TWI547468B - An amorphous metal oxide semiconductor layer forming precursor composition, an amorphous metal oxide semiconductor layer, a method for manufacturing the same, and a semiconductor device - Google Patents
An amorphous metal oxide semiconductor layer forming precursor composition, an amorphous metal oxide semiconductor layer, a method for manufacturing the same, and a semiconductor device Download PDFInfo
- Publication number
- TWI547468B TWI547468B TW100126515A TW100126515A TWI547468B TW I547468 B TWI547468 B TW I547468B TW 100126515 A TW100126515 A TW 100126515A TW 100126515 A TW100126515 A TW 100126515A TW I547468 B TWI547468 B TW I547468B
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- TW
- Taiwan
- Prior art keywords
- semiconductor layer
- metal oxide
- oxide semiconductor
- amorphous metal
- precursor composition
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims description 131
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 112
- 150000004706 metal oxides Chemical class 0.000 title claims description 112
- 239000002243 precursor Substances 0.000 title claims description 112
- 239000005300 metallic glass Substances 0.000 title claims description 102
- 239000000203 mixture Substances 0.000 title claims description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title description 31
- 229910052751 metal Inorganic materials 0.000 claims description 67
- 239000002184 metal Substances 0.000 claims description 67
- 150000003839 salts Chemical class 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 19
- -1 inorganic acid salt Chemical class 0.000 claims description 18
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- MYMLGBAVNHFRJS-UHFFFAOYSA-N trifluoromethanamine Chemical compound NC(F)(F)F MYMLGBAVNHFRJS-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
-
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Description
本發明係關於藉由各種塗佈法用以形成非晶質金屬氧化物半導體層之前驅物組成物、藉此所得之非晶質金屬氧化物半導體層與其製造方法、以及含有該半導體層之半導體裝置。
非專利文獻1、2中,係揭示有藉由濺鍍法或CVD法形成非晶質金屬氧化物半導體層來製造出薄膜電晶體之例子。當使用濺鍍法等之真空蒸鍍系的成膜裝置來形成非晶質金屬氧化物半導體層時,圖型形成主要是使用依據遮罩蒸鍍或微影技術所進行之蝕刻法,但該方法被指出具有基板大型化花費較高成本且步驟繁瑣等問題點。此外,亦有人提出由此等方法所製作之非晶質金屬氧化物半導體層,該基板面內與基板間存在較大變動,為了降低該變動而須在高溫下進行燒結之問題。
近年來,相對於此等方法,於非專利文獻3~6和專利文獻1~3中,係揭示有藉由塗佈法來進行金屬氧化物半導體層的成膜,以製造出薄膜電晶體之例子。
在此等使用塗佈法之製造方法中,係將金屬錯合物溶入於基質溶劑來形成前驅物組成物,並藉由旋轉塗佈或噴墨塗佈法等之塗佈法塗佈於基板上後,藉由燒結來形成金屬氧化物半導體層。然而,當使用塑膠基板等之耐熱性弱的基板時,為了防止熱伸縮或劣化或是基板本身的分解,係要求一種可在更低溫下,再高也須在較300℃更低之溫度下形成緊密的非晶質金屬氧化物半導體層之前驅物組成物。
因此,非專利文獻3中,係揭示有預先藉由對前驅物組成物進行熱分析來確認其熱分解動作,藉以選擇不會引起因熱重量減少或熱反應所導致的放熱及吸熱之燒結溫度,來決定最適燒結溫度之內容。然而,非專利文獻4中,係指出當未在遠較引起前驅物組成物的熱重量減少或熱反應之溫度更高的溫度下進行燒結時,殘留於膜內之雜質會對裝置的動作產生影響,與藉由真空蒸鍍法所製作之金屬氧化物半導體層相比,該性能會降低。
此外,專利文獻1及3,係提出一種不使用可能有產生此等殘留物質的疑慮之高沸點有機溶劑,而是使用低沸點的醇或水之薄膜半導體層的製造方法。然而,此等方法中,無法製造出緊密的非晶質金屬氧化物半導體層。
再者,非專利文獻5及6中,於塗佈燒結後在膜表面上觀察到塗佈不良,並未形成非晶質狀態之緊密的膜。因此,雖提出限制材料濃度之方法,但仍存在無法形成充分膜厚的非晶質金屬氧化物半導體層之問題。
專利文獻1:日本國際公開第2009/081862號手冊
專利文獻2:日本國際公開第2009/119968號手冊
專利文獻3:日本特開2010-098303號公報
非專利文獻1:細野秀雄,透明氧化物功能材料與其應用,CMC出版,2006年
非專利文獻2:細野秀雄,2010年氧化物半導體的最前線及徹底解說,電子Journal,2010年
非專利文獻3:David S. Ginley,et al,Solution Synthesis and Characterization of Indium-Zinc Formate Precursors for Transparent Conducting Oxides,Inorg. Chem. 49,5424-5431,2010.
