CN108417495A - 一种金属氧化物钝化的薄膜晶体管的制备 - Google Patents
一种金属氧化物钝化的薄膜晶体管的制备 Download PDFInfo
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- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 23
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- 238000004528 spin coating Methods 0.000 claims abstract description 32
- 239000004065 semiconductor Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
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- 239000000047 product Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910009112 xH2O Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910003134 ZrOx Inorganic materials 0.000 claims description 3
- 238000006303 photolysis reaction Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
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- H01L21/44—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/38 - H01L21/428
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Abstract
本发明公开了一种金属氧化物钝化的薄膜晶体管的制备,本发明采用溶胶凝胶的制备方法,以Al(NO3)3·9H2O为溶质、N,N‑二甲基甲酰胺为溶剂的前驱体溶液在衬底上进行旋涂,制备出Al2O3薄膜,并进一步制备出以Al2O3薄膜为钝化层、In2O3薄膜为半导体沟道层,用ZrO2薄膜作为栅介电层的金属氧化物薄膜晶体管。本发明的有益效果是提高器件的操作稳定性,延长器件的使用寿命,增大电容密度和减少栅极漏电流,降低器件操作电压,减少能源消耗。
Description
技术领域
本发明属于薄膜晶体管制备技术领域,涉及一种金属氧化物钝化的薄膜晶体管的制备方法,用于金属氧化物半导体薄膜晶体管的钝化处理场合。
背景技术
近年来,金属氧化物薄膜晶体管(Metal-Oxide Thin-Film Transistor,简称MOTFT)在有源矩阵驱动液晶显示器件(Active Matrix Liquid Crystal Display,简称AMLCD)中发挥了重要作用。从低温非晶硅薄膜晶体管到高温多晶硅薄膜晶体管,技术越来越成熟,应用对象也从只能驱动液晶显示器件(Liquid Crystal Display,简称LCD)发展到既可以驱动LCD又可以驱动有机发光显示器(Organic Light Emitting Display,简称OLED),甚至电子纸。薄膜晶体管(简称TFT)已经成为平板显示行业的核心部件,每台显示器都集成了数百万甚至上亿个TFT器件。目前研究与应用最多的金属氧化物材料为ZnO、SnO2和In2O3体系(Nature,432488,2004;Nature Materials,10382,2011)。在之前的报道中,这些体系的MOTFT极易受到外界环境(如空气中的水分、氧气等)的影响,导致TFT的操作稳定性很差(IEEE Electron Device Lett.,38,4,2017),极大限制了MOTFT在CMOS集成电路上的广泛应用。Al2O3作为一种致密性很强的金属氧化物,能有效隔绝器件与外界环境的接触,增强器件的操作稳定性。基于以上原因,发展金属氧化物作为TFT器件的钝化层对于大规模CMOS集成电路具有十分重要的意义。
