接觸型)的構成的概略圖。 3 is a schematic view showing a configuration of an example of a thin film transistor (bottom gate-top contact type) manufactured by the present invention.

圖4為表示藉由本發明所製造的薄膜電晶體的一例(底部閘極-底部接觸型)的構成的概略圖。 4 is a schematic view showing a configuration of an example of a thin film transistor (bottom gate-bottom contact type) manufactured by the present invention.

圖5為表示實施形態的液晶顯示裝置的一部分的概略剖面圖。 Fig. 5 is a schematic cross-sectional view showing a part of a liquid crystal display device of the embodiment.

圖6為圖5所示的液晶顯示裝置的電氣配線的概略構成圖。 Fig. 6 is a schematic configuration diagram of electrical wiring of the liquid crystal display device shown in Fig. 5;

圖7為表示實施形態的有機電致發光(Electro Luminescence，EL)顯示裝置的一部分的概略剖面圖。 Fig. 7 is a schematic cross-sectional view showing a part of an organic electroluminescence (EL) display device according to an embodiment.

圖8為圖7所示的有機EL顯示裝置的電氣配線的概略構成圖。 FIG. 8 is a schematic configuration diagram of electric wiring of the organic EL display device shown in FIG. 7.

圖9為表示實施形態的X射線感測器陣列的一部分的概略剖面圖。 Fig. 9 is a schematic cross-sectional view showing a part of an X-ray sensor array of the embodiment.

圖10為圖9所示的X射線感測器陣列的電氣配線的概略構成圖。 Fig. 10 is a schematic block diagram showing electrical wiring of the X-ray sensor array shown in Fig. 9;

圖11為表示實施例1~實施例3中製作的簡易型TFT的Vg-Id特性的圖。 Fig. 11 is a graph showing the V g - I d characteristics of the simple TFTs produced in Examples 1 to 3.

圖12為表示關於實施例1及比較例1中製作的金屬氧化物膜的X射線光電子分光(X-ray Photoelectron Spectroscopy，XPS)光譜(歸屬於氧的1 s電子的結合能為525eV~540ev的範圍) 的圖。 Fig. 12 is a view showing X-ray photoelectron spectroscopy (XPS) spectra of the metal oxide films produced in Example 1 and Comparative Example 1 (the binding energy of 1 s electrons attributed to oxygen is 525 eV to 540 ev). range) Figure.

圖13為表示實施例7、實施例8中製作的簡易型TFT的Vg-Id特性的圖。 Fig. 13 is a graph showing the V g - I d characteristics of the simple TFTs produced in Example 7 and Example 8.

以下，一面參照隨附的圖式，一面對本發明的金屬氧化物膜的製造方法、以及藉由本發明所製造的金屬氧化物膜、薄膜電晶體及電子元件加以具體說明。 Hereinafter, a method for producing a metal oxide film of the present invention, and a metal oxide film, a thin film transistor, and an electronic device produced by the present invention will be specifically described with reference to the accompanying drawings.

再者，圖中對具有相同或對應功能的構件(構成要素)標註相同的符號而適當省略說明。又，在本說明書中由記號「~」來表示數值範圍的情形時，包括作為下限值及上限值而記載的數值。 In the drawings, members (components) having the same or corresponding functions are denoted by the same reference numerals, and their description will be appropriately omitted. In the case where the numerical value range is indicated by the symbol "~" in the present specification, the numerical values described as the lower limit value and the upper limit value are included.

又，本發明可應用於製造作為導電膜或半導體膜的金屬氧化物膜，作為代表例，主要對半導體膜的製造方法進行說明。 Moreover, the present invention can be applied to the production of a metal oxide film as a conductive film or a semiconductor film. As a representative example, a method of manufacturing a semiconductor film will be mainly described.

本發明者等人亦認為在使用含有銦作為金屬成分的溶液形成金屬氧化物前驅物膜後，藉由加熱等使其轉化為金屬氧化物膜的情形時，氣體環境中的氧濃度高者可獲得緻密且導電性高的金屬氧化物膜，但反覆實驗後發現，在對前驅物膜進行加熱處理的條件下，實施紫外線照射而使其轉化為金屬氧化物膜的情形時，氣體環境中的氧濃度越低，可獲得導電性越高的金屬氧化物膜。 The present inventors have also considered that when a metal oxide precursor film is formed using a solution containing indium as a metal component and then converted into a metal oxide film by heating or the like, the oxygen concentration in the gas atmosphere is high. A dense and highly conductive metal oxide film is obtained, but after repeated experiments, it is found that in the case of heat treatment of the precursor film, when it is irradiated with ultraviolet rays and converted into a metal oxide film, in a gaseous environment The lower the oxygen concentration, the higher the conductivity of the metal oxide film.

<金屬氧化物膜的製造方法> <Method for Producing Metal Oxide Film>

本發明的金屬氧化物膜的製造方法包括：前驅物膜形成步驟，將含有溶劑及至少含有銦作為金屬成分的溶液塗佈於基板上 而形成金屬氧化物前驅物膜；轉化步驟，於將金屬氧化物前驅物膜加熱的狀態下，在氧濃度為80000ppm以下(8%以下)的氣體環境下進行紫外線照射，藉此使金屬氧化物前驅物膜轉化為金屬氧化物膜。 The method for producing a metal oxide film of the present invention comprises: a precursor film forming step of applying a solution containing a solvent and at least containing indium as a metal component to a substrate a metal oxide precursor film is formed; and the conversion step is performed by irradiating ultraviolet rays in a gas atmosphere having an oxygen concentration of 80,000 ppm or less (8% or less) in a state where the metal oxide precursor film is heated, thereby causing the metal oxide The precursor film is converted into a metal oxide film.

藉由本發明的方法可獲得導電性高的金屬氧化物膜的理由雖不明確，但可如以下般推測。 Although the reason why a highly conductive metal oxide film can be obtained by the method of the present invention is not clear, it can be estimated as follows.

可認為，於使用至少含有銦作為金屬成分的溶液形成前驅物膜的情形時，若在加熱條件下照射紫外線，則藉由光化學反應，膜中產生活性氧，產生In-O鍵而生成氧化銦。另一方面，可認為，氣體環境中的氧亦因紫外線照射而生成臭氧並分解，氧濃度越高，氣體環境中的活性氧的濃度越高。因此可認為，氣體環境中的氧濃度越高，在膜中活性氧的生成越受到抑制，變得容易產生In-O鍵以外的鍵，反之，氣體環境中的氧濃度越低，在膜中越容易生成活性氧，而變得越容易產生In-O鍵。 In the case where a precursor film is formed using a solution containing at least indium as a metal component, when ultraviolet rays are irradiated under heating conditions, active oxygen is generated in the film by photochemical reaction, and an In-O bond is generated to generate oxidation. indium. On the other hand, it is considered that oxygen in a gaseous environment generates ozone by ultraviolet irradiation and decomposes, and the higher the oxygen concentration, the higher the concentration of active oxygen in the gas atmosphere. Therefore, it is considered that the higher the oxygen concentration in the gas atmosphere, the more the generation of active oxygen in the film is suppressed, and the bonds other than the In—O bond are easily generated. Conversely, the lower the oxygen concentration in the gas environment, the more the film is in the film. It is easy to generate active oxygen, and it becomes easier to generate an In-O bond.

以下，對各步驟進行具體說明。 Hereinafter, each step will be specifically described.

[前驅物膜形成步驟] [Precursor film formation step]

首先，準備含有溶劑及至少含有銦作為金屬成分的溶液(金屬氧化物前驅物溶液)，塗佈於基板上而形成金屬氧化物前驅物膜。 First, a solution (metal oxide precursor solution) containing a solvent and at least indium as a metal component is prepared and applied onto a substrate to form a metal oxide precursor film.

(基板) (substrate)

基板的形狀、結構、大小等並無特別限制，可根據目的而適當選擇。基板的結構可為單層結構，亦可為積層結構。 The shape, structure, size, and the like of the substrate are not particularly limited and may be appropriately selected depending on the purpose. The structure of the substrate may be a single layer structure or a laminate structure.

構成基板的材料並無特別限定，可使用包含以下材料的基板：玻璃、釔穩定氧化鋯(Yttria-Stabilized Zirconia，YSZ)等無機材料，樹脂、樹脂複合材料等。其中，就輕量的方面、具有可撓性的方面而言，較佳為樹脂基板或包含樹脂複合材料的基板(樹脂複合材料基板)。 The material constituting the substrate is not particularly limited, and a substrate containing the following materials: glass, an inorganic material such as Yttria-Stabilized Zirconia (YSZ), a resin, a resin composite material, or the like can be used. Among them, a resin substrate or a substrate (resin composite substrate) containing a resin composite material is preferred in terms of light weight and flexibility.

具體而言，可列舉：聚對苯二甲酸丁二酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚苯乙烯、聚碳酸酯、聚碸、聚醚碸、聚芳酯、烯丙基二甘醇碳酸酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚吲哚(polybenzazole)、聚苯硫醚、聚環烯烴、降冰片烯樹脂、聚氯三氟乙烯等氟樹脂、液晶聚合物、丙烯酸系樹脂、環氧樹脂、矽酮樹脂、離子聚合物樹脂、氰酸酯樹脂、交聯富馬酸二酯、環狀聚烯烴、芳香族醚、馬來醯亞胺-烯烴、纖維素、環硫化合物等合成樹脂基板。 Specific examples thereof include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and poly Bismuth, polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimine, polyamidimide, polyether phthalimide, polybenzazole, polyphenylene Fluororesin, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, cross-linked rich A synthetic resin substrate such as a horse acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound.

又，作為無機材料與樹脂的複合材料所含的無機材料，可列舉：氧化矽粒子、金屬奈米粒子、無機氧化物奈米粒子、無機氮化物奈米粒子等無機粒子，碳纖維、碳奈米管等碳材料，玻璃薄片、玻璃纖維、玻璃珠等玻璃材料。 In addition, examples of the inorganic material contained in the composite material of the inorganic material and the resin include inorganic particles such as cerium oxide particles, metal nanoparticles, inorganic oxide nanoparticles, and inorganic nitride nanoparticles, and carbon fibers and carbon nanoparticles. Carbon materials such as tubes, glass materials such as glass flakes, glass fibers, and glass beads.

又，可列舉：樹脂與黏土礦物的複合塑膠材料、樹脂與具有雲母衍生結晶結構的粒子的複合塑膠材料、於樹脂與薄玻璃之間具有至少1個接合界面的積層塑膠材料、藉由將無機層與有機層交替積層而具有至少1個接合界面且具有阻障性能的複合材料等。 Further, a composite plastic material of a resin and a clay mineral, a composite plastic material having a resin and a particle having a mica-derived crystal structure, a laminated plastic material having at least one joint interface between the resin and the thin glass, and an inorganic material may be mentioned. A composite material in which a layer and an organic layer are alternately laminated to have at least one joint interface and have barrier properties.

又，亦可使用不鏽鋼基板或將不鏽鋼與不同種類的金屬積層 而成的金屬多層基板、鋁基板或藉由對表面實施氧化處理(例如陽極氧化處理)而提高了表面的絕緣性的帶有氧化皮膜的鋁基板、帶有氧化膜的矽基板等。 Also, you can use a stainless steel substrate or laminate stainless steel with different types of metals. The metal multilayer substrate, the aluminum substrate, or an aluminum substrate with an oxide film having an insulating property on the surface by an oxidation treatment (for example, anodization treatment), an oxide film-containing germanium substrate, or the like.

又，樹脂基板或樹脂複合材料基板較佳為耐熱性、尺寸穩定性、耐溶劑性、電氣絕緣性、加工性、低通氣性、及低吸濕性等優異。樹脂基板或樹脂複合材料基板亦可具有用以防止水分、氧等的透過的阻氣層、或用以提高基板的平坦性或與下部電極的密接性的底塗層等。 Further, the resin substrate or the resin composite substrate is preferably excellent in heat resistance, dimensional stability, solvent resistance, electrical insulating properties, workability, low air permeability, and low moisture absorption. The resin substrate or the resin composite substrate may have a gas barrier layer for preventing transmission of moisture, oxygen, or the like, or an undercoat layer for improving the flatness of the substrate or the adhesion to the lower electrode.

本發明中所使用的基板的厚度並無特別限制，較佳為50μm以上且500μm以下。若基板的厚度為50μm以上，則基板自身的平坦性進一步提高。又，若基板的厚度為500μm以下，則基板自身的可撓性進一步提高，更容易用作可撓性元件用基板。 The thickness of the substrate used in the present invention is not particularly limited, but is preferably 50 μm or more and 500 μm or less. When the thickness of the substrate is 50 μm or more, the flatness of the substrate itself is further improved. In addition, when the thickness of the substrate is 500 μm or less, the flexibility of the substrate itself is further improved, and it is easier to use as a substrate for a flexible element.