非專利文獻4:Jooho Moon,et al,Compositional influence on sol-gel-derived amorphous oxide semiconductor thin transistor,Appl. Phys. Lett. 95,103501,2009.
非專利文獻5:Sung Kyu Park,et al,Effect of Metallic Composition on Electrical Properties of Solution-Processed Indium-Gallium-Zinc-Oxide Thin-Film Transistors,IEEE Transaction on Electron Devices,57,No.5,May,2010.
非專利文獻6:Chung-Chih Wu,et al,The Influence of Channel Compositions on the Electrical Properties of Solution-Processed Indium-Zinc-Oxide Thin-Film Transistors,Jour. of Display Technology,5,No.12,December,2009.
本發明在於提供一種可在大氣壓下,藉由塗佈法於低溫下形成緊密的非晶質金屬氧化物半導體層之非晶質金屬氧化物半導體層形成用前驅物組成物、非晶質金屬氧化物半導體層與其製造方法、以及半導體裝置。
本發明之第1觀點,是一種含有以金屬鹽與一級醯胺與以水為主體之溶劑之非晶質金屬氧化物半導體層形成用前驅物組成物;
第2觀點,是如第1觀點之非晶質金屬氧化物半導體層形成用前驅物組成物,其中前述一級醯胺的含量,相對於前述金屬鹽為0.1~100質量%;
第3觀點,是如第1觀點或第2觀點之非晶質金屬氧化物半導體層形成用前驅物組成物,其中前述一級醯胺是由下列一般式(I)表示之化合物,
[化1]
(式(I)中,R1表示氫原子或是碳原子數1~6之分枝或直鏈的烷基,鍵結有氫原子或是碳原子數1~6之分枝或直鏈的烷基之氧原子,或者是鍵結有氫原子、氧原子或是碳原子數1~6之分枝或直鏈的烷基之氮原子);
第4觀點,是如第1觀點至第3觀點中任一觀點之非晶質金屬氧化物半導體層形成用前驅物組成物,其中前述金屬鹽的金屬,係選自由Li、Be、B、Na、Mg、Al、Si、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Rb、Sr、Y、Zr、Nb、Mo、Cd、In、Ir、Sn、Sb、Cs、Ba、La、Hf、Ta、W、Tl、Pb、Bi、Ce、Pr、Nd、Pm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu所組成之群組的至少1種;
第5觀點,是如第1觀點至第4觀點中任一觀點之非晶質金屬氧化物半導體層形成用前驅物組成物,其中前述金屬鹽為無機酸鹽;
第6觀點,是如第5觀點之非晶質金屬氧化物半導體層形成用前驅物組成物,其中前述無機酸鹽,係選自由硝酸鹽、硫酸鹽、磷酸鹽、碳酸鹽、碳酸氫鹽、硼酸鹽、鹽酸鹽及氫氟酸鹽所組成之群組的至少1種;
第7觀點,是如第1觀點至第6觀點中任一觀點之非晶質金屬氧化物半導體層形成用前驅物組成物,其係酸性;
第8觀點,是如第7觀點之非晶質金屬氧化物半導體層形成用前驅物組成物,其中pH值為1~3;
第9觀點,是一種非晶質金屬氧化物半導體層的製造方法,其特徵係將塗佈如第1觀點至第8觀點中任一觀點之非晶質金屬氧化物半導體層形成用前驅物組成物所形成之前驅物薄膜,在150℃以上且未達300℃下進行燒結;
第10觀點,是一種非晶質金屬氧化物半導體層,其特徵係藉由如第9觀點之非晶質金屬氧化物半導體層的製造方法所製造出;
第11觀點,是一種具有如第10觀點之非晶質金屬氧化物半導體層之半導體裝置。
根據本發明,藉由形成含有金屬鹽與一級醯胺與以水為主體之溶劑之組成物,可成為一種能夠在大氣壓下,藉由塗佈法於低溫下形成緊密的非晶質金屬氧化物半導體層之非晶質金屬氧化物半導體層形成用前驅物組成物。此外,若使用該非晶質金屬氧化物半導體層形成用前驅物組成物,則可藉由低溫下的燒結而得到緊密的非晶質金屬氧化物半導體層,並且得到含有非晶質金屬氧化物半導體層之半導體裝置。
本發明之非晶質金屬氧化物半導體層形成用前驅物組成物(以下亦記載為「前驅物組成物」),是含有以金屬鹽與一級醯胺與以水為主體之溶劑之組成物。前述一級醯胺的含量,相對於前述金屬鹽為0.1~100質量%,較佳為5~50質量%。
本發明之非晶質金屬氧化物半導體層形成用前驅物組成物所含有之一級醯胺,可列舉出由下列一般式(I)表示之化合物。所謂鍵結有氫原子或是碳原子數1~6之分枝或直鏈的烷基之氧原子,為-OH或-OR2(R2為碳原子數1~6之分枝或直鏈的烷基)。此外,所謂鍵結有氫原子、氧原子或是碳原子數1~6之分枝或直鏈的烷基之氮原子,例如為-NH2、-NHR3、或-NR4R5(R3、R4及R5分別獨立地為碳原子數1~6之分枝或直鏈的烷基)。
[化2]
(式(I)中,R1表示氫原子或是碳原子數1~6之分枝或直鏈的烷基,鍵結有氫原子或是碳原子數1~6之分枝或直鏈的烷基之氧原子,或者是鍵結有氫原子、氧原子或是碳原子數1~6之分枝或直鏈的烷基之氮原子)
