CN108777249A - 一种溶液法制备高密度氧化锆绝缘层薄膜的方法 - Google Patents
一种溶液法制备高密度氧化锆绝缘层薄膜的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000010409 thin film Substances 0.000 title claims abstract description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 title abstract description 8
- 238000004528 spin coating Methods 0.000 claims abstract description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010408 film Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 abstract description 7
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 abstract description 7
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 abstract description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- -1 Boron ion Chemical class 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02189—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing zirconium, e.g. ZrO2
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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Abstract
本发明属于薄膜晶体管制备技术领域，公开了一种溶液法制备高密度氧化锆绝缘层薄膜的方法。将Zr(NO3)4·5H2O和H3BO3溶于乙二醇单甲醚中，搅拌老化得到前驱体溶液；在ITO玻璃衬底上旋涂所得前驱体溶液，然后退火处理，得到高密度ZrO2绝缘层薄膜。本发明在硝酸锆溶液中加入H3BO3，利用退火过程中形成的B‑O(硼氧键)来提高薄膜的致密度，使得能够基于溶液法制备高密度ZrO2薄膜。
Description
技术领域
本发明属于薄膜晶体管制备技术领域，具体涉及一种溶液法制备高密度氧化锆绝缘层薄膜的方法。
背景技术
薄膜晶体管(Thin Film Transistor,TFT)是一种三端场效应器件，可以组成显示的驱动电路，从而实现平板显示大尺寸、超高清和全彩高刷新显示。TFT中绝缘层能起到存储电容和防止信号串扰等作用，其不仅影响TFT器件的转移性能，同时影响稳定性和寿命等。ZrO2有高的相对介电常数(～27)、较宽的禁带(7.8eV)，是一种常用的介质层材料。相比于真空制备技术，如气相沉积、磁控溅射等，利用旋涂法制备的薄膜具有性价比高、节能、污染低等优点，因此旋涂法制备金属氧化物薄膜吸引了越来越多的关注。然而由于孔洞和有机杂质等的存在，溶液法制备的薄膜常常存在密度较低的问题，这极大地影响了薄膜的性能。
发明内容
针对以上现有技术存在的缺点和不足之处，本发明的目的在于提供一种溶液法制备高密度氧化锆绝缘层薄膜的方法。
本发明目的通过以下技术方案实现：
一种溶液法制备高密度ZrO2绝缘层薄膜的方法，包括如下制备步骤：
(1)将Zr(NO3)4·5H2O(五水合硝酸锆)和H3BO3(硼酸)溶于乙二醇单甲醚(2-MOE)中，搅拌老化得到前驱体溶液；
(2)在ITO玻璃衬底上旋涂步骤(1)所得前驱体溶液，然后退火处理，得到高密度ZrO2绝缘层薄膜。
优选地，步骤(1)中所述前驱体溶液中Zr(NO3)4·5H2O的浓度为0.3～0.6mol/L，H3BO3加入的摩尔量为Zr(NO3)4·5H2O的7％～9％。
优选地，步骤(2)中所述旋涂的工艺条件为：转速4000～6000rpm，旋涂次数3～5次，每次旋涂时间30～40s，每次旋涂之间退火温度300℃，时间3～5min。
优选地，步骤(2)中所述退火处理的温度为300℃，时间为1～2h。
本发明的原理为：将Zr(NO3)4·5H2O和H3BO3溶于乙二醇单甲醚中，可以得到含硼离子的硝酸锆溶液。在薄膜后退火过程中硼离子与氧离子结合形成B-O(硼氧键)，由于B-O(硼氧键)的结合能(192.7kcal/mol)比Zr-O(锆氧键)的结合能(180.6kcal/mol)高，同时硼离子的离子半径(r0＝41pm)比锆离子的离子半径(r0＝86pm)小，因此硼氧键可以提高薄膜的致密度，从而实现高密度ZrO2薄膜的溶液法制备。B-O(硼氧键)和Zr-O(锆氧键)的示意图如图1所示。
本发明的制备方法具有如下优点及有益效果：
本发明在硝酸锆溶液中加入H3BO3，利用退火过程中形成的B-O(硼氧键)来提高薄膜的致密度，使得能够基于溶液法制备高密度ZrO2薄膜。
附图说明
图1是B-O(硼氧键)和Zr-O(锆氧键)的示意图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
(1)前驱体配制：将2.576g Zr(NO3)4·5H2O(五水合硝酸锆)和0.02596g H3BO3(硼酸)溶于10ml乙二醇单甲醚(2-MOE)中，搅拌老化24h得到浓度为0.6mol/L的前驱体溶液。
(2)衬底制备：在玻璃基板表面沉积一层150nm的ITO电极，清洗烘干，得到ITO玻璃衬底。
(3)在ITO玻璃衬底按所选工艺参数旋涂步骤(1)所得的前驱体溶液，旋涂转速6000rpm，每次匀胶时间40s，匀胶次数5次，每次匀胶之间退火温度300℃，时间4min，然后在300℃退火处理1h，得到高密度的氧化锆绝缘层薄膜。
使用XRR(X射线衍射)测试所得氧化锆薄膜的密度为4.82g/cm3，相比不加入硼酸所得氧化锆薄膜的密度(4.63g/cm3)有较大的提升。
实施例2
(1)前驱体配制：将1.288g Zr(NO3)4·5H2O(五水合硝酸锆)和0.01669g H3BO3(硼酸)溶于10ml乙二醇单甲醚(2-MOE)中，搅拌老化24h得到浓度为0.3mol/L的前驱体溶液。
(2)衬底制备：在玻璃基板表面沉积一层150nm的ITO电极，清洗烘干，得到ITO玻璃衬底。
(3)在ITO玻璃衬底按所选工艺参数旋涂步骤(1)所得的前驱体溶液，旋涂转速4000rpm，每次匀胶时间30s，匀胶次数3次，每次匀胶之间退火温度300℃，时间5min，然后在300℃退火处理2h，得到高密度的氧化锆绝缘层薄膜。
使用XRR(X射线衍射)测试所得氧化锆薄膜的密度为4.75g/cm3，相比不加入硼酸所得氧化锆薄膜的密度(4.63g/cm3)有较大的提升。
实施例3
(1)前驱体配制：将2.147g Zr(NO3)4·5H2O(五水合硝酸锆)和0.02472g H3BO3(硼酸)溶于10ml乙二醇单甲醚(2-MOE)中，搅拌老化24h得到浓度为0.5mol/L的前驱体溶液。
(2)衬底制备：在玻璃基板表面沉积一层150nm的ITO电极，清洗烘干，得到ITO玻璃衬底。
(3)在ITO玻璃衬底按所选工艺参数旋涂步骤(1)所得的前驱体溶液，旋涂转速5000rpm，每次匀胶时间40s，匀胶次数4次，每次匀胶之间退火温度300℃，时间3min，然后在300℃退火处理1.5h，得到高密度的氧化锆