(溶液) (solution)

本發明中所使用的溶液含有溶劑、及作為金屬成分的銦，亦可視需要而含有銦以外的其他金屬成分。 The solution used in the present invention contains a solvent and indium as a metal component, and may contain other metal components other than indium as needed.

溶液中所含的銦較佳為以銦離子的形式含有。再者，本發明中的銦離子亦可為配位有溶劑分子等配位子的銦錯離子。又，溶液中所含的銦以外的其他金屬成分亦較佳為以離子的形式含有。 The indium contained in the solution is preferably contained in the form of indium ions. Further, the indium ion in the present invention may be an indium counter ion in which a ligand such as a solvent molecule is coordinated. Further, other metal components other than indium contained in the solution are preferably contained in the form of ions.

本發明所使用的溶液是以溶液成為所需濃度的方式秤量成為原料的金屬鹽等溶質，並於溶劑中攪拌、溶解而獲得。進行攪拌的時間只要可將溶質充分溶解，則無特別限制。 The solution used in the present invention is obtained by weighing a solute such as a metal salt as a raw material in such a manner that the solution becomes a desired concentration, and stirring and dissolving in a solvent. The stirring time is not particularly limited as long as the solute can be sufficiently dissolved.

溶液中的銦的含量較佳為溶液中所含的金屬成分的50 atom%以上。藉由使用含有所述濃度範圍的銦的溶液，可獲得膜中的金屬成分的50atom%以上成為銦的金屬氧化物膜，而可容易地製造電子傳遞特性高的金屬氧化物膜。 The content of indium in the solution is preferably 50 of the metal component contained in the solution. Above atom%. By using a solution containing indium in the above concentration range, a metal oxide film having 50 atom% or more of a metal component in the film to be indium can be obtained, and a metal oxide film having high electron transport characteristics can be easily produced.

使用含金屬原子的化合物作為本發明的溶液中所含的銦及視需要而含有的其他金屬成分的原料。作為含金屬原子的化合物，可列舉金屬鹽、金屬鹵化物、有機金屬化合物。作為金屬鹽，可列舉硫酸鹽、磷酸鹽、碳酸鹽、乙酸鹽、草酸鹽等，作為金屬鹵化物，可列舉氯化物、碘化物、溴化物等，作為有機金屬化合物，可列舉金屬烷氧化物、有機酸鹽、金屬β-二酮酸鹽等。 A metal atom-containing compound is used as a raw material of indium contained in the solution of the present invention and other metal components contained as needed. Examples of the metal atom-containing compound include metal salts, metal halides, and organometallic compounds. Examples of the metal salt include a sulfate, a phosphate, a carbonate, an acetate, and an oxalate. Examples of the metal halide include a chloride, an iodide, and a bromide. Examples of the organometallic compound include metal alkoxide. Compound, organic acid salt, metal β-diketonate, and the like.

本發明的溶液除了含有銦以外，較佳為含有硝酸根離子，更佳為至少溶解有硝酸銦的溶液。塗佈溶解有硝酸銦的溶液所獲得的金屬氧化物前驅物膜可高效地吸收紫外光，可容易地形成含銦的氧化物膜。再者，硝酸銦亦可為水合物。 The solution of the present invention preferably contains a nitrate ion in addition to indium, and more preferably a solution in which at least indium nitrate is dissolved. The metal oxide precursor film obtained by coating a solution in which indium nitrate is dissolved can efficiently absorb ultraviolet light, and an indium-containing oxide film can be easily formed. Further, indium nitrate may also be a hydrate.

較佳為溶液含有選自鋅、錫、鎵及鋁中的至少一種金屬成分作為銦以外的金屬成分。藉由本發明的溶液適量含有銦與銦以外的所述任意金屬成分，可提高所獲得的金屬氧化物膜的電氣穩定性。 Preferably, the solution contains at least one metal component selected from the group consisting of zinc, tin, gallium, and aluminum as a metal component other than indium. The electric stability of the obtained metal oxide film can be improved by the proper amount of the solution of the present invention containing any of the above-described metal components other than indium and indium.

又，於藉由本發明所製造的金屬氧化物半導體膜中，亦可將臨限電壓控制為所需的值。 Further, in the metal oxide semiconductor film produced by the present invention, the threshold voltage can be controlled to a desired value.

作為含有銦與其他金屬元素的金屬氧化物膜(導體膜或半導體膜)，可列舉：In-Ga-Zn-O(氧化銦鎵鋅(Indium Gallium Zinc Oxide，IGZO))、In-Zn-O(氧化銦鋅(Indium Zinc Oxide，IZO))、 In-Ga-O(氧化銦鎵(Indium Gallium Oxide，IGO))、In-Sn-O(氧化銦錫(Indium Tin Oxide，ITO))、In-Sn-Zn-O(氧化銦錫鋅(Indium Tin Zinc Oxide，ITZO))等。 Examples of the metal oxide film (conductor film or semiconductor film) containing indium and other metal elements include In-Ga-Zn-O (Indium Gallium Zinc Oxide (IGZO)) and In-Zn-O. (Indium Zinc Oxide (IZO)), In-Ga-O (Indium Gallium Oxide (IGO)), In-Sn-O (Indium Tin Oxide (ITO)), In-Sn-Zn-O (Indium Tin Zinc (Indium) Tin Zinc Oxide, ITZO)) and so on.

再者，本發明的溶液較佳為使用溶液中不含金屬氧化物半導體粒子等不溶物的溶液。藉由使用溶液中不含金屬氧化物半導體粒子等不溶物的溶液，形成金屬氧化物膜時的表面粗糙度變小，可形成面內均勻性優異的金屬氧化物膜。 Further, the solution of the present invention is preferably a solution containing no insoluble matter such as metal oxide semiconductor particles in the solution. By using a solution containing no insoluble matter such as metal oxide semiconductor particles in the solution, the surface roughness at the time of forming the metal oxide film is small, and a metal oxide film excellent in in-plane uniformity can be formed.

本發明的溶液所使用的溶劑只要為溶解用作溶質的含金屬原子的化合物者，則無特別限制，可列舉：水、醇溶劑(甲醇、乙醇、丙醇、乙二醇等)、醯胺溶劑(N,N-二甲基甲醯胺等)、酮溶劑(丙酮、N-甲基吡咯啶酮、環丁碸、N,N-二甲基咪唑啶酮等)、醚溶劑(四氫呋喃、甲氧基乙醇等)、腈溶劑(乙腈等)、其他所述以外的含雜原子的溶劑等。尤其就溶解性、塗佈性、成本、環境負荷的觀點而言，較佳為使用甲醇、甲氧基乙醇、或水。 The solvent to be used in the solution of the present invention is not particularly limited as long as it dissolves a metal atom-containing compound used as a solute, and examples thereof include water, an alcohol solvent (methanol, ethanol, propanol, ethylene glycol, etc.) and guanamine. Solvent (N,N-dimethylformamide, etc.), ketone solvent (acetone, N-methylpyrrolidone, cyclobutyl hydrazine, N,N-dimethylimidazolidinone, etc.), ether solvent (tetrahydrofuran, A methoxyethanol or the like, a nitrile solvent (such as acetonitrile), or a hetero atom-containing solvent other than the above. In particular, methanol, methoxyethanol, or water is preferably used from the viewpoints of solubility, coatability, cost, and environmental load.

溶液中的金屬成分的濃度可根據黏度或欲獲得的膜厚而任意選擇，就薄膜的平坦性及生產性的觀點而言，溶液中的金屬成分的濃度較佳為0.01mol/L以上且1.0mol/L以下，更佳為0.01mol/L以上且0.5mol/L以下。 The concentration of the metal component in the solution can be arbitrarily selected depending on the viscosity or the film thickness to be obtained. From the viewpoint of flatness and productivity of the film, the concentration of the metal component in the solution is preferably 0.01 mol/L or more and 1.0. The mol/L or less is more preferably 0.01 mol/L or more and 0.5 mol/L or less.

(塗佈) (coating)

作為將溶液塗佈於基板上的方法，可列舉：噴霧塗佈法、旋轉塗佈法、刮刀塗佈法、浸漬塗佈法、澆鑄法、輥式塗佈法、棒式塗佈法、模式塗佈法、薄霧(mist)法、噴墨法、分配器法、網 版印刷法、凸版印刷法、及凹版印刷法等。尤其就容易形成微細圖案的觀點而言，較佳為使用選自噴墨法、分配器法、凸版印刷法、及凹版印刷法中的至少一種塗佈法。 Examples of the method of applying the solution onto the substrate include a spray coating method, a spin coating method, a knife coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, and a mode. Coating method, mist method, inkjet method, dispenser method, net Printing method, letterpress printing method, gravure printing method, and the like. In particular, from the viewpoint of easily forming a fine pattern, at least one coating method selected from the group consisting of an inkjet method, a dispenser method, a relief printing method, and a gravure printing method is preferably used.

(乾燥) (dry)

將溶液塗佈於基板上後，亦可進行自然乾燥而製成金屬氧化物前驅物膜，但較佳為藉由將基板溫度設為35℃以上且100℃以下的加熱處理使其乾燥而獲得金屬氧化物前驅物膜。藉由乾燥，可降低塗佈膜的流動性，提高最終獲得的金屬氧化物膜的平坦性。又，藉由選擇合適的乾燥溫度(35℃以上且100℃以下)，最終可獲得更緻密的金屬氧化物膜。加熱處理的方法並無特別限定，可自加熱板加熱、電爐加熱、紅外線加熱、微波加熱等中選擇。 After the solution is applied onto a substrate, it may be naturally dried to form a metal oxide precursor film. However, it is preferably obtained by drying the substrate at a temperature of 35° C. or higher and 100° C. or lower. Metal oxide precursor film. By drying, the fluidity of the coating film can be lowered, and the flatness of the finally obtained metal oxide film can be improved. Further, by selecting an appropriate drying temperature (35 ° C or more and 100 ° C or less), a more dense metal oxide film can be finally obtained. The method of the heat treatment is not particularly limited, and may be selected from the group consisting of heating plate heating, electric furnace heating, infrared heating, microwave heating, and the like.

就均勻地保持膜的平坦性的觀點而言，乾燥較佳為將溶液塗佈於基板上後於5分鐘以內開始。 From the viewpoint of uniformly maintaining the flatness of the film, drying is preferably started within 5 minutes after the solution is applied onto the substrate.

進行乾燥的時間並無特別限制，就膜的均勻性、生產性的觀點而言，較佳為15秒以上且10分鐘以下。 The time for drying is not particularly limited, and from the viewpoint of film uniformity and productivity, it is preferably 15 seconds or longer and 10 minutes or shorter.

進行乾燥的氣體環境並無特別限制，就製造成本等觀點而言，較佳為於大氣壓下、大氣中進行。 The gas atmosphere to be dried is not particularly limited, and is preferably carried out in the atmosphere at atmospheric pressure from the viewpoint of production cost and the like.

[轉化步驟] [conversion step]

繼而，於將金屬氧化物前驅物膜加熱的狀態下，在氧濃度為80000ppm以下的氣體環境下進行紫外線照射，藉此使金屬氧化物前驅物膜轉化為金屬氧化物膜。藉由於對金屬氧化物前驅物膜進 行加熱處理的條件下進行紫外線照射而向金屬氧化物膜轉化，此時，藉由將氣體環境中的氧濃度抑制為80000ppm以下，可提高電子傳遞特性。 Then, in a state where the metal oxide precursor film is heated, ultraviolet irradiation is performed in a gas atmosphere having an oxygen concentration of 80,000 ppm or less, thereby converting the metal oxide precursor film into a metal oxide film. By virtue of the metal oxide precursor film The metal oxide film is converted by ultraviolet irradiation under the conditions of heat treatment. In this case, by suppressing the oxygen concentration in the gas atmosphere to 80,000 ppm or less, the electron transport characteristics can be improved.

(加熱處理) (heat treatment)

轉化步驟中的基板溫度較佳為保持為超過120℃，又，較佳為保持為低於200℃。若將轉化步驟中的基板溫度保持為超過120℃，則可於更短時間內獲得高電子傳遞特性的金屬氧化物膜。另一方面，若將轉化步驟中的基板溫度保持為200℃以下，則可抑制熱能增大，而抑制為低的製造成本，又，變得容易應用於耐熱性低的樹脂基板。 The substrate temperature in the conversion step is preferably maintained at more than 120 ° C, and more preferably maintained at less than 200 ° C. When the substrate temperature in the conversion step is maintained to exceed 120 ° C, a metal oxide film having high electron transport characteristics can be obtained in a shorter time. On the other hand, when the substrate temperature in the conversion step is maintained at 200 ° C or lower, the increase in thermal energy can be suppressed, and the manufacturing cost can be suppressed, and the resin substrate having low heat resistance can be easily applied.