一級醯胺的具體例,可列舉出乙醯胺、乙醯脲、丙烯醯胺、己二酸二醯胺、乙醯醛、半卡腙、偶氮二羧醯胺、4-胺基-2,3,5,6-四氟苯甲醯胺、β-丙胺酸醯胺鹽酸鹽、L-丙胺酸醯胺鹽酸鹽、苯甲醯胺、苄基脲、二脲、縮二脲、丁基醯胺、3-溴丙酸醯胺、丁基脲、3,5-雙(三氟甲基)苯甲醯胺、胺基甲酸三級丁酯、己烷醯胺、胺基甲酸銨、胺基甲酸乙酯、2-氯乙醯胺、2-氯乙基脲、巴豆醯胺、2-氰基乙醯胺、胺基甲酸丁酯、胺基甲酸異丙酯、胺基甲酸甲酯、氰基乙醯脲、環丙烷碳醯胺、環己基脲、2,2-二氯醯胺、磷酸二胺二脒、硫酸胍基脲、1,1-二甲基脲、2,2-二甲氧丙酸醯胺、乙基脲、氟乙醯胺、甲醯胺、富馬醯胺、甘胺酸醯胺鹽酸鹽、羥基脲、乙內醯脲酸、2-羥乙基脲、七氟丁基醯胺、2-羥基異丁基醯胺、異丁酸醯胺、乳酸醯胺、馬來醯胺、丙二醯胺、1-甲基脲、硝基脲、草醯胺酸、草醯胺酸乙酯、草醯胺、草醯胺酸醯肼、草醯胺酸丁酯、苯基脲、鄰苯二甲醯胺、丙酸醯胺、新戊酸醯胺、五氟苯甲醯胺、五氟丙酸醯胺、氨基脲鹽酸鹽、琥珀酸醯胺、三氯乙醯胺、三氟甲醯胺、硝酸脲、脲、戊醯胺等。當中較佳為甲醯胺、脲、胺基甲酸銨。此等可使用1種或組合2種以上使用。
本發明之非晶質金屬氧化物半導體層形成用前驅物組成物所含有之金屬鹽的金屬,例如為選自由Li、Be、B、Na、Mg、Al、Si、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Rb、Sr、Y、Zr、Nb、Mo、Cd、In、Ir、Sn、Sb、Cs、Ba、La、Hf、Ta、W、Tl、Pb、Bi、Ce、Pr、Nd、Pm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu所組成之群組的至少1種。上述列舉出之金屬中,較佳係含有銦(In)、錫(Sn)、鋅(Zn)中的任一種,可進一步含有鎵(Ga)或鋁(Al)。
藉由本發明之非晶質金屬氧化物半導體層形成用前驅物組成物所得之非晶質金屬氧化物半導體,可列舉出氧化銦鎵鋅、氧化銦鎵、氧化銦錫鋅、氧化鎵鋅、氧化銦錫、氧化銦鋅、氧化錫鋅、氧化鋅、氧化錫,例如為InGaZnOx、InGaOx、InSnZnOx、GaZnOx、InSnOx、InZnOx、SnZnOx(均為x>0)、ZnO、SnO2等。
此外,所使用之金屬鹽較佳為無機酸鹽。無機酸鹽例如可使用選自由硝酸鹽、硫酸鹽、磷酸鹽、碳酸鹽、碳酸氫鹽、硼酸鹽、鹽酸鹽及氫氟酸鹽所組成之群組的至少1種。此外,為了在更低溫下進行塗佈後的加熱處理(燒結),無機酸鹽較佳為鹽酸鹽、硝酸鹽。
當本發明之非晶質金屬氧化物半導體層形成用前驅物組成物含有複數種金屬時,各金屬的比率(組成比),只要可形成期望的非晶質金屬氧化物半導體層者即可,並無特別限定,例如,選自In或Sn的金屬鹽之鹽中所含有的金屬(金屬A),與選自Zn的金屬鹽之鹽中所含有的金屬(金屬B),與選自Ga或Al的金屬鹽之鹽中所含有的金屬(金屬C)之莫耳比率,較佳係滿足金屬A:金屬B:金屬C:=1:0.05~1:0~1。例如,由於金屬鹽最佳為硝酸鹽,故以使莫耳比率滿足金屬A:金屬B:金屬C:=1:0.05~1:0~1之方式,將各金屬的硝酸鹽溶解於詳細如後述之以水為主成分之溶劑,然後進一步構成為含有上述一般式(I)等之一級醯胺之水溶液。
本發明之非晶質金屬氧化物半導體層形成用前驅物組成物的溶劑,係以水為主體。亦即意味著主溶劑,亦即溶劑的50質量%以上為水。只要以水為主體即可,可僅以水作為溶劑,或使用水與有機溶劑之混合溶劑。水以外所含有之有機溶劑的具體例,可列舉出丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單丙醚、丁酮、乳酸乙酯、環己酮、γ-丁內酯、N-甲基吡咯啶酮、甲醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-2-吡咯啶酮、N-甲基己內醯胺、二甲基亞碸、四甲基脲、吡啶、二甲基碸、六甲基亞碸、甲醇、乙醇、1-丙醇、異丙醇、正丁醇、2-丁醇、三級丁醇、1-戊醇、2-戊醇、3-戊醇、正己醇、環己醇、2-甲基-2-丁醇、3-甲基-2-丁醇、2-甲基-1-丁醇、3-甲基-1-丁醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-甲基-3-戊醇、3-甲基-1-戊醇、3-甲基-2-戊醇、3-甲基-3-戊醇、4-甲基-1-戊醇、4-甲基-2-戊醇、2,2-二甲基-3-戊醇、2,3-二甲基-3-戊醇、2,4-二甲基-3-戊醇、4,4-二甲基-2-戊醇、3-乙基-3-戊醇、1-庚醇、2-庚醇、3-庚醇、2-甲基-2-己醇、2-甲基-3-己醇、5-甲基-1-己醇、5-甲基-2-己醇、2-乙基-1-己醇、4-甲基-3-庚醇、6-甲基-2-庚醇、1-辛醇、2-辛醇、3-辛醇、2-丙基-1-戊醇、2,4,4-三甲基-1-戊醇、2,6-二甲基-4-庚醇、3-乙基-2,2-二甲基-戊醇、1-壬醇、2-壬醇、3,5,5-三甲基-1-己醇、1-癸醇、2-癸醇、4-癸醇、3,7-二甲基-1-辛醇、3,7-二甲基-3-辛醇等。此等有機溶劑可組合2種以上。
本發明之非晶質金屬氧化物半導體層形成用前驅物組成物中的固體含量濃度為0.1質量%以上,較佳為0.3質量%以上,尤佳為0.5質量%以上。此外,本發明之非晶質金屬氧化物半導體層形成用前驅物組成物中的固體含量濃度為30.0質量%以下,較佳為20.0質量%以下,尤佳為15.0質量%以下。所謂固體含量濃度,是指金屬鹽與一級醯胺的合計濃度。