随着大规模集成电路的发展,作为硅基集成电路核心器件的TFT的特征尺寸一直不断减小。当超大规模集成电路的特征尺寸小于0.1μm时,SiO2介电层的厚度必须小于1.5nm,因此很难控制SiO2薄膜的针孔密度,从而导致较大的漏电流。研究表明SiO2厚度由3.5nm减至1.5nm时栅极漏电流由10-12A/cm2增大到10A/cm2(IEEE Electron DeviceLetters,18209,1997)。较大的漏电流会引起高功耗及相应的散热问题,这对于器件集成度、可靠性和寿命都造成不利的影响。目前,在集成电路工艺中广泛采用高介电常数(高k)栅介电材料来增大电容密度和减少栅极漏电流,高k材料因其较大的介电常数,在与SiO2具有相同等效栅氧化层厚度(EOT)的情况下,其实际厚度比SiO2大的多,从而解决了SiO2因接近物理厚度极限而产生的量子遂穿效应(Journal ofApplied Physics,895243,2001)。因此制备新型、高性能高k材料替代SiO2作为栅介电材料成为实现大规模集成电路的首要任务。
发明内容
本发明的目的在于提供一种金属氧化物钝化的薄膜晶体管的制备,本发明的有益效果是改善器件的调控能力和提高器件的稳定性。
本发明所采用的技术方案是按照以下步骤进行:
(1)清洗硅衬底:选取重掺杂p型硅作为衬底,并依次使用丙酮、无水乙醇和去离子水清洗,接着用氮气吹干备用;
(2)溶胶凝胶法制备栅介电层:将Zr(NO3)4·5H2O溶于乙二醇甲醚中,搅拌形成澄清透明的栅介电层前驱体溶液,将硅衬底放入等离子清洗机内清洗,然后将栅介电层前驱体溶液旋涂在清洗后的硅衬底上形成薄膜,放入烤胶台烘烤,进行紫外光退火处理,再热处理,制得均匀连续的ZrO2薄膜成品,完成ZrO2栅介电层的制备;
(3)溶胶凝胶法制备半导体沟道层:In(NO3)3·xH2O溶解于乙二醇甲醚溶剂中,搅拌形成澄清透明的半导体层前驱体溶液,将配置好的半导体层前驱体溶液旋涂在ZrO2栅介电层上,旋涂结束后将制得的In2O3薄膜半成品热处理,制得均匀连续的In2O3薄膜成品,完成In2O3半导体沟道层的制备;
(4)溶胶凝胶法制备钝化层:将Al(NO3)3·9H2O溶于N,N-二甲基甲酰胺中,搅拌形成澄清透明的钝化层前驱体溶液,将配置好的钝化层前驱体溶液旋涂在In2O3半导体沟道层上,旋涂结束后将制得的Al2O3薄膜半成品热处理制得均匀连续的Al2O3薄膜成品,完成Al2O3钝化层的制备。
进一步,步骤(1)中衬底为电阻率为0.001Ω·cm的重掺杂p型硅。
进一步,步骤(2)中0.5-5mmol Zr(NO3)4·5H2O溶于10mL乙二醇甲醚中
进一步,步骤(2)中旋涂时在3000-6000转/分转速下旋涂5-30秒,每旋涂1次将增加薄膜厚度5-30nm。
进一步,步骤(2)中将薄膜放入烤胶台100-200℃,热处理10-60min,然后将样品放到高压汞灯下进行紫外光退火处理10-60min。
进一步,步骤(2)中使薄膜光解和固化形成ZrOx薄膜的半成品,其中x的取值范围在1-2
进一步,步骤(3)中称取0.5-5mmolIn(NO3)3·xH2O溶解于10mL乙二醇甲醚溶剂中;旋涂速度为3000-6000转/分,旋涂时间为5-30秒,旋转次数为1-5次,每旋涂一次薄膜厚度将增加5-20nm。
进一步,步骤(3)中旋涂结束后将制得的In2O3薄膜半成品先放入烤胶台中在100-200℃热处理10-60min,然后再放入马弗炉在300-400℃下热处理1-3h。
进一步,步骤(4)中将0.1-1mmolAl(NO3)3·9H2O溶于10mLN,N-二甲基甲酰胺中。
进一步,步骤(4)中旋涂结束后将制得的Al2O3薄膜半成品先放入烤胶台中在100-200℃热处理10-60min,然后再放入马弗炉在300-400℃下热处理1-3h。
附图说明
图1为本发明涉及的金属氧化物钝化的薄膜晶体管的主体结构原理示意图;