轉化步驟中對基板的加熱手段並無特別限定，可自加熱板加熱、電爐加熱、紅外線加熱、微波加熱等中選擇。 The heating means for the substrate in the conversion step is not particularly limited, and may be selected from the group consisting of heating plate heating, electric furnace heating, infrared heating, microwave heating, and the like.

照射紫外線前的加熱處理時間並無特別限制，就生產性的觀點而言，較佳為短時間，具體而言較佳為5分鐘以內。 The heat treatment time before the irradiation of the ultraviolet rays is not particularly limited, and from the viewpoint of productivity, it is preferably a short time, and specifically, it is preferably within 5 minutes.

(紫外線照射) (UV irradiation)

於對基板上的金屬氧化物前驅物膜進行加熱的條件下，在氧濃度為80000ppm以下的氣體環境中照射紫外線。 Under the condition that the metal oxide precursor film on the substrate is heated, ultraviolet rays are irradiated in a gas atmosphere having an oxygen concentration of 80,000 ppm or less.

若在加熱條件下對金屬氧化物前驅物膜進行紫外線照射的氣體環境的氧濃度為80000ppm以下，則可獲得電子傳遞特性高的金屬氧化物膜。就提高電子傳遞特性的觀點而言，較佳為進行所述紫外線照射的氣體環境中的氧濃度為30000ppm以下(3%以下)。 When the oxygen concentration of the gas atmosphere in which the metal oxide precursor film is irradiated with ultraviolet light under heating is 80000 ppm or less, a metal oxide film having high electron transport characteristics can be obtained. From the viewpoint of improving the electron transport characteristics, it is preferred that the oxygen concentration in the gas atmosphere in which the ultraviolet irradiation is performed is 30,000 ppm or less (3% or less).

再者，作為將紫外線照射時的氣體環境中的氧濃度調整為80000ppm以下的手段，例如可列舉以下方法：調整向對基板上的金屬氧化物前驅物膜進行加熱及紫外線照射的處理室內供給的氮氣等惰性氣體的流速的方法；調整向處理室內供給的氣體中的氧濃度的方法；預先將處理室內抽為真空，向其中填充所需氧濃度的氣體的方法等。 In addition, as means for adjusting the oxygen concentration in the gas atmosphere at the time of ultraviolet irradiation to 80,000 ppm or less, for example, a method of adjusting the supply to the processing chamber for heating and ultraviolet irradiation of the metal oxide precursor film on the substrate is exemplified. A method of adjusting the flow rate of an inert gas such as nitrogen; a method of adjusting the oxygen concentration in the gas supplied to the processing chamber; a method of evacuating the inside of the processing chamber to a vacuum, and filling a gas having a desired oxygen concentration therein.

較佳為以10mW/cm2以上的照度對金屬氧化物前驅物膜的膜面照射波長300nm以下的紫外光。藉由以10mW/cm2以上的照度對金屬氧化物前驅物膜照射波長300nm以下的紫外光，可於更短的時間內進行由金屬氧化物前驅物膜向金屬氧化物膜的轉化。射向金屬氧化物前驅物膜的膜面的紫外光的照度較佳為10mW/cm2以上，更佳為100mW/cm2以上。若射向金屬氧化物前驅物膜的膜面的紫外光的照度為10mW/cm2以上，則可獲得電子傳遞特性高的金屬氧化物膜，若為100mW/cm2以上，則可於更短時間內獲得電子傳遞特性高的金屬氧化物膜。再者，就裝置成本的觀點而言，照度的上限較佳為500mW/cm2以下。 It is preferred that the film surface of the metal oxide precursor film is irradiated with ultraviolet light having a wavelength of 300 nm or less at an illuminance of 10 mW/cm 2 or more. By irradiating the metal oxide precursor film with ultraviolet light having a wavelength of 300 nm or less at an illuminance of 10 mW/cm 2 or more, conversion from the metal oxide precursor film to the metal oxide film can be performed in a shorter period of time. The illuminance of the ultraviolet light incident on the film surface of the metal oxide precursor film is preferably 10 mW/cm 2 or more, more preferably 100 mW/cm 2 or more. When the illuminance of the ultraviolet light incident on the film surface of the metal oxide precursor film is 10 mW/cm 2 or more, a metal oxide film having high electron transport characteristics can be obtained, and if it is 100 mW/cm 2 or more, it can be made shorter. A metal oxide film having high electron transfer characteristics is obtained in time. Further, from the viewpoint of device cost, the upper limit of the illuminance is preferably 500 mW/cm 2 or less.

作為加熱處理中的紫外線照射的光源，可列舉UV燈、UV雷射等，就利用廉價的設備大面積地均勻進行紫外線照射的觀點而言，較佳為UV燈。作為UV燈，例如可列舉：準分子燈、氘燈、低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、氦燈、碳弧燈、鎘燈、無電極放電燈等，尤其若使用低壓水銀燈，則可容易地進行由金屬氧化物前驅物膜向金屬氧化物膜的轉化， 故較佳。 The light source for the ultraviolet ray irradiation in the heat treatment is, for example, a UV lamp or a UV laser, and is preferably a UV lamp from the viewpoint of uniformly irradiating the ultraviolet ray uniformly over a large area. Examples of the UV lamp include an excimer lamp, a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a cadmium lamp, an electrodeless discharge lamp, and the like, especially if a low pressure is used. Mercury lamp can easily convert from a metal oxide precursor film to a metal oxide film. Therefore, it is better.

又，就達成高的電子傳遞特性的觀點而言，較佳為將紫外線照射中的基板升溫或降溫的速度設為±0.5℃/min以內，更佳為將紫外線照射中的基板溫度設為恆定。 Further, from the viewpoint of achieving high electron transport characteristics, it is preferable that the substrate is heated or cooled at a rate of ±0.5 ° C/min, and more preferably the substrate temperature during ultraviolet irradiation is constant. .

紫外線照射中的基板溫度可藉由對基板進行加熱的加熱板等加熱單元進行調整。 The substrate temperature in the ultraviolet irradiation can be adjusted by a heating unit such as a heating plate that heats the substrate.

轉化步驟中的紫外線照射進行至金屬氧化物前驅物膜轉化為金屬氧化物膜即可。雖亦取決於前驅物膜的組成、加熱溫度、紫外線照度等，但就生產性的觀點而言，紫外線照射時間較佳為5分鐘以上且120分鐘以下，更佳為60分鐘以下。 The ultraviolet irradiation in the conversion step is carried out until the metal oxide precursor film is converted into a metal oxide film. Although it depends on the composition of the precursor film, the heating temperature, the ultraviolet illuminance, etc., from the viewpoint of productivity, the ultraviolet irradiation time is preferably 5 minutes or longer and 120 minutes or shorter, more preferably 60 minutes or shorter.

<薄膜電晶體> <Thin Film Transistor>

藉由本發明的實施形態所製作的金屬氧化物膜顯示出導電性或半導體性(較佳為0.2cm2/Vs以上，更佳為0.5cm2/Vs以上，進而較佳為1cm2/Vs以上)，故可較佳地用於薄膜電晶體(TFT)的電極(源極電極、汲極電極、或閘極電極)或活性層(氧化物半導體層)。 The metal oxide film produced by the embodiment of the present invention exhibits conductivity or semiconductivity (preferably 0.2 cm 2 /Vs or more, more preferably 0.5 cm 2 /Vs or more, still more preferably 1 cm 2 /Vs or more). Therefore, it can be preferably used for an electrode (source electrode, a gate electrode, or a gate electrode) or an active layer (oxide semiconductor layer) of a thin film transistor (TFT).

以下，對將藉由本發明的製造方法所製作的金屬氧化物膜用作薄膜電晶體的活性層的情形時的實施形態進行說明。再者，本發明的金屬氧化物膜的製造方法及藉由所述製造方法所製造的金屬氧化物膜並不限定於TFT的活性層。 Hereinafter, an embodiment in the case where the metal oxide film produced by the production method of the present invention is used as an active layer of a thin film transistor will be described. Further, the method for producing a metal oxide film of the present invention and the metal oxide film produced by the above production method are not limited to the active layer of the TFT.

本發明的TFT的元件結構並無特別限定，根據閘極電極的位置，可為所謂逆交錯結構(亦可稱為底部閘極型)及交錯結 構(亦可稱為頂部閘極型)的任一態樣。又，根據活性層與源極電極及汲極電極(適當稱為「源極電極、汲極電極」)的接觸部分，可為所謂頂部接觸型、底部接觸型的任一態樣。 The element structure of the TFT of the present invention is not particularly limited, and may be a so-called reverse staggered structure (also referred to as a bottom gate type) and an interleaved junction depending on the position of the gate electrode. Any aspect of the structure (also known as the top gate type). Further, the contact portion between the active layer and the source electrode and the drain electrode (referred to as "source electrode, drain electrode" as appropriate) may be either a top contact type or a bottom contact type.

所謂頂部閘極型，是指於將形成有TFT的基板設為最下層時，於閘極絕緣膜的上側配置有閘極電極，於閘極絕緣膜的下側形成有活性層的形態，所謂底部閘極型，是指於閘極絕緣膜的下側配置有閘極電極，於閘極絕緣膜的上側形成有活性層的形態。又，所謂底部接觸型，是指較活性層而先形成源極電極、汲極電極，活性層的下表面與源極電極、汲極電極接觸的形態，所謂頂部接觸型，是指較源極電極、汲極電極而先形成活性層，活性層的上表面與源極電極、汲極電極接觸的形態。 In the case of the top gate type, when the substrate on which the TFT is formed is the lowermost layer, a gate electrode is disposed on the upper side of the gate insulating film, and an active layer is formed on the lower side of the gate insulating film. The bottom gate type is a form in which a gate electrode is disposed on the lower side of the gate insulating film and an active layer is formed on the upper side of the gate insulating film. In addition, the bottom contact type refers to a form in which a source electrode and a drain electrode are formed first, and a lower surface of the active layer is in contact with a source electrode and a drain electrode, and the top contact type refers to a source. The electrode and the drain electrode form an active layer first, and the upper surface of the active layer is in contact with the source electrode and the drain electrode.

圖1為表示頂部閘極結構且為頂部接觸型的本發明的TFT的一例的示意圖。於圖1所示的TFT 10中，於基板12的一個主面上積層有作為活性層14的上文所述的氧化物半導體膜。此外，於該活性層14上彼此隔開而設置有源極電極16及汲極電極18，進而於該些構件上依序積層有閘極絕緣膜20及閘極電極22。 Fig. 1 is a schematic view showing an example of a TFT of the present invention which has a top gate structure and is of a top contact type. In the TFT 10 shown in FIG. 1, the above-described oxide semiconductor film as the active layer 14 is laminated on one main surface of the substrate 12. Further, the source electrode 16 and the drain electrode 18 are provided on the active layer 14 so as to be spaced apart from each other, and the gate insulating film 20 and the gate electrode 22 are sequentially laminated on the members.

圖2為表示頂部閘極結構且為底部接觸型的本發明的TFT的一例的示意圖。於圖2所示的TFT 30中，於基板12的一個主面上彼此隔開而設置有源極電極16及汲極電極18。此外，依序積層有作為活性層14的上文所述的氧化物半導體膜、閘極絕緣膜20及閘極電極22。 Fig. 2 is a schematic view showing an example of a TFT of the present invention which has a top gate structure and is of a bottom contact type. In the TFT 30 shown in FIG. 2, the source electrode 16 and the drain electrode 18 are provided on one main surface of the substrate 12 to be spaced apart from each other. Further, the above-described oxide semiconductor film, gate insulating film 20, and gate electrode 22 as the active layer 14 are laminated in this order.

圖3為表示底部閘極結構且為頂部接觸型的本發明的 TFT的一例的示意圖。於圖3所示的TFT 40中，於基板12的一個主面上依序積層有閘極電極22、閘極絕緣膜20及作為活性層14的上文所述的氧化物半導體膜。此外，於該活性層14的表面上彼此隔開而設置有源極電極16及汲極電極18。 3 is a view showing the bottom gate structure and the top contact type of the present invention A schematic diagram of an example of a TFT. In the TFT 40 shown in FIG. 3, a gate electrode 22, a gate insulating film 20, and the above-described oxide semiconductor film as the active layer 14 are sequentially laminated on one main surface of the substrate 12. Further, a source electrode 16 and a drain electrode 18 are provided on the surface of the active layer 14 so as to be spaced apart from each other.