本發明之非晶質金屬氧化物半導體層形成用前驅物組成物較佳為酸性。此外,本發明之非晶質金屬氧化物半導體層形成用前驅物組成物的pH值較佳為1~3。為了使pH達到酸性,可使用選自由硝酸、硫酸、磷酸、碳酸、硼酸、鹽酸及氫氟酸所組成之群組的至少1種。
本發明之非晶質金屬氧化物半導體層形成用前驅物組成物的製造方法並無特別限定,例如可將金屬鹽與一級醯胺混合於以水為主體之溶劑。
在將本發明之非晶質金屬氧化物半導體層形成用前驅物組成物塗佈於基板來形成前驅物薄膜後,可在低溫下,例如150℃以上且未達300℃下進行燒結而製造出緊密的非晶質金屬氧化物半導體層。於燒結步驟前,為了先去除殘存溶劑,較佳係在50℃以上且未達150℃下進行乾燥步驟作為前處理。
本發明之非晶質金屬氧化物半導體層形成用前驅物組成物的塗佈方法,可應用一般所知的方法,例如可列舉出旋轉塗佈、浸泡塗佈、網版印刷、輥塗佈、噴墨塗佈、壓模塗佈、轉印印刷法、噴霧法、狹縫塗佈法等。藉由各種塗佈方法塗佈前述前驅物組成物所得之前驅物薄膜的厚度,為1nm~1μm,較佳為10~100nm。當無法藉由一次的塗佈及燒結處理得到期望的厚度時,可重複進行塗佈及燒結處理的步驟直至成為期望的厚度。
非晶質金屬氧化物半導體層的形成中,前述塗佈後之前驅物薄膜的燒結乃為必要,但本發明之非晶質金屬氧化物半導體層形成用前驅物組成物,即使在較以往要求300℃以上的燒結溫度更低之溫度下,亦可形成緊密的非晶質金屬氧化物半導體層。
該前驅物薄膜的燒結為用以使金屬鹽進行氧化反應之步驟。該燒結溫度較佳為150℃以上且未達300℃,尤佳為150℃以上275℃以下。當然,即使在300℃以上且例如500℃以下進行燒結,亦可製造出非晶質金屬氧化物半導體層。燒結時間並無特別限定,例如為3分鐘~24小時。
藉由如此燒結,可形成非晶質金屬氧化物半導體層。非晶質金屬氧化物半導體層的厚度並無特別限定,例如為5~100nm。
在此,專利文獻1等,係揭示一種使用大氣壓電漿裝置或微波加熱裝置,在未達300℃的燒結(退火)溫度下進行燒結而製得半導體層之手段。然而,此等裝置的泛用性低且昂貴,因而要求一種可使用加熱板、IR爐、烘烤箱等之泛用性高且便宜之裝置,在未達300℃的燒結溫度下進行燒結而製得半導體層之技術。藉由使用本發明之非晶質金屬氧化物半導體層形成用前驅物組成物,可使用加熱板、IR爐、烘烤箱等之泛用性高且便宜之加熱裝置,在未達300℃的燒結溫度下製得品質高之非晶質金屬氧化物半導體層。具體而言,該燒結可使用加熱板、烘烤箱、IR爐等。
此外,進行前述前驅物薄膜的燒結之氣體環境,不僅在空氣中或氧氣等之氧化氣體環境中,亦可在氮氣、氦氣、氬氣等非活性氣體中進行。
讓前述前驅物薄膜形成之基板並無特別限定,例如可列舉出矽基板、金屬基板、鎵基板、透明電極基板、有機薄膜基板、塑膠基板、玻璃基板等。具體而言,例如可列舉出聚醯亞胺、聚碳酸酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等之塑膠薄膜;不鏽鋼箔、玻璃等。此外,亦可為形成有配線層或電晶體等的電路元件之半導體基板等。
本發明之半導體裝置,係含有:在將本發明之非晶質金屬氧化物半導體層形成用前驅物組成物塗佈於基板來形成前驅物薄膜後,在低溫下進行燒結而得之非晶質金屬氧化物半導體層之半導體裝置。
含有本發明之非晶質金屬氧化物半導體層之半導體裝置,電子載子濃度的下限值為1012/cm3,藉由控制非晶質金屬氧化物的組成(構成元素)、組成比、製造條件等,可調整電子載子濃度。電子載子濃度的下限值為1012/cm3以上,較佳為1013/cm3以上。此外,電子載子濃度的下限值為1016/cm3以下。
含有本發明之非晶質金屬氧化物半導體層之半導體裝置的薄膜電晶體,只要為使用前述非晶質金屬氧化物半導體層者即可,該構成並無特別限定。作為一例,第1圖~第3圖係顯示使用本發明之非晶質金屬氧化物半導體層之薄膜電晶體的構成例。
第1圖及第2圖的例子中,本發明之薄膜電晶體,係於基板1上形成有閘極電極2,閘極電極2由閘極絕緣膜3所覆蓋。此外,第1圖的例子中,於閘極絕緣膜3上設置有源極電極4與汲極電極5,並以覆蓋此等源極電極4與汲極電極5之方式形成有本發明之非晶質金屬氧化物半導體層6。另一方面,第2圖的例子中,於閘極絕緣膜3上形成有非晶質金屬氧化物半導體層6,並於該上方設置源極電極4與汲極電極5。此外,第3圖的例子中,於基板1上形成有非晶質金屬氧化物半導體層6,並以覆蓋非晶質金屬氧化物半導體層6與基板1兩者之方式設置源極電極4與汲極電極5。然後,閘極絕緣膜3形成於非晶質金屬氧化物半導體層6與源極電極4與汲極電極5上,並於該上方設置閘極電極2而構成。
薄膜電晶體中所使用之電極材料(閘極電極2、源極電極4和汲極電極5的材料),例如可列舉出金、銀、銅、鋁、鉬、鈦等之金屬;ITO、IZO、碳黑、富勒烯類、碳奈米管等之無機材料;聚噻吩、聚苯胺、聚吡咯、聚芴及此等的衍生物等之有機π共軛聚合物等。此等電極材料可使用1種,但以薄膜電晶體的場效遷移、導通/關閉比的提升為目的,或是以臨限值電壓的控制為目的,亦可組合複數種材料。此外,閘極電極、源極電極、汲極電極可分別使用不同電極材料。
此外,閘極絕緣膜3例如可列舉出氧化矽、氮化矽、氧化鋁、氧化鉿、氧化釔等之無機絕緣膜;聚醯亞胺、聚甲基丙烯酸甲酯、聚乙烯酚、苯環丁烯等之有機絕緣膜。此等閘極絕緣膜,可使用1種,但以薄膜電晶體的場效遷移、導通/關閉比的提升為目的,或是以臨限值電壓的控制為目的,亦可組合複數種膜。
此外,基板1可列舉出與讓上述前驅物薄膜形成之基板相同的基板。