图2是本发明制备的Al/Al2O3/In2O3/ZrO2/Si结构的薄膜晶体管的转移特性曲线图。
具体实施方式
图1为金属氧化物钝化的薄膜晶体管的主体结构。下面结合具体实施方式对本发明进行详细说明:
(1)清洗硅衬底:首先选取电阻率为0.001Ω·cm的重掺杂p型硅作为衬底,并依次使用丙酮、无水乙醇和去离子水清洗,接着用纯度为99.99%的氮气吹干备用。
(2)溶胶凝胶法制备栅介电层:将0.5-5mmol Zr(NO3)4·5H2O溶于10mL乙二醇甲醚中,在10-100℃下搅拌1-100小时形成澄清透明的栅介电层前驱体溶液,其中[Zr4+]的摩尔浓度为0.5-5mol/L。将步骤(1)处理好的硅衬底放入等离子清洗机内,并将等离子清洗机腔内抽真空至0.5-10Pa,通入10-50sccm纯度为99.99%的氧气,清洗功率为30-100Watt,清洗时间为1-10min。然后将之前配置好的栅介电层前驱体溶液旋涂在清洗后的硅衬底上,旋涂1-10次在硅衬底表面上形成薄膜,旋涂时在3000-6000转/分转速下旋涂5-30秒,每旋涂1次将增加薄膜厚度5-30nm。先将薄膜放入烤胶台100-200℃热处理10-60min,然后将样品放到高压汞灯下进行紫外光退火处理10-60min,使薄膜光解和固化形成ZrOx薄膜的半成品,其中x的取值范围在1-2;再放入马弗炉在300-500℃下热处理1-3h,制得均匀连续的ZrO2薄膜成品,完成ZrO2栅介电层的制备。
(3)溶胶凝胶法制备半导体沟道层:称取0.5-5mmolIn(NO3)3·xH2O溶解于10mL乙二醇甲醚溶剂中,在10-100℃下搅拌1-100小时形成澄清透明的半导体层前驱体溶液,其中[In3+]的摩尔浓度为0.5-5mol/L。将配置好的半导体层前驱体溶液旋涂在步骤(2)制得的ZrO2栅介电薄膜上,旋涂速度为3000-6000转/分,旋涂时间为5-30秒,旋转次数为1-5次,每旋涂一次薄膜厚度将增加5-20nm。旋涂结束后将制得的In2O3薄膜半成品先放入烤胶台中在100-200℃热处理10-60min,然后再放入马弗炉在300-400℃下热处理1-3h,制得均匀连续的In2O3薄膜成品,完成In2O3半导体沟道层的制备。
(4)溶胶凝胶法制备钝化层:将0.1-1mmolAl(NO3)3·9H2O溶于10mLN,N-二甲基甲酰胺中,在10-100℃下搅拌20-200小时形成澄清透明的钝化层前驱体溶液,其中[Al3+]的摩尔浓度为0.01-0.1mol/L。将配置好的钝化层前驱体溶液旋涂在步骤(3)制得的样品上,旋涂速度为3000-6000转/分,旋涂时间为5-30秒,旋转次数为1-5次,每旋涂一次薄膜厚度将增加5-10nm。旋涂结束后将制得的Al2O3薄膜半成品先放入烤胶台中在100-200℃热处理10-60min,然后再放入马弗炉在300-400℃下热处理1-3h,制得均匀连续的Al2O3薄膜成品,完成Al2O3钝化层的制备。
(5)加热蒸发法制备源漏电极:最后,在Al2O3薄膜钝化层上用1000/100μm的掩膜版制备50-200nm厚的金属Al作为源、漏电极,制得Al/Al2O3/In2O3/ZrO2/Si底栅顶结构的薄膜晶体管。
图2是本发明制备的Al/Al2O3/In2O3/ZrO2/Si结构的薄膜晶体管的转移特性曲线图。其中In2O3/ZrO2、Al2O3/In2O3/ZrO2分别为钝化前、钝化后的转移特性曲线。
本发明与已有技术相比,其具有以下优点:
1.采用“溶胶凝胶法”制备栅介电层ZrO2替代传统的SiO2,能够增大电容密度和减少栅极漏电流,降低器件操作电压,减小功耗,从而降低使用成本,能够满足未来电子器件发展的需要。
2.采用“溶胶凝胶法”制备的钝化层Al2O3覆盖在In2O3半导体沟道层的上面,有效隔绝半导体层与外界环境(如空气中的水分、氧气)的接触,减少外界环境对半导体层的影响,从而增加器件在外界环境(尤其是恶劣环境)下的操作稳定性,延长器件的使用寿命。
3.采用的“溶胶凝胶法”不依赖昂贵的设备和苛刻的真空条件,能有效降低成本。