圖4為表示底部閘極結構且為底部接觸型的本發明的TFT的一例的示意圖。於圖4所示的TFT 50中，於基板12的一個主面上依序積層有閘極電極22及閘極絕緣膜20。此外，於該閘極絕緣膜20的表面上彼此隔開而設置有源極電極16及汲極電極18，進而於該些構件上積層有作為活性層14的上文所述的氧化物半導體膜。 4 is a schematic view showing an example of a TFT of the present invention which has a bottom gate structure and is of a bottom contact type. In the TFT 50 shown in FIG. 4, a gate electrode 22 and a gate insulating film 20 are sequentially laminated on one main surface of the substrate 12. Further, the source electrode 16 and the drain electrode 18 are provided on the surface of the gate insulating film 20, and the above-described oxide semiconductor film as the active layer 14 is laminated on the members. .

以下的實施形態中，主要對圖1所示的頂部閘極型的薄膜電晶體10進行說明，但本發明的薄膜電晶體並不限定於頂部閘極型，亦可為底部閘極型的薄膜電晶體。 In the following embodiments, the top gate type thin film transistor 10 shown in FIG. 1 is mainly described. However, the thin film transistor of the present invention is not limited to the top gate type, and may be a bottom gate type film. Transistor.

(活性層) (active layer)

於製造本實施形態的薄膜電晶體10的情形時，首先經由所述的前驅物膜形成步驟及轉化步驟而於基板12上形成金屬氧化物半導體膜。 In the case of manufacturing the thin film transistor 10 of the present embodiment, a metal oxide semiconductor film is first formed on the substrate 12 via the precursor film forming step and the conversion step.

將金屬氧化物半導體膜圖案化為活性層的形狀。再者，圖案化可藉由所述的噴墨法、分配器法、凸版印刷法、及凹版印刷法預先形成具有活性層的圖案的金屬氧化物前驅物膜，並轉化為金屬氧化物半導體膜，亦可藉由光微影及蝕刻將金屬氧化物半導體膜圖案化為活性層的形狀。於藉由光微影及蝕刻進行圖案形 成時，例如藉由光微影於金屬氧化物半導體膜的作為活性層而殘存的部分上形成抗蝕劑圖案，藉由鹽酸、硝酸、稀硫酸或者磷酸、硝酸及乙酸的混合液等酸溶液進行蝕刻，藉此形成活性層14的圖案。 The metal oxide semiconductor film is patterned into the shape of the active layer. Further, the patterning may be performed by forming the metal oxide precursor film having the pattern of the active layer in advance by the inkjet method, the dispenser method, the relief printing method, and the gravure printing method, and converting into a metal oxide semiconductor film. The metal oxide semiconductor film can also be patterned into the shape of the active layer by photolithography and etching. Patterning by photolithography and etching At the time of formation, a resist pattern is formed on a portion of the metal oxide semiconductor film remaining as an active layer by photolithography, and an acid solution such as hydrochloric acid, nitric acid, dilute sulfuric acid or a mixture of phosphoric acid, nitric acid, and acetic acid is used. Etching is performed, thereby forming a pattern of the active layer 14.

就平坦性及膜形成所需的時間的觀點而言，活性層14的厚度較佳為5nm以上且50nm以下。 The thickness of the active layer 14 is preferably 5 nm or more and 50 nm or less from the viewpoint of flatness and time required for film formation.

又，就獲得高的遷移率的觀點而言，活性層14中的銦的含量較佳為活性層14所含的金屬成分的50atom%以上，更佳為80atom%以上。 Further, from the viewpoint of obtaining a high mobility, the content of indium in the active layer 14 is preferably 50 atom% or more, more preferably 80 atom% or more, of the metal component contained in the active layer 14.

(保護層) (The protective layer)

較佳為於活性層14上形成用以於源極電極16、汲極電極18的蝕刻時保護活性層14的保護層(未圖示)。保護層的成膜方法並無特別限定，可與金屬氧化物半導體膜連續進行成膜，亦可於金屬氧化物半導體膜的圖案化後形成。 Preferably, a protective layer (not shown) for protecting the active layer 14 during etching of the source electrode 16 and the drain electrode 18 is formed on the active layer 14. The film formation method of the protective layer is not particularly limited, and it can be formed continuously with the metal oxide semiconductor film, or can be formed after patterning of the metal oxide semiconductor film.

作為保護層，可為金屬氧化物層，亦可為如樹脂般的有機材料。再者，保護層亦可於形成源極電極16及汲極電極18(適當記作「源極電極、汲極電極」)後去除。 The protective layer may be a metal oxide layer or an organic material such as a resin. Further, the protective layer may be removed after forming the source electrode 16 and the drain electrode 18 (referred to as "source electrode, drain electrode" as appropriate).

(源極電極、汲極電極) (source electrode, drain electrode)

於活性層14上形成源極電極16、汲極電極18。源極電極16、汲極電極18分別使用以作為電極而發揮功能的方式具有高的導電性者，可使用Al、Mo、Cr、Ta、Ti、Ag、Au等金屬，Al-Nd，Ag合金，氧化錫、氧化鋅、氧化銦、氧化銦錫(ITO)、氧化鋅銦(IZO)、 In-Ga-Zn-O等金屬氧化物導電膜等來形成。 A source electrode 16 and a drain electrode 18 are formed on the active layer 14. Each of the source electrode 16 and the drain electrode 18 has high conductivity so as to function as an electrode, and metals such as Al, Mo, Cr, Ta, Ti, Ag, and Au, and Al-Nd, Ag alloy can be used. , tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), zinc indium oxide (IZO), A metal oxide conductive film such as In-Ga-Zn-O is formed.

於形成源極電極16、汲極電極18的情形時，只要依照考慮到與所使用的材料的適性而自印刷方式、塗佈方式等濕式方式，真空蒸鍍法、濺鍍法、離子鍍覆(ion plating)法等物理方式，化學氣相沈積(Chemical Vapor Deposition，CVD)、電漿CVD法等化學方式等中適當選擇的方法來成膜即可。 In the case of forming the source electrode 16 and the drain electrode 18, vacuum deposition, sputtering, or ion plating may be employed in a wet manner such as a printing method or a coating method in consideration of suitability with a material to be used. A film may be formed by a physical method such as ion plating or a chemical method such as chemical vapor deposition (CVD) or plasma CVD.

若考慮到成膜性、藉由蝕刻或舉離(lift-off)法的圖案化性、導電性等，則源極電極16、汲極電極18的膜厚較佳為設為10nm以上且1000nm以下，更佳為設為50nm以上且100nm以下。 The film thickness of the source electrode 16 and the drain electrode 18 is preferably 10 nm or more and 1000 nm in consideration of film formability, patterning property by etching or lift-off method, conductivity, and the like. Hereinafter, it is more preferably 50 nm or more and 100 nm or less.

源極電極16、汲極電極18可於形成導電膜後，例如藉由蝕刻或舉離法以既定的形狀進行圖案化而形成，亦可藉由噴墨法等直接形成圖案。此時，較佳為將源極電極16、汲極電極18及連接於該些電極的配線(未圖示)同時圖案化。 The source electrode 16 and the drain electrode 18 may be formed by patterning in a predetermined shape by, for example, etching or lift-off after forming a conductive film, or may be directly patterned by an inkjet method or the like. In this case, it is preferable to simultaneously pattern the source electrode 16 and the drain electrode 18 and the wiring (not shown) connected to the electrodes.

(閘極絕緣膜) (gate insulating film)

形成源極電極16、汲極電極18及配線(未圖示)後，形成閘極絕緣膜20。閘極絕緣膜20較佳為具有高的絕緣性者，例如可製成SiO2、SiNx、SiON、Al2O3、Y2O3、Ta2O5、HfO2等絕緣膜或含有該些化合物的兩種以上的絕緣膜。 After the source electrode 16, the drain electrode 18, and the wiring (not shown) are formed, the gate insulating film 20 is formed. The gate insulating film 20 preferably has high insulating properties, and for example, can be made of an insulating film such as SiO 2 , SiN x , SiON, Al 2 O 3 , Y 2 O 3 , Ta 2 O 5 , HfO 2 or the like. Two or more insulating films of these compounds.

閘極絕緣膜20的形成只要依照考慮到與所使用的材料的適性而自印刷方式、塗佈方式等濕式方式，真空蒸鍍法、濺鍍法、離子鍍覆法等物理方式，CVD、電漿CVD法等化學方式等中適當選 擇的方法來成膜即可。 The gate insulating film 20 is formed by a wet method such as a vacuum deposition method, a sputtering method, or an ion plating method in accordance with a wet method such as a printing method or a coating method in consideration of suitability with a material to be used, CVD, Appropriate selection in chemical methods such as plasma CVD The method of choice can be used to form a film.

再者，閘極絕緣膜20必須具有用以降低洩漏(leak)電流及提高耐電壓性的厚度，另一方面，若閘極絕緣膜20的厚度過大，則會導致驅動電壓的上升。閘極絕緣膜20亦取決於材質，但閘極絕緣膜20的厚度較佳為10nm~10μm，更佳為50nm~1000nm，尤佳為100nm~400nm。 Further, the gate insulating film 20 must have a thickness for reducing leakage current and improving withstand voltage. On the other hand, if the thickness of the gate insulating film 20 is too large, the driving voltage is increased. The gate insulating film 20 is also dependent on the material, but the thickness of the gate insulating film 20 is preferably 10 nm to 10 μm, more preferably 50 nm to 1000 nm, and particularly preferably 100 nm to 400 nm.

(閘極電極) (gate electrode)

形成閘極絕緣膜20後，形成閘極電極22。閘極電極22使用具有高的導電性者，可使用Al、Mo、Cr、Ta、Ti、Ag、Au等金屬，Al-Nd，Ag合金，氧化錫、氧化鋅、氧化銦、氧化銦錫(ITO)、氧化鋅銦(IZO)、IGZO等金屬氧化物導電膜等來形成。作為閘極電極22，可將該些導電膜以單層結構或2層以上的積層結構的形式來使用。 After the gate insulating film 20 is formed, the gate electrode 22 is formed. When the gate electrode 22 is made to have high conductivity, a metal such as Al, Mo, Cr, Ta, Ti, Ag, Au, Al-Nd, Ag alloy, tin oxide, zinc oxide, indium oxide, or indium tin oxide may be used. A metal oxide conductive film such as ITO), indium zinc oxide (IZO) or IGZO is formed. As the gate electrode 22, these conductive films can be used in the form of a single layer structure or a laminated structure of two or more layers.

閘極電極22是依照考慮到與所使用的材料的適性而自印刷方式、塗佈方式等濕式方式，真空蒸鍍法、濺鍍法、離子鍍覆法等物理方式，CVD、電漿CVD法等化學方式等中適當選擇的方法來成膜。 The gate electrode 22 is in a wet manner such as a printing method or a coating method in consideration of the suitability of the material to be used, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, and CVD or plasma CVD. A film is formed by a method selected as appropriate in a chemical method such as a method.

若考慮到成膜性、藉由蝕刻或舉離法的圖案化性、導電性等，則用以形成閘極電極22的金屬膜的膜厚較佳為設為10nm以上且1000nm以下，更佳為設為50nm以上且200nm以下。 The film thickness of the metal film for forming the gate electrode 22 is preferably 10 nm or more and 1000 nm or less, more preferably in consideration of film formation property, patterning property by etching or lift-off method, conductivity, and the like. It is set to 50 nm or more and 200 nm or less.

成膜後，可藉由利用蝕刻或舉離法以既定的形狀進行圖案化而形成閘極電極22，亦可藉由噴墨法等直接形成圖案。此時，較 佳為將閘極電極22及閘極配線(未圖示)同時圖案化。 After the film formation, the gate electrode 22 can be formed by patterning in a predetermined shape by etching or lift-off, and the pattern can be directly formed by an inkjet method or the like. At this time, It is preferable to simultaneously pattern the gate electrode 22 and the gate wiring (not shown).

對以上所說明的本實施形態的薄膜電晶體10的用途並無特別限定，由於顯示出高的傳輸特性，故可應用於各種電子元件。具體而言，適於製作液晶顯示裝置、有機電致發光(Electro Luminescence，EL)顯示裝置、無機EL顯示裝置等顯示裝置中的驅動元件、使用耐熱性低的樹脂基板的可撓性顯示器。 The use of the thin film transistor 10 of the present embodiment described above is not particularly limited, and since it exhibits high transmission characteristics, it can be applied to various electronic components. Specifically, it is suitable for producing a driving element in a display device such as a liquid crystal display device, an organic electroluminescence (EL) display device, or an inorganic EL display device, and a flexible display using a resin substrate having low heat resistance.