閘極電極2、源極電極4和汲極電極5的形成方法,一般係使用真空蒸鍍、濺鍍等,但為了製造方法的簡化,亦可為噴霧塗佈、印刷法、噴墨法等之塗佈法。此外,閘極絕緣膜3一般係使用真空蒸鍍、濺鍍等,但為了製造方法的簡化,亦可為噴霧塗佈、印刷法、噴墨法等之塗佈法,當原料為矽時,亦可藉由熱氧化來形成。
[實施例1]
將硝酸銦(III)三水合物0.36g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.10g(Aldrich公司製、99.999% trace metals basis)與脲0.05g(關東化學公司製、特級99.0%)添加於超純水4.50g,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-1。前驅物組成物-1的pH為2.0。藉由旋轉塗佈法將前驅物組成物-1塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[實施例2]
將硝酸銦(III)三水合物0.36g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.10g(Aldrich公司製、99.999% trace metals basis)與甲醯胺0.05g(東京化成工業公司製、98.5%)添加於超純水4.50g,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-2。前驅物組成物-2的pH為2.2。藉由旋轉塗佈法將前驅物組成物-2塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[實施例3]
將硝酸銦(III)三水合物0.36g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.10g(Aldrich公司製、99.999% trace metals basis)與脲0.05g(關東化學公司製、特級99.0%)添加於超純水4.28g與乙醇0.23g之混合溶液中,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-3。前驅物組成物-3的pH為2.0。藉由旋轉塗佈法將前驅物組成物-3塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[實施例4]
將硝酸銦(III)三水合物0.27g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.08g(Aldrich公司製、99.999% trace metals basis)與硝酸鎵(III)八水合物0.10g(Aldrich公司製、99.999% trace metals basis)與脲0.05g(關東化學公司製、特級99.0%)添加於超純水4.50g,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-4。前驅物組成物-4的pH為2.2。藉由旋轉塗佈法將前驅物組成物-4塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於290℃的加熱板上燒結15分鐘。
[實施例5]
將硝酸銦(III)三水合物0.27g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.08g(Aldrich公司製、99.999% trace metals basis)與硝酸鎵(III)八水合物0.10g(Aldrich公司製、99.999% trace metals basis)與脲0.05g(關東化學公司製、特級99.0%)添加於超純水4.28g與乙醇0.23g之混合溶液中,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-5。前驅物組成物-5的pH為2.2。藉由旋轉塗佈法將前驅物組成物-5塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[實施例6]
將硝酸銦(III)三水合物0.36g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.10g(Aldrich公司製、99.999% trace metals basis)與甲醯胺0.05g(東京化成工業公司製、98.5%)添加於超純水4.28g與乙醇0.23g之混合溶液中,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-6。前驅物組成物-6的pH為2.0。藉由旋轉塗佈法將前驅物組成物-6塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[實施例7]
將硝酸銦(III)三水合物0.27g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.08g(Aldrich公司製、99.999% trace metals basis)與硝酸鎵(III)八水合物0.10g(Aldrich公司製、99.999% trace metals basis)與甲醯胺0.05g(東京化成工業公司製、98.5%)添加於超純水4.50g,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-7。前驅物組成物-7的pH為2.2。藉由旋轉塗佈法將前驅物組成物-7塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[實施例8]