因此,本发明在CMOS集成、低能耗可携带电子领域具有很好的应用前景,其原理可靠,工艺简单,成本低廉,节能环保,可大面积工业化生产,具有广阔的市场前景。
以上所述仅是对本发明的较佳实施方式而已,并非对本发明作任何形式上的限制,凡是依据本发明的技术实质对以上实施方式所做的任何简单修改,等同变化与修饰,均属于本发明技术方案的范围内。
Claims (10)
1.一种金属氧化物钝化的薄膜晶体管的制备,其特征在于按照以下步骤进行:
(1)清洗硅衬底:选取重掺杂p型硅作为衬底,并依次使用氢氟酸、丙酮、无水乙醇和去离子水清洗,接着用氮气吹干备用;
(2)溶胶凝胶法制备栅介电层:将Zr(NO3)4·5H2O溶于乙二醇甲醚中,搅拌形成澄清透明的栅介电层前驱体溶液,将硅衬底放入等离子清洗机内清洗,然后将栅介电层前驱体溶液旋涂在清洗后的硅衬底上形成薄膜,先将薄膜热处理,然后进行紫外光退火处理,再热处理,制得均匀连续的ZrO2薄膜成品,完成ZrO2栅介电层的制备;
(3)溶胶凝胶法制备半导体沟道层:In(NO3)3·xH2O溶解于乙二醇甲醚溶剂中,搅拌形成澄清透明的半导体层前驱体溶液,将配置好的半导体层前驱体溶液旋涂在ZrO2栅介电层上,旋涂结束后将制得的In2O3薄膜半成品热处理,制得均匀连续的In2O3薄膜成品,完成In2O3半导体沟道层的制备;
(4)溶胶凝胶法制备钝化层:将Al(NO3)3·9H2O溶于N,N-二甲基甲酰胺中,搅拌形成澄清透明的钝化层前驱体溶液,将配置好的钝化层前驱体溶液旋涂在In2O3半导体沟道层上,旋涂结束后将制得的Al2O3薄膜半成品热处理制得均匀连续的Al2O3薄膜成品,完成Al2O3钝化层的制备。
2.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(1)中衬底为电阻率为0.001Ω·cm的重掺杂p型硅。
3.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(2)中0.5-5mmol Zr(NO3)4·5H2O溶于10mL乙二醇甲醚中。
4.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(2)中旋涂时在3000-6000转/分转速下旋涂5-30秒,每旋涂1次将增加薄膜厚度5-30nm。
5.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(2)中将薄膜放入烤胶台100-200℃热处理10-60min,然后将样品放到高压汞灯下进行紫外光退火处理10-60min。
6.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(2)中使薄膜光解和固化形成ZrOx薄膜的半成品,其中x的取值范围在1-2。
7.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(3)中称取0.5-5mmolIn(NO3)3·xH2O溶解于10mL乙二醇甲醚溶剂中;旋涂速度为3000-6000转/分,旋涂时间为5-30秒,旋转次数为1-5次,每旋涂一次薄膜厚度将增加5-20nm。
8.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(3)中旋涂结束后将制得的In2O3薄膜半成品先放入烤胶台中在100-200℃热处理10-60min,然后再放入马弗炉在300-400℃下热处理1-3h。
9.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(4)中将0.1-1mmolAl(NO3)3·9H2O溶于10mLN,N-二甲基甲酰胺中。
10.按照权利要求1所述一种金属氧化物钝化的薄膜晶体管的制备,其特征在于:所述步骤(4)中旋涂结束后将制得的Al2O3薄膜半成品先放入烤胶台中在100-200℃热处理10-60min,然后再放入马弗炉在300-400℃下热处理1-3h。
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