進而，藉由本發明所製造的薄膜電晶體可較佳地用作X射線感測器、影像感測器等各種感測器、微機電系統(Micro Electro Mechanical System，MEMS)等各種電子元件中的驅動元件(驅動電路)。 Further, the thin film transistor manufactured by the present invention can be preferably used as various sensors such as an X-ray sensor and an image sensor, and various electronic components such as a Micro Electro Mechanical System (MEMS). Drive element (drive circuit).

<液晶顯示裝置> <Liquid crystal display device>

關於作為本發明的一實施形態的液晶顯示裝置，圖5表示其一部分的概略剖面圖，圖6表示電氣配線的概略構成圖。 FIG. 5 is a schematic cross-sectional view showing a part of a liquid crystal display device according to an embodiment of the present invention, and FIG. 6 is a schematic configuration view of the electric wiring.

如圖5所示，本實施形態的液晶顯示裝置100為以下構成：具備圖1所示的頂部閘極結構且為頂部接觸型的TFT 10、於TFT 10的經鈍化層102保護的閘極電極22上由畫素下部電極104及其對向上部電極106所夾持的液晶層108、及用以與各畫素相對應地發出不同顏色的紅(R)綠(G)藍(B)的彩色濾光片110，且於TFT 10的基板12側及RGB彩色濾光片110上分別具備偏光板112a、偏光板112b。 As shown in FIG. 5, the liquid crystal display device 100 of the present embodiment has a top gate-type TFT 10 having a top gate structure as shown in FIG. 1, and a gate electrode protected by the passivation layer 102 of the TFT 10. 22 is composed of a pixel lower electrode 104 and a liquid crystal layer 108 sandwiched between the upper electrode 106 and red (R) green (G) blue (B) for emitting different colors corresponding to respective pixels. The color filter 110 includes a polarizing plate 112a and a polarizing plate 112b on the substrate 12 side of the TFT 10 and the RGB color filter 110, respectively.

又，如圖6所示，本實施形態的液晶顯示裝置100具備彼此平行的多條閘極配線112、及與該閘極配線112交叉且彼此平 行的資料配線114。此處，閘極配線112與資料配線114經電性絕緣。於閘極配線112與資料配線114的交叉部附近，具備TFT 10。 Further, as shown in FIG. 6, the liquid crystal display device 100 of the present embodiment includes a plurality of gate wirings 112 that are parallel to each other, and intersects with the gate wirings 112 and are flat with each other. Line data wiring 114. Here, the gate wiring 112 and the data wiring 114 are electrically insulated. The TFT 10 is provided in the vicinity of the intersection of the gate wiring 112 and the data wiring 114.

TFT 10的閘極電極22連接於閘極配線112，TFT 10的源極電極16連接於資料配線114。又，TFT 10的汲極電極18經由設置於閘極絕緣膜20中的接觸孔116(於接觸孔116中填埋有導電體)而連接於畫素下部電極104。該畫素下部電極104與經接地的對向上部電極106一起構成電容器118。 The gate electrode 22 of the TFT 10 is connected to the gate wiring 112, and the source electrode 16 of the TFT 10 is connected to the data wiring 114. Further, the drain electrode 18 of the TFT 10 is connected to the pixel lower electrode 104 via a contact hole 116 provided in the gate insulating film 20 (a conductor is buried in the contact hole 116). The pixel lower electrode 104 and the grounded pair upper electrode 106 together form a capacitor 118.

<有機EL顯示裝置> <Organic EL display device>

關於本發明的一實施形態的主動式矩陣方式的有機EL顯示裝置，圖7表示一部分的概略剖面圖，圖8表示電氣配線的概略構成圖。 FIG. 7 is a schematic cross-sectional view showing a part of the active matrix type organic EL display device according to the embodiment of the present invention, and FIG. 8 is a schematic configuration view of the electric wiring.

本實施形態的主動式矩陣方式的有機EL顯示裝置200成為以下構成：於具備鈍化層202的基板12上，具備圖1所示的頂部閘極結構的TFT 10作為驅動用TFT 10a及開關用TFT 10b，於TFT 10a、TFT 10b上具備有機EL發光元件214，所述有機EL發光元件214包含由下部電極208及上部電極210所夾持的有機發光層212，上表面亦由鈍化層216保護。 In the active matrix type organic EL display device 200 of the present embodiment, the TFT 10 having the top gate structure shown in FIG. 1 is provided as the driving TFT 10a and the switching TFT on the substrate 12 including the passivation layer 202. 10b, an organic EL light-emitting element 214 is provided on the TFT 10a and the TFT 10b. The organic EL light-emitting element 214 includes an organic light-emitting layer 212 sandwiched between the lower electrode 208 and the upper electrode 210, and the upper surface is also protected by a passivation layer 216.

又，如圖8所示，本實施形態的有機EL顯示裝置200具備彼此平行的多條閘極配線220、及與該閘極配線220交叉且彼此平行的資料配線222及驅動配線224。此處，閘極配線220與資料配線222、驅動配線224經電性絕緣。開關用TFT 10b的閘極電極22連接於閘極配線220，開關用TFT 10b的源極電極16連接於 資料配線222。又，開關用TFT 10b的汲極電極18連接於驅動用TFT 10a的閘極電極22，並且藉由使用電容器226而將驅動用TFT 10a保持為接通(on)狀態。驅動用TFT 10a的源極電極16連接於驅動配線224，汲極電極18連接於有機EL發光元件214。 Moreover, as shown in FIG. 8, the organic EL display device 200 of the present embodiment includes a plurality of gate wirings 220 that are parallel to each other, and a data wiring 222 and a driving wiring 224 that are parallel to the gate wiring 220 and are parallel to each other. Here, the gate wiring 220 is electrically insulated from the data wiring 222 and the driving wiring 224. The gate electrode 22 of the switching TFT 10b is connected to the gate wiring 220, and the source electrode 16 of the switching TFT 10b is connected to Data wiring 222. Further, the drain electrode 18 of the switching TFT 10b is connected to the gate electrode 22 of the driving TFT 10a, and the driving TFT 10a is kept in an on state by using the capacitor 226. The source electrode 16 of the driving TFT 10a is connected to the driving wiring 224, and the drain electrode 18 is connected to the organic EL light emitting element 214.

再者，於圖7所示的有機EL顯示裝置中，可將上部電極210作為透明電極而設為頂部發光型，亦可藉由將下部電極208及TFT的各電極作為透明電極而設為底部發光型。 Further, in the organic EL display device shown in FIG. 7, the upper electrode 210 may be a top emission type as a transparent electrode, or the bottom electrode 208 and each electrode of the TFT may be used as a transparent electrode. Light type.

<X射線感測器> <X-ray sensor>

關於作為本發明的一實施形態的X射線感測器，圖9表示其一部分的概略剖面圖，圖10表示其電氣配線的概略構成圖。 FIG. 9 is a schematic cross-sectional view showing a part of an X-ray sensor according to an embodiment of the present invention, and FIG. 10 is a schematic configuration view of the electric wiring.

本實施形態的X射線感測器300是具備以下構件而構成：形成於基板12上的TFT 10及電容器310、形成於電容器310上的電荷收集用電極302、X射線轉換層304及上部電極306。於TFT 10上設置有鈍化膜308。 The X-ray sensor 300 of the present embodiment includes the TFT 10 and the capacitor 310 formed on the substrate 12, the charge collecting electrode 302 formed on the capacitor 310, the X-ray conversion layer 304, and the upper electrode 306. . A passivation film 308 is provided on the TFT 10.

電容器310成為由電容器用下部電極312與電容器用上部電極314來夾持絕緣膜316的結構。電容器用上部電極314經由設置於絕緣膜316中的接觸孔318而與TFT 10的源極電極16及汲極電極18中的任一者(圖9中為汲極電極18)連接。 The capacitor 310 has a structure in which the insulating film 316 is sandwiched between the capacitor lower electrode 312 and the capacitor upper electrode 314. The capacitor upper electrode 314 is connected to any one of the source electrode 16 and the drain electrode 18 of the TFT 10 (the gate electrode 18 in FIG. 9) via a contact hole 318 provided in the insulating film 316.

電荷收集用電極302設置於電容器310的電容器用上部電極314上，與電容器用上部電極314接觸。 The charge collection electrode 302 is provided on the capacitor upper electrode 314 of the capacitor 310, and is in contact with the capacitor upper electrode 314.

X射線轉換層304為包含非晶硒的層，以覆蓋TFT 10及電容器310的方式設置。 The X-ray conversion layer 304 is a layer containing amorphous selenium, and is disposed to cover the TFT 10 and the capacitor 310.

上部電極306設置於X射線轉換層304上，與X射線轉換層304接觸。 The upper electrode 306 is disposed on the X-ray conversion layer 304 and is in contact with the X-ray conversion layer 304.

如圖10所示，本實施形態的X射線感測器300具備彼此平行的多條閘極配線320、及與閘極配線320交叉且彼此平行的多條資料配線322。此處，閘極配線320與資料配線322經電性絕緣。於閘極配線320與資料配線322的交叉部附近具備TFT 10。 As shown in FIG. 10, the X-ray sensor 300 of the present embodiment includes a plurality of gate wirings 320 that are parallel to each other, and a plurality of data wirings 322 that are parallel to each other and that are parallel to the gate wirings 320. Here, the gate wiring 320 and the data wiring 322 are electrically insulated. The TFT 10 is provided in the vicinity of the intersection of the gate wiring 320 and the data wiring 322.

TFT 10的閘極電極22連接於閘極配線320，TFT 10的源極電極16連接於資料配線322。又，TFT 10的汲極電極18連接於電荷收集用電極302，進而該電荷收集用電極302連接於電容器310。 The gate electrode 22 of the TFT 10 is connected to the gate wiring 320, and the source electrode 16 of the TFT 10 is connected to the data wiring 322. Further, the drain electrode 18 of the TFT 10 is connected to the charge collection electrode 302, and the charge collection electrode 302 is connected to the capacitor 310.

於本實施形態的X射線感測器300中，X射線於圖9中自上部電極306側入射，於X射線轉換層304中生成電子-電洞對。預先藉由上部電極306對X射線轉換層304施加高電場，藉此所生成的電荷蓄積於電容器310中，藉由依序掃描TFT 10而讀出。 In the X-ray sensor 300 of the present embodiment, X-rays are incident from the upper electrode 306 side in FIG. 9, and an electron-hole pair is generated in the X-ray conversion layer 304. A high electric field is applied to the X-ray conversion layer 304 by the upper electrode 306 in advance, whereby the generated charges are accumulated in the capacitor 310, and are read by sequentially scanning the TFT 10.

再者，於所述實施形態的液晶顯示裝置100、有機EL顯示裝置200、及X射線感測器300中，設為具備頂部閘極結構的TFT，但TFT並不限定於此，亦可為圖2~圖4所示的結構的TFT。 Further, in the liquid crystal display device 100, the organic EL display device 200, and the X-ray sensor 300 of the above-described embodiment, a TFT having a top gate structure is used, but the TFT is not limited thereto, and may be The TFT of the structure shown in FIGS. 2 to 4.

[實施例] [Examples]

以下對實施例進行說明，但本發明不受該些實施例任何限定。 The embodiments are described below, but the invention is not limited by the examples.

<實施例1> <Example 1>

製作如以下般的試樣，並進行評價。 A sample as described below was produced and evaluated.

使硝酸銦(In(NO3)3．xH2O，4N，高純度化學研究所公司製造)溶解於2-甲氧基乙醇(試劑特級，和光純藥工業公司製造)中，製作濃度0.1mol/L的硝酸銦溶液。 Indium nitrate (In(NO 3 ) 3 .xH 2 O, 4N, manufactured by High Purity Chemical Research Co., Ltd.) was dissolved in 2-methoxyethanol (reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a concentration of 0.1 mol. /L solution of indium nitrate.

製作使用帶有熱氧化膜的p型矽基板作為基板、使用熱氧化膜作為閘極絕緣膜的簡易型的TFT。 A simple TFT using a p-type tantalum substrate with a thermal oxide film as a substrate and a thermal oxide film as a gate insulating film was produced.

於帶有熱氧化膜的p型矽1吋見方的基板上，以1500rpm的轉速將所製作的硝酸銦溶液旋轉塗佈30秒後，於加熱至60℃的加熱板上進行1分鐘乾燥。 The produced indium nitrate solution was spin-coated on a substrate having a p-type 热1 square with a thermal oxide film at 1,500 rpm for 30 seconds, and then dried on a hot plate heated to 60 ° C for 1 minute.

於下述條件下將所得的金屬氧化物前驅物膜轉化為金屬氧化物膜。 The obtained metal oxide precursor film was converted into a metal oxide film under the following conditions.