將基板1構成為上部形成有熱氧化膜(SiO2、閘極絕緣膜3)之p型過剩摻雜的矽晶圓(電阻值0.02Ω‧cm以下、熱氧化膜200nm、KST World股份有限公司製),並藉由1500mJ/cm2的UV臭氧產生裝置予以洗淨。該基板亦具有閘極電極的功能。藉由旋轉塗佈法將前驅物組成物-1塗佈於該基板1上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結60分鐘,而形成非晶質金屬氧化物半導體層6。然後,在所形成的非晶質金屬氧化物半導體層6上,透過通道長度90μm、通道寬度2000μm、膜厚100nm的遮罩,藉由真空蒸鍍法來製作鋁電極,以該2點作為源極電極4、汲極電極5,另一方面,藉由金剛石切割刀將基板1表面刮除至熱氧化膜為止,並以該處作為閘極電極而製作出薄膜電晶體。該薄膜電晶體的構造如第4圖的概略剖面圖所示。
[實施例9]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-2塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結60分鐘,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[實施例10]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-3塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結60分鐘,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[實施例11]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-6塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結60分鐘,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[實施例12]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-7塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結60分鐘,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[實施例13]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-2塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於275℃的加熱板上燒結12小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[實施例14]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-6塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於275℃的加熱板上燒結12小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[實施例15]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-1塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於250℃的加熱板上燒結24小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[實施例16]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-2塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於250℃的加熱板上燒結24小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[實施例17]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-6塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於250℃的加熱板上燒結24小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[比較例1]
將硝酸銦(III)三水合物0.27g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.08g(Aldrich公司製、99.999% trace metals basis)添加於超純水4.50g,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-R1。前驅物組成物-R1的pH為1.9。藉由旋轉塗佈法將前驅物組成物-R1塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[比較例2]