使用具備低壓水銀燈的真空紫外光(Vacuum Ultraviolet，VUV)乾式處理器(奧克製作所(Orc Manufacturing)公司製造，VUE-3400-F)作為紫外線照射裝置。 A vacuum ultraviolet (Vucuum Ultraviolet (VUV) dry type processor (VC-3400-F, manufactured by Orc Manufacturing Co., Ltd.) equipped with a low-pressure mercury lamp was used as the ultraviolet irradiation device.

將於基板上形成有金屬氧化物前驅物膜的試樣設置於裝置內的表面溫度經加熱至160℃的加熱板上後，等待5分鐘。期間，藉由於裝置處理室內流過(flow)50L/min的氮氣，將處理室內的氧濃度保持為50ppm以下。 A sample in which a metal oxide precursor film was formed on the substrate was placed on a hot plate heated to 160 ° C in the apparatus, and waited for 5 minutes. During this period, the oxygen concentration in the treatment chamber was maintained at 50 ppm or less by flowing 50 L/min of nitrogen gas into the apparatus processing chamber.

再者，裝置處理室內的氧濃度是使用氧濃度計(橫河電機公司製造，OX100)進行測定。 In addition, the oxygen concentration in the apparatus processing chamber was measured using an oxygen concentration meter (manufactured by Yokogawa Electric Corporation, OX100).

等待5分鐘後，打開裝置內的光閘(shutter)，進行90分鐘、160℃的加熱處理下的紫外線照射處理，藉此獲得金屬氧化 物半導體膜。於加熱處理下的紫外線照射處理期間一直流過50L/min的氮氣。又，使用紫外線光量計(奧克製作所公司製造，UV-M10，受光器UV-25)測定試樣位置處的波長254nm的紫外線照度，結果為20mW/cm2。 After waiting for 5 minutes, the shutter in the apparatus was opened, and ultraviolet irradiation treatment under heat treatment for 90 minutes and 160 ° C was performed, whereby a metal oxide semiconductor film was obtained. Nitrogen gas of 50 L/min was passed during the ultraviolet irradiation treatment under heat treatment. Further, the ultraviolet illuminance at a wavelength of 254 nm at the sample position was measured using an ultraviolet light meter (UV-M10, light receiver UV-25), and it was 20 mW/cm 2 .

藉由蒸鍍於所述獲得的金屬氧化物半導體膜上來將源極電極、汲極電極成膜。源極電極、汲極電極的成膜是藉由使用金屬遮罩的圖案成膜來進行，以50nm的厚度將Ti成膜。源極電極、汲極電極的尺寸分別設為1mm見方，電極間距離設為0.2mm。 The source electrode and the drain electrode are formed by vapor deposition on the obtained metal oxide semiconductor film. The film formation of the source electrode and the drain electrode was performed by forming a film using a pattern of a metal mask, and Ti was formed into a film with a thickness of 50 nm. The sizes of the source electrode and the drain electrode were set to 1 mm square, and the distance between the electrodes was set to 0.2 mm.

<實施例2、實施例3、比較例1、比較例2> <Example 2, Example 3, Comparative Example 1, Comparative Example 2>

(對紫外線照射時的氧濃度加以變更的實施例、比較例) (Examples and Comparative Examples in which the oxygen concentration at the time of ultraviolet irradiation is changed)

藉由與實施例1相同的方法，改變氮氣的流量而製作簡易型TFT。 A simple TFT was produced by changing the flow rate of nitrogen gas in the same manner as in Example 1.

於實施例2、實施例3及比較例1、比較例2中任一者的條件中，5分鐘的等待過程中處理室內的氧濃度均成為大致恆定。再者，改變UV燈與基板之間的距離以使向膜面照射的UV光的照度不因氧濃度而發生變化，從而於僅氣體環境中的氧濃度不同的條件下製作各試樣。 In the conditions of any of Example 2, Example 3, Comparative Example 1, and Comparative Example 2, the oxygen concentration in the treatment chamber during the 5-minute waiting period was substantially constant. Further, the distance between the UV lamp and the substrate was changed so that the illuminance of the UV light irradiated to the film surface was not changed by the oxygen concentration, and each sample was produced under the condition that only the oxygen concentration in the gas atmosphere was different.

將實施例1~實施例3、比較例1、比較例2中的紫外線照射時的氮氣流量與處理室內的氧濃度示於表1。 Table 1 shows the flow rates of nitrogen gas during ultraviolet irradiation and the oxygen concentration in the treatment chamber in Examples 1 to 3, Comparative Example 1, and Comparative Example 2.

[評價] [Evaluation]

(電晶體特性) (Cell crystal characteristics)

對所述獲得的簡易型TFT使用半導體參數分析儀4156C(安捷倫科技公司製造)進行電晶體特性Vg-Id的測定。 The obtained simple TFT was measured for the transistor characteristics V g - I d using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies, Inc.).

Vg-Id特性的測定是藉由以下方式進行：將汲極電壓(Vd)固定為+1V，使閘極電壓(Vg)於-15V~+15V的範圍內變化，測定各閘極電壓下的汲極電流(Id)。 The V g -I d characteristic is measured by fixing the gate voltage (V d ) to +1 V and changing the gate voltage (V g ) in the range of -15 V to +15 V to measure each gate. The drain current (I d ) at the pole voltage.

將實施例1~實施例3中製作的簡易型TFT的Vg-Id特性示於圖11。又，將由實施例、比較例的Vg-Id特性求出的線性遷移率(以下有時記作「遷移率」)示於表2。 The V g -I d characteristics of the simple TFTs produced in Examples 1 to 3 are shown in Fig. 11 . Further, the linear mobility (hereinafter sometimes referred to as "mobility") obtained from the V g - I d characteristics of the examples and the comparative examples is shown in Table 2.

於加熱處理下的紫外線照射處理中，若氧濃度為30000ppm以下，則可獲得遷移率為4cm2/Vs以上的高的特性，若為 80000ppm以下，則可獲得遷移率為1cm2/Vs以上的特性。 In the ultraviolet irradiation treatment under the heat treatment, when the oxygen concentration is 30,000 ppm or less, a high mobility of 4 cm 2 /Vs or more can be obtained, and when it is 80,000 ppm or less, a mobility of 1 cm 2 /Vs or more can be obtained. characteristic.

(X射線光電子分光分析) (X-ray photoelectron spectroscopy)

對實施例1及比較例1所分別製作的金屬氧化物膜進行X射線光電子分光(XPS)分析。測定裝置為愛發科(ULVAC PHI)製造的QUANTERA SXM，作為測定條件，X射線源設為單色化AlKα(100μmφ，25W，15kV)、分析直徑為100μmφ、光電子取出角(take-off angle)為45℃。 The metal oxide film produced in each of Example 1 and Comparative Example 1 was subjected to X-ray photoelectron spectroscopy (XPS) analysis. The measuring device was QUANTER SXM manufactured by ULVAC PHI. As a measurement condition, the X-ray source was monochromatic AlKα (100 μmφ, 25 W, 15 kV), the analysis diameter was 100 μmφ, and the photoelectron take-off angle was taken. It is 45 ° C.

將實施例1及比較例1的XPS光譜(歸屬於氧的1 s電子的結合能為525eV~540eV的範圍)示於圖12。關於實施例1，低能量側(530eV附近具有峰頂的成分)的峰相對較強，可知為主要存在In-O-In鍵的緻密的氧化物膜。另一方面，關於比較例1，高能量側(532eV附近具有峰頂的成分)的峰相對較強，可知為主要存在In-O-H等的稀疏的氧化物膜。 The XPS spectrum of Example 1 and Comparative Example 1 (the binding energy of 1 s electrons attributed to oxygen is in the range of 525 eV to 540 eV) is shown in Fig. 12 . In Example 1, the peak of the low energy side (component having a peak top in the vicinity of 530 eV) was relatively strong, and it was found that a dense oxide film mainly having an In-O-In bond was present. On the other hand, in Comparative Example 1, the peak on the high energy side (the component having a peak top in the vicinity of 532 eV) was relatively strong, and it was found that a sparse oxide film such as In—O—H was mainly present.

<實施例4> <Example 4>

(將紫外線照射時的基板溫度設為120℃的實施例) (Example in which the substrate temperature at the time of ultraviolet irradiation is 120 ° C)

製作如以下般的試樣，並進行評價。 A sample as described below was produced and evaluated.

使硝酸銦(In(NO3)3．xH2O，4N，高純度化學研究所公司製造)溶解於2-甲氧基乙醇(試劑特級，和光純藥工業製造)中，製作0.1mol/L的濃度的硝酸銦溶液。 Indium nitrate (In(NO 3 ) 3 .xH 2 O, 4N, manufactured by High Purity Chemical Research Co., Ltd.) was dissolved in 2-methoxyethanol (reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare 0.1 mol/L. The concentration of indium nitrate solution.

製作使用帶有熱氧化膜的p型矽基板作為基板、使用熱氧化膜作為閘極絕緣膜的簡易型的TFT。於帶有熱氧化膜的p型矽1吋見方的基板上，以1500rpm的轉速將所製作的硝酸銦溶液 旋轉塗佈30秒後，於加熱至60℃的加熱板上進行1分鐘乾燥。 A simple TFT using a p-type tantalum substrate with a thermal oxide film as a substrate and a thermal oxide film as a gate insulating film was produced. The indium nitrate solution was prepared at a speed of 1500 rpm on a p-type substrate with a thermal oxide film. After spin coating for 30 seconds, it was dried on a hot plate heated to 60 ° C for 1 minute.

於下述條件下將所得的金屬氧化物前驅物膜轉化為金屬氧化物膜。裝置是使用具備低壓水銀燈的VUV乾式處理器(奧克製作所公司製造，VUE-3400-F)。 The obtained metal oxide precursor film was converted into a metal oxide film under the following conditions. The device is a VUV dry processor (VUE-3400-F, manufactured by Oak Industries, Inc.) equipped with a low-pressure mercury lamp.

將試樣設置於裝置內的表面溫度經加熱至120℃的加熱板上後，等待5分鐘。期間，藉由於裝置處理室內流過50L/min的氮氣，將處理室內的氧濃度設為50ppm以下。 After the sample was placed on a hot plate heated to 120 ° C on the surface of the apparatus, it was waited for 5 minutes. During this period, the oxygen concentration in the treatment chamber was set to 50 ppm or less by flowing 50 L/min of nitrogen gas into the apparatus processing chamber.

等待5分鐘後，打開裝置內的光閘，藉由進行90分鐘、120℃的加熱處理下的紫外線照射處理而獲得金屬氧化物半導體膜。於加熱處理下的紫外線照射處理期間一直流過50L/min的氮氣。試樣位置處的波長254nm的紫外線照度是使用紫外線光量計(奧克製作所公司製造，UV-M10，受光器UV-25)進行測定，為20mW/cm2。 After waiting for 5 minutes, the shutter in the apparatus was opened, and a metal oxide semiconductor film was obtained by performing ultraviolet irradiation treatment under heat treatment for 90 minutes and 120 °C. Nitrogen gas of 50 L/min was passed during the ultraviolet irradiation treatment under heat treatment. The ultraviolet illuminance at a wavelength of 254 nm at the sample position was measured using an ultraviolet light meter (UV-M10, light receiver UV-25 manufactured by Oak Industries, Inc.) at 20 mW/cm 2 .

藉由蒸鍍於所述獲得的金屬氧化物半導體膜上來將源極電極、汲極電極成膜。源極電極、汲極電極是藉由使用金屬遮罩的圖案成膜進行製作，以50nm的厚度將Ti成膜。源極電極、汲極電極的尺寸分別設為1mm見方，電極間距離設為0.2mm。 The source electrode and the drain electrode are formed by vapor deposition on the obtained metal oxide semiconductor film. The source electrode and the drain electrode were formed by pattern formation using a metal mask, and Ti was formed into a film with a thickness of 50 nm. The sizes of the source electrode and the drain electrode were set to 1 mm square, and the distance between the electrodes was set to 0.2 mm.

[評價] [Evaluation]

(電晶體特性) (Cell crystal characteristics)

對所述獲得的簡易型TFT使用半導體參數分析儀4156C(安捷倫科技公司製造)進行電晶體特性Vg-Id的測定。 The obtained simple TFT was measured for the transistor characteristics V g - I d using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies, Inc.).

Vg-Id特性的測定是藉由以下方式進行：將汲極電壓(Vd)固 定為+1V，使閘極電壓(Vg)於-15V~+15V的範圍內變化，測定各閘極電壓下的汲極電流(Id)。 The V g -I d characteristic is measured by fixing the gate voltage (V d ) to +1 V and changing the gate voltage (V g ) in the range of -15 V to +15 V to measure each gate. The drain current (I d ) at the pole voltage.

將由實施例4的Vg-Id特性求出的線性遷移率示於表3。 The linear mobility determined by the V g -I d characteristic of Example 4 is shown in Table 3.

<實施例5、實施例6> <Example 5, Example 6>

(含有In與Zn或Ga的實施例) (Example containing In and Zn or Ga)

-實施例5- - Example 5 -

製作如以下般的試樣，並進行評價。 A sample as described below was produced and evaluated.

使硝酸銦(In(NO3)3．xH2O，4N，高純度化學研究所公司製造)及硝酸鋅(Zn(NO3)2．6H2O，3N，高純度化學研究所公司製造)溶解於2-甲氧基乙醇(試劑特級，和光純藥工業製造)中，製作硝酸銦濃度0.095mol/L、硝酸鋅濃度0.005mol/L的濃度的硝酸銦/硝酸鋅混合溶液。 Indium nitrate (In(NO 3 ) 3 .xH 2 O, 4N, manufactured by High Purity Chemical Research Co., Ltd.) and zinc nitrate (Zn(NO 3 ) 2 .6H 2 O, 3N, manufactured by High Purity Chemical Research Institute) It was dissolved in 2-methoxyethanol (special grade of reagent, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a mixed solution of indium nitrate/zinc nitrate at a concentration of indium nitrate of 0.095 mol/L and a zinc nitrate concentration of 0.005 mol/L.

製作使用帶有熱氧化膜的p型矽基板作為基板、使用熱氧化膜作為閘極絕緣膜的簡易型的TFT。於帶有熱氧化膜的p型矽1吋見方的基板上，以1500rpm的轉速將所製作的硝酸銦/硝酸鋅混合溶液旋轉塗佈30秒後，於加熱至60℃的加熱板上進行1分鐘乾燥。 A simple TFT using a p-type tantalum substrate with a thermal oxide film as a substrate and a thermal oxide film as a gate insulating film was produced. The prepared indium nitrate/zinc nitrate mixed solution was spin-coated on a substrate having a thermal oxide film on a p-type 吋1吋 square substrate at 1,500 rpm for 30 seconds, and then heated on a hot plate heated to 60 ° C. Dry in minutes.

於下述條件下將所得的金屬氧化物前驅物膜轉化為金 屬氧化物膜。裝置是使用具備低壓水銀燈的VUV乾式處理器(奧克製作所公司製造，VUE-3400-F)。 The resulting metal oxide precursor film is converted into gold under the following conditions Is an oxide film. The device is a VUV dry processor (VUE-3400-F, manufactured by Oak Industries, Inc.) equipped with a low-pressure mercury lamp.

將試樣設置於裝置內的表面溫度經加熱至160℃的加熱板上後，等待5分鐘。期間，藉由於裝置處理室內流過50L/min的氮氣，將處理室內的氧濃度設為50ppm以下。 The sample was placed on a hot plate heated to 160 ° C on the surface of the apparatus, and waited for 5 minutes. During this period, the oxygen concentration in the treatment chamber was set to 50 ppm or less by flowing 50 L/min of nitrogen gas into the apparatus processing chamber.

等待5分鐘後，打開裝置內的光閘，進行90分鐘、160℃的加熱處理下的紫外線照射處理，藉此獲得金屬氧化物半導體膜。於加熱處理下的紫外線照射處理期間一直流過50L/min的氮氣。試樣位置處的波長254nm的紫外線照度是使用紫外線光量計(奧克製作所公司製造，UV-M10，受光器UV-25)進行測定，為20mW/cm2。 After waiting for 5 minutes, the shutter in the apparatus was opened, and ultraviolet irradiation treatment was performed for 90 minutes and heat treatment at 160 ° C, whereby a metal oxide semiconductor film was obtained. Nitrogen gas of 50 L/min was passed during the ultraviolet irradiation treatment under heat treatment. The ultraviolet illuminance at a wavelength of 254 nm at the sample position was measured using an ultraviolet light meter (UV-M10, light receiver UV-25 manufactured by Oak Industries, Inc.) at 20 mW/cm 2 .

藉由蒸鍍於所述獲得的金屬氧化物半導體膜上來將源極電極、汲極電極成膜。源極電極、汲極電極是藉由使用金屬遮罩的圖案成膜進行製作，以50nm的厚度將Ti成膜。源極電極、汲極電極的尺寸分別設為1mm見方，電極間距離設為0.2mm。 The source electrode and the drain electrode are formed by vapor deposition on the obtained metal oxide semiconductor film. The source electrode and the drain electrode were formed by pattern formation using a metal mask, and Ti was formed into a film with a thickness of 50 nm. The sizes of the source electrode and the drain electrode were set to 1 mm square, and the distance between the electrodes was set to 0.2 mm.

-實施例6- - Example 6 -

製作如以下般的試樣，並進行評價。 A sample as described below was produced and evaluated.

使硝酸銦(In(NO3)3．xH2O，4N，高純度化學研究所公司製造)及硝酸鎵(Ga(NO3)2．xH2O，3N，高純度化學研究所公司製造)溶解於2-甲氧基乙醇(試劑特級，和光純藥工業製造)中，製作硝酸銦濃度0.095mol/L、硝酸鎵濃度0.005mol/L的濃度的硝酸銦/硝酸鎵混合溶液。 Indium nitrate (In(NO 3 ) 3 .xH 2 O, 4N, manufactured by High Purity Chemical Research Co., Ltd.) and gallium nitrate (Ga(NO 3 ) 2 .xH 2 O, 3N, manufactured by High Purity Chemical Research Institute) The solution was dissolved in 2-methoxyethanol (special grade of reagent, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a mixed solution of indium nitrate/gallium nitrate having a concentration of indium nitrate of 0.095 mol/L and a concentration of gallium nitrate of 0.005 mol/L.

製作使用帶有熱氧化膜的p型矽基板作為基板、使用熱氧化膜作為閘極絕緣膜的簡易型的TFT。於帶有熱氧化膜的p型矽1吋見方的基板上，以1500rpm的轉速將所製作的硝酸銦/硝酸鎵混合溶液旋轉塗佈30秒後，於加熱至60℃的加熱板上進行1分鐘乾燥。 A simple TFT using a p-type tantalum substrate with a thermal oxide film as a substrate and a thermal oxide film as a gate insulating film was produced. The prepared indium nitrate/gallium nitrate mixed solution was spin-coated on a substrate having a p-type 吋1 square with a thermal oxide film at 1,500 rpm for 30 seconds, and then heated on a hot plate heated to 60 ° C. Dry in minutes.

於下述條件下將所得的金屬氧化物前驅物膜轉化為金屬氧化物膜。裝置是使用具備低壓水銀燈的VUV乾式處理器(奧克製作所公司製造，VUE-3400-F)。 The obtained metal oxide precursor film was converted into a metal oxide film under the following conditions. The device is a VUV dry processor (VUE-3400-F, manufactured by Oak Industries, Inc.) equipped with a low-pressure mercury lamp.

將試樣設置於裝置內的表面溫度經加熱至160℃的加熱板上後，等待5分鐘。期間，藉由於裝置處理室內流過50L/min的氮氣，將處理室內的氧濃度設為50ppm以下。 The sample was placed on a hot plate heated to 160 ° C on the surface of the apparatus, and waited for 5 minutes. During this period, the oxygen concentration in the treatment chamber was set to 50 ppm or less by flowing 50 L/min of nitrogen gas into the apparatus processing chamber.

等待5分鐘後，打開裝置內的光閘，進行90分鐘、160℃的加熱處理下的紫外線照射處理，藉此獲得金屬氧化物半導體膜。於加熱處理下的紫外線照射處理期間一直流過50L/min的氮氣。試樣位置處的波長254nm的紫外線照度是使用紫外線光量計(奧克製作所公司製造，UV-M10，受光器UV-25)進行測定，為20mW/cm2。 After waiting for 5 minutes, the shutter in the apparatus was opened, and ultraviolet irradiation treatment was performed for 90 minutes and heat treatment at 160 ° C, whereby a metal oxide semiconductor film was obtained. Nitrogen gas of 50 L/min was passed during the ultraviolet irradiation treatment under heat treatment. The ultraviolet illuminance at a wavelength of 254 nm at the sample position was measured using an ultraviolet light meter (UV-M10, light receiver UV-25 manufactured by Oak Industries, Inc.) at 20 mW/cm 2 .

藉由蒸鍍於所述獲得的金屬氧化物半導體膜上來將源極電極、汲極電極成膜。源極電極、汲極電極是藉由使用金屬遮罩的圖案成膜進行製作，以50nm的厚度將Ti成膜。源極電極、汲極電極的尺寸分別設為1mm見方，電極間距離設為0.2mm。 The source electrode and the drain electrode are formed by vapor deposition on the obtained metal oxide semiconductor film. The source electrode and the drain electrode were formed by pattern formation using a metal mask, and Ti was formed into a film with a thickness of 50 nm. The sizes of the source electrode and the drain electrode were set to 1 mm square, and the distance between the electrodes was set to 0.2 mm.

[評價] [Evaluation]

(電晶體特性) (Cell crystal characteristics)

對所述獲得的簡易型TFT使用半導體參數分析儀4156C(安捷倫科技公司製造)進行電晶體特性Vg-Id的測定。 The obtained simple TFT was measured for the transistor characteristics V g - I d using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies, Inc.).

Vg-Id特性的測定是藉由以下方式進行：將汲極電壓(Vd)固定為+1V，使閘極電壓(Vg)於-15V~+15V的範圍內變化，測定各閘極電壓下的汲極電流(Id)。 The V g -I d characteristic is measured by fixing the gate voltage (V d ) to +1 V and changing the gate voltage (V g ) in the range of -15 V to +15 V to measure each gate. The drain current (I d ) at the pole voltage.

將由實施例5、實施例6的Vg-Id特性求出的線性遷移率示於表4。 The linear mobility determined by the V g -I d characteristics of Example 5 and Example 6 is shown in Table 4.

<實施例7> <Example 7>

(於紫外線照射中升溫的實施例) (Example of temperature rise in ultraviolet irradiation)

製作如以下般的試樣，並進行評價。 A sample as described below was produced and evaluated.

使硝酸銦(In(NO3)3．xH2O，4N，高純度化學研究所製造)溶解於2-甲氧基乙醇(試劑特級，和光純藥工業製造)中，製作濃度0.1mol/L的硝酸銦溶液。 Indium nitrate (In(NO 3 ) 3 .xH 2 O, 4N, manufactured by High Purity Chemical Research Institute) was dissolved in 2-methoxyethanol (reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a concentration of 0.1 mol/L. Indium nitrate solution.

製作使用帶有熱氧化膜的p型矽基板作為基板、使用熱氧化膜作為閘極絕緣膜的簡易型的TFT。於帶有熱氧化膜的p型矽1吋見方的基板上，以1500rpm的轉速將所製作的硝酸銦溶液旋轉塗佈30秒後，於加熱至60℃的加熱板上進行1分鐘乾燥。 A simple TFT using a p-type tantalum substrate with a thermal oxide film as a substrate and a thermal oxide film as a gate insulating film was produced. The produced indium nitrate solution was spin-coated on a substrate having a p-type 热1 square with a thermal oxide film at 1,500 rpm for 30 seconds, and then dried on a hot plate heated to 60 ° C for 1 minute.

於下述條件下將所得的金屬氧化物前驅物膜轉化為金屬氧化物膜。裝置是使用具備低壓水銀燈的VUV乾式處理器(奧克製作所公司製造，VUE-3400-F)。 The obtained metal oxide precursor film was converted into a metal oxide film under the following conditions. The device is a VUV dry processor (VUE-3400-F, manufactured by Oak Industries, Inc.) equipped with a low-pressure mercury lamp.

將試樣設置於裝置內的表面溫度經加熱至124℃的加熱板上後，等待5分鐘。期間，藉由於裝置處理室內流過50L/min的氮氣，將處理室內的氧濃度設為50ppm以下。 After the sample was placed on a hot plate heated to 124 ° C on the surface of the apparatus, it was waited for 5 minutes. During this period, the oxygen concentration in the treatment chamber was set to 50 ppm or less by flowing 50 L/min of nitrogen gas into the apparatus processing chamber.

等待5分鐘後，打開裝置內的光閘，以0.4℃/min的升溫速度進行90分鐘紫外線照射處理，藉此獲得金屬氧化物半導體膜。於(90分鐘後達到160℃的)加熱處理下的紫外線照射處理期間一直流過50L/min的氮氣。試樣位置處的波長254nm的紫外線照度是使用紫外線光量計(奧克製作所製造，UV-M10，受光器UV-25)進行測定，為20mW/cm2。 After waiting for 5 minutes, the shutter in the apparatus was opened, and ultraviolet irradiation treatment was performed for 90 minutes at a temperature elevation rate of 0.4 ° C / min, whereby a metal oxide semiconductor film was obtained. Nitrogen gas of 50 L/min was passed during the ultraviolet irradiation treatment under heat treatment (after reaching 90 ° C after 90 minutes). The ultraviolet illuminance at a wavelength of 254 nm at the sample position was measured using an ultraviolet light meter (manufactured by Oak Industries, UV-M10, light receiver UV-25) to be 20 mW/cm 2 .