將硝酸銦(III)三水合物0.27g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.08g(Aldrich公司製、99.999% trace metals basis)添加於2-甲氧乙醇4.50g(東京化成工業公司製、99.0%),攪拌至溶液完全呈透明而形成溶液,將此設為前驅物組成物-R2。前驅物組成物-R2的pH,由於為有機溶劑組成物,故無法測定。藉由旋轉塗佈法將前驅物組成物-R2塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[比較例3]
將硝酸銦(III)三水合物0.27g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.08g(Aldrich公司製、99.999% trace metals basis)添加於乙醇4.50g(關東化學公司製、特級99.5%),攪拌至溶液完全呈透明而形成溶液,將此設為前驅物組成物-R3。前驅物組成物-R3的pH,由於為有機溶劑組成物,故無法測定。藉由旋轉塗佈法將前驅物組成物-R3塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[比較例4]
將硝酸銦(III)三水合物0.36g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.10g(Aldrich公司製、99.999% trace metals basis)與2-胺基乙醇0.05g(東京化成工業公司製、99.0%)添加於超純水4.50g,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-R4。前驅物組成物-R4的pH為2.5。藉由旋轉塗佈法將前驅物組成物-R4塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[比較例5]
將硝酸銦(III)三水合物0.36g(Aldrich公司製、99.999% trace metals basis)與硝酸鋅六水合物0.10g(Aldrich公司製、99.999% trace metals basis)與甘油0.05g(東京化成工業公司製、99.0%)添加於超純水4.50g,攪拌至溶液完全呈透明而形成水溶液,將此設為前驅物組成物-R5。前驅物組成物-R5的pH為2.1。藉由旋轉塗佈法將前驅物組成物-R5塗佈於無鹼玻璃上,然後在室溫下靜置30秒後,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結15分鐘。
[比較例6]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-R3塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結60分鐘,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[比較例7]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-R4塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結60分鐘,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[比較例8]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-R5塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於300℃的加熱板上燒結60分鐘,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[比較例9]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-R5塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於275℃的加熱板上燒結12小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[比較例10]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-R3塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於250℃的加熱板上燒結24小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[比較例11]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-R4塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於250℃的加熱板上燒結24小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