藉由蒸鍍於所述獲得的金屬氧化物半導體膜上來將源極電極、汲極電極成膜。源極電極、汲極電極是藉由使用金屬遮罩的圖案成膜進行製作，以50nm的厚度將Ti成膜。源極電極、汲極電極的尺寸分別設為1mm見方，電極間距離設為0.2mm。 The source electrode and the drain electrode are formed by vapor deposition on the obtained metal oxide semiconductor film. The source electrode and the drain electrode were formed by pattern formation using a metal mask, and Ti was formed into a film with a thickness of 50 nm. The sizes of the source electrode and the drain electrode were set to 1 mm square, and the distance between the electrodes was set to 0.2 mm.

<實施例8> <Example 8>

(對紫外線照射開始時的基板溫度與紫外線照射過程中的升溫速度加以變更的實施例) (Example in which the substrate temperature at the start of ultraviolet irradiation and the temperature increase rate during ultraviolet irradiation are changed)

於實施例7中，將紫外線照射處理開始時的基板溫度變更為79℃，將紫外線照射中的升溫速度變更為0.9℃/min(紫外線照射時間：90分鐘，紫外線照射處理結束時溫度：160℃)，除此以外， 藉由與實施例7相同的方法製作金屬氧化物半導體膜，並製作簡易型TFT。 In the seventh embodiment, the temperature of the substrate at the start of the ultraviolet irradiation treatment was changed to 79 ° C, and the temperature increase rate during the ultraviolet irradiation was changed to 0.9 ° C / min (ultraviolet irradiation time: 90 minutes, and the temperature at the end of the ultraviolet irradiation treatment: 160 ° C) ), in addition to this, A metal oxide semiconductor film was produced in the same manner as in Example 7 to fabricate a simple TFT.

[評價] [Evaluation]

(電晶體特性) (Cell crystal characteristics)

對所述獲得的簡易型TFT使用半導體參數分析儀4156C(安捷倫科技公司製造)進行電晶體特性Vg-Id的測定。 The obtained simple TFT was measured for the transistor characteristics V g - I d using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies, Inc.).

Vg-Id特性的測定是藉由以下方式進行：將汲極電壓(Vd)固定為+1V，使閘極電壓(Vg)於-15V~+15V的範圍內變化，測定各閘極電壓下的汲極電流(Id)。 The V g -I d characteristic is measured by fixing the gate voltage (V d ) to +1 V and changing the gate voltage (V g ) in the range of -15 V to +15 V to measure each gate. The drain current (I d ) at the pole voltage.

將實施例7、實施例8中製作的簡易型TFT的Vg-Id特性示於圖13。又，將實施例7、實施例8的金屬氧化物半導體膜(活性層)的轉化步驟中的紫外線照射處理開始溫度及升溫速度、以及由Vg-Id特性求出的線性遷移率示於表5。 The V g -I d characteristics of the simple TFTs produced in Example 7 and Example 8 are shown in Fig. 13 . Further, the ultraviolet irradiation treatment start temperature and the temperature increase rate in the conversion step of the metal oxide semiconductor film (active layer) of the seventh embodiment and the eighth embodiment, and the linear mobility obtained from the V g -I d characteristic are shown in table 5.

<比較例3> <Comparative Example 3>

(未進行紫外線照射的比較例) (Comparative example without ultraviolet irradiation)

製作如以下般的試樣，並進行評價。 A sample as described below was produced and evaluated.

使硝酸銦(In(NO3)3．xH2O，4N，高純度化學研究所公司製造)溶解於2-甲氧基乙醇(試劑特級，和光純藥工業製造)中，製作 濃度0.1mol/L的硝酸銦溶液。 Indium nitrate (In(NO 3 ) 3 .xH 2 O, 4N, manufactured by High Purity Chemical Research Co., Ltd.) was dissolved in 2-methoxyethanol (reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a concentration of 0.1 mol/ L indium nitrate solution.

製作使用帶有熱氧化膜的p型矽基板作為基板、使用熱氧化膜作為閘極絕緣膜的簡易型的TFT。於帶有熱氧化膜的p型矽1吋見方的基板上，以1500rpm的轉速將所製作的硝酸銦溶液旋轉塗佈30秒後，於加熱至60℃的加熱板上進行1分鐘乾燥。 A simple TFT using a p-type tantalum substrate with a thermal oxide film as a substrate and a thermal oxide film as a gate insulating film was produced. The produced indium nitrate solution was spin-coated on a substrate having a p-type 热1 square with a thermal oxide film at 1,500 rpm for 30 seconds, and then dried on a hot plate heated to 60 ° C for 1 minute.

於下述條件下將所得的金屬氧化物前驅物膜轉化為金屬氧化物膜。裝置是使用具備低壓水銀燈的VUV乾式處理器(奧克製作所公司製造，VUE-3400-F)。 The obtained metal oxide precursor film was converted into a metal oxide film under the following conditions. The device is a VUV dry processor (VUE-3400-F, manufactured by Oak Industries, Inc.) equipped with a low-pressure mercury lamp.

將試樣設置於裝置內的表面溫度經加熱至160℃的加熱板上後，等待5分鐘。期間，藉由於裝置處理室內流過50L/min的氮氣，將處理室內的氧濃度設為50ppm以下。 The sample was placed on a hot plate heated to 160 ° C on the surface of the apparatus, and waited for 5 minutes. During this period, the oxygen concentration in the treatment chamber was set to 50 ppm or less by flowing 50 L/min of nitrogen gas into the apparatus processing chamber.

等待5分鐘後，不打開裝置內的光閘，進行90分鐘、160℃的加熱處理。加熱處理期間一直流過50L/min的氮氣。試樣位置處的波長254nm的紫外線照度是使用紫外線光量計(奧克製作所公司製造，UV-M10，受光器UV-25)進行測定，為0.1mW/cm2以下。 After waiting for 5 minutes, the shutter in the apparatus was not opened, and heat treatment was performed for 90 minutes and 160 °C. Nitrogen gas of 50 L/min was passed through during the heat treatment. The ultraviolet illuminance at a wavelength of 254 nm at the sample position was measured using an ultraviolet light meter (UV-M10, light receiver UV-25 manufactured by Oak Industries, Inc.), and was 0.1 mW/cm 2 or less.

藉由蒸鍍於所述獲得的金屬氧化物半導體膜上來將源極電極、汲極電極成膜。源極電極、汲極電極是藉由使用金屬遮罩的圖案成膜進行製作，以50nm的厚度將Ti成膜。源極電極、汲極電極的尺寸分別設為1mm見方，電極間距離設為0.2mm。 The source electrode and the drain electrode are formed by vapor deposition on the obtained metal oxide semiconductor film. The source electrode and the drain electrode were formed by pattern formation using a metal mask, and Ti was formed into a film with a thickness of 50 nm. The sizes of the source electrode and the drain electrode were set to 1 mm square, and the distance between the electrodes was set to 0.2 mm.

[評價] [Evaluation]

(電晶體特性) (Cell crystal characteristics)

對所述獲得的簡易型TFT使用半導體參數分析儀4156C(安捷倫科技公司製造)進行電晶體特性Vg-Id的測定。 The obtained simple TFT was measured for the transistor characteristics V g - I d using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies, Inc.).

Vg-Id特性的測定是藉由以下方式進行：將汲極電壓(Vd)固定為+1V，使閘極電壓(Vg)於-15V~+15V的範圍內變化，測定各閘極電壓下的汲極電流(Id)。 The V g -I d characteristic is measured by fixing the gate voltage (V d ) to +1 V and changing the gate voltage (V g ) in the range of -15 V to +15 V to measure each gate. The drain current (I d ) at the pole voltage.

關於比較例3，並未確認到電晶體動作。 Regarding Comparative Example 3, the transistor operation was not confirmed.

將日本專利申請案2014-038995所揭示的全部內容以參照的方式併入至本說明書中。 The entire disclosure of Japanese Patent Application No. 2014-038995 is incorporated herein by reference.

關於本說明書中記載的全部文獻、專利、專利申請案、及技術標準，是與以下情況同樣地以參照的方式併入至本說明書中，所述情況為具體且分別記載將各文獻、專利、專利申請案、及技術標準以參照的方式併入的情況。 All the documents, patents, patent applications, and technical standards described in the present specification are incorporated into the specification in the same manner as the following, which is specific and separately describes each document, patent, The patent application, and the technical standards are incorporated by reference.

Claims (12)

一種金屬氧化物膜的製造方法，其包括：前驅物膜形成步驟，將含有溶劑及至少含有銦作為金屬成分的溶液塗佈於基板上而形成金屬氧化物前驅物膜；轉化步驟，於將所述金屬氧化物前驅物膜加熱的狀態下，在氧濃度為30000ppm以下的氣體環境下，以20mW/cm2以上且500mW/cm2以下的照度進行波長為300nm以下的紫外光的紫外線照射，藉此使所述金屬氧化物前驅物膜轉化為金屬氧化物膜，其中所述轉化步驟中的基板的溫度保持在160℃以上且低於200℃。 A method for producing a metal oxide film, comprising: a precursor film forming step of applying a solvent and a solution containing at least indium as a metal component to a substrate to form a metal oxide precursor film; and converting the step state where said metal oxide precursor film is heated in an oxygen concentration of a gaseous environment 30000ppm or less to 2 or less and an illuminance of 500mW / cm 2 or more 20mW / cm ultraviolet irradiation of ultraviolet light having a wavelength of 300nm or less, by This converts the metal oxide precursor film into a metal oxide film in which the temperature of the substrate in the conversion step is maintained above 160 ° C and below 200 ° C. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中所述溶液中所含的銦為銦離子。 The method for producing a metal oxide film according to claim 1, wherein the indium contained in the solution is indium ions. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中所述溶液含有硝酸根離子。 The method for producing a metal oxide film according to claim 1, wherein the solution contains nitrate ions. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中將所述紫外線照射中的所述基板升溫或降溫的速度設為±0.5℃/min以內。 The method for producing a metal oxide film according to claim 1, wherein a speed at which the substrate is heated or lowered in the ultraviolet irradiation is set to be within ±0.5 ° C/min. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中所述溶液中所含的金屬成分的50atom%以上為銦。 The method for producing a metal oxide film according to claim 1, wherein 50 atom% or more of the metal component contained in the solution is indium. 如申請專利範圍第3項所述的金屬氧化物膜的製造方法，其中所述溶液為至少溶解有硝酸銦的溶液。 The method for producing a metal oxide film according to claim 3, wherein the solution is a solution in which at least indium nitrate is dissolved. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法， 其中所述溶液更含有選自鋅、錫、鎵及鋁中的至少一種金屬成分。 The method for producing a metal oxide film according to claim 1, Wherein the solution further contains at least one metal component selected from the group consisting of zinc, tin, gallium, and aluminum. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中所述溶劑為甲醇、甲氧基乙醇、或水。 The method for producing a metal oxide film according to claim 1, wherein the solvent is methanol, methoxyethanol, or water. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中所述溶液中的金屬成分的濃度為0.01mol/L以上且1.0mol/L以下。 The method for producing a metal oxide film according to the first aspect of the invention, wherein the concentration of the metal component in the solution is 0.01 mol/L or more and 1.0 mol/L or less. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中用於所述紫外線照射的光源為低壓水銀燈。 The method for producing a metal oxide film according to claim 1, wherein the light source for the ultraviolet irradiation is a low pressure mercury lamp. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中所述前驅物膜形成步驟是將所述溶液塗佈於所述基板上，將所述基板加熱至35℃以上且100℃以下而將其乾燥，藉此形成所述金屬氧化物前驅物膜。 The method for producing a metal oxide film according to claim 1, wherein the precursor film forming step is to apply the solution onto the substrate, and heat the substrate to 35 ° C or higher and 100 It is dried below °C, thereby forming the metal oxide precursor film. 如申請專利範圍第1項所述的金屬氧化物膜的製造方法，其中於所述前驅物膜形成步驟中，藉由選自噴墨法、分配器法、凸版印刷法、及凹版印刷法中的至少一種塗佈法，將所述溶液塗佈於所述基板上。 The method for producing a metal oxide film according to the first aspect of the invention, wherein the precursor film forming step is selected from the group consisting of an inkjet method, a dispenser method, a letterpress printing method, and a gravure printing method. At least one coating method of applying the solution onto the substrate.
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