[比較例12]
藉由1500mJ/cm2的UV臭氧產生裝置來洗淨與實施例8相同的基板。藉由旋轉塗佈法將前驅物組成物-R5塗佈於該基板上以使燒結後的膜厚成為10nm,於大氣中置於150℃的加熱板上乾燥5分鐘後,置於250℃的加熱板上燒結24小時,而形成非晶質金屬氧化物半導體層。然後進行與實施例8相同的操作而製作出薄膜電晶體。
藉由掃描型電子顯微鏡(Hitachi High Technologies股份有限公司製S4800),將在實施例1~7及比較例1~5中所製作之無鹼玻璃基板上之金屬氧化物半導體層的表面擴大25,000倍來進行觀察。作為該結果的例子,實施例1如第5圖所示,比較例1如第6圖所示,實施例4如第7圖所示。該結果係表示出在實施例1~7中所製作之金屬氧化物半導體層,其整體為緊密且均一之非晶質層。另一方面,比較例1及2中,係觀察到存在凹凸且不均一,與實施例1~7相比,形成有緊密性顯著劣化之層。且,在實施例1~7所作成的膜為非晶質的事實,藉由電子束繞射(奈米束電子束繞射),可觀察到對來自非晶質之暈環而得到確認。此外,比較例1及比較例2,並非非晶質,而是結晶的金屬氧化物半導體層。
對實施例1~7及比較例1~5,藉由TG-DAT來求取形成各金屬氧化物半導體層之溫度。測定係使用TG-DTA分析裝置(Bruker AXS股份有限公司製、TG-DTA/MS9610),取得以每分鐘升溫5℃從室溫至450℃之TG-DTA曲線。作為該結果的例子,實施例1如第8圖所示。如第8圖所示,由於DTA曲線的最後吸熱峰值溫度(第8圖中記載為D1)與TG曲線之重量減少的停止溫度幾乎一致,因此將D1(℃)設為「燒結下限溫度」。燒結下限溫度,為前驅物組成物中的金屬鹽開始進行氧化反應而形成金屬氧化物半導體層之溫度。該結果為:實施例1~7及比較例1的前驅物組成物中,燒結下限溫度未達300℃,具體而言為240℃以下,相對於此,比較例2~5中係超過300℃。
對於在實施例8~17及比較例6~12中所製作之薄膜電晶體,係在真空(5×10-2Pa)的屏蔽箱中,使用半導體參數分析儀HP4156C(Agilent Technology股份有限公司製)來進行電特性評估。閘極偏壓係從-20V至+20V進行掃描(Sweep),汲極偏壓則觀測+20V時之汲極電流的增加(傳達特性)。從測定出之數據中來算出遷移率(cm2/Vs)與ON/OFF比(LOG值)。薄膜電晶體的測定,係在調整為室溫23±3℃、溼度40%±10%之恆溫室中進行。
該結果為:在實施例8~17及比較例10中所製作之薄膜電晶體,當將閘極偏壓往加(正)側進行掃描時,顯示出n型的強化動作,可確認其作為n型半導體來進行動作。此外,通常含有鎵之非晶質金屬氧化物半導體的遷移率較小,但使用本發明之非晶質金屬氧化物半導體層形成用前驅物組成物之實施例12中,該遷移率相對較高,可充分用作為薄膜電晶體之值。另一方面,比較例6~9、11、12中,未顯示出n型的強化動作,其未作為n型半導體來進行動作。
根據本發明,可藉由低溫下的燒結來形成均一且緊密的非晶質金屬氧化物半導體層,含有本發明之非晶質金屬氧化物半導體層之半導體裝置,可應用作為家電、電腦、汽車、機械等所有領域的半導體裝置。
1...基板
2...閘極電極
3...閘極絕緣膜
4...源極電極
5...汲極電極
6...非晶質金屬氧化物半導體層
第1圖係顯示薄膜電晶體之構造的一例之概略剖面圖。
第2圖係顯示薄膜電晶體之構造的一例之概略剖面圖。
第3圖係顯示薄膜電晶體之構造的一例之概略剖面圖。
第4圖係顯示實施例及比較例之薄膜電晶體的構造之概略剖面圖。
第5圖為實施例1中所得之非晶質金屬氧化物層之掃描型電子顯微鏡照片。
第6圖為比較例1中所得之金屬氧化物層之掃描型電子顯微鏡照片。
第7圖為實施例4中所得之非晶質金屬氧化物層之掃描型電子顯微鏡照片。
第8圖為實施例1中所得之前驅物組成物-1之TG-DTA曲線。
Claims (10)
- 一種非晶質金屬氧化物半導體層形成用前驅物組成物,其特徵係含有含In及Zn的金屬鹽與一級醯胺與以水為主體之溶劑。
- 如申請專利範圍第1項之非晶質金屬氧化物半導體層形成用前驅物組成物,其中前述一級醯胺的含量,相對於前述金屬鹽為0.1~100質量%。
- 如申請專利範圍第1項之非晶質金屬氧化物半導體層形成用前驅物組成物,其中一級醯胺是由下列一般式(I)表示之化合物,
- 如申請專利範圍第1項之非晶質金屬氧化物半導體層形成用前驅物組成物,其中前述金屬鹽為無機酸鹽。
- 如申請專利範圍第4項之非晶質金屬氧化物半導體層形成用前驅物組成物,其中前述無機酸鹽,係選自由硝 酸鹽、硫酸鹽、磷酸鹽、碳酸鹽、碳酸氫鹽、硼酸鹽、鹽酸鹽及氫氟酸鹽所組成之群組的至少1種。
- 如申請專利範圍第1項之非晶質金屬氧化物半導體層形成用前驅物組成物,其係酸性。
- 如申請專利範圍第6項之非晶質金屬氧化物半導體層形成用前驅物組成物,其中pH值為1~3。
- 一種非晶質金屬氧化物半導體層的製造方法,其特徵為:將塗佈如申請專利範圍第1至7項中任一項之非晶質金屬氧化物半導體層形成用前驅物組成物所形成之前驅物薄膜,在150℃以上且未達300℃下進行燒結。
- 一種非晶質金屬氧化物半導體層,其特徵為:藉由如申請專利範圍第8項之非晶質金屬氧化物半導體層的製造方法所製造出。
- 一種半導體裝置,其特徵為:具有如申請專利範圍第9項之非晶質金屬氧化物半導體層。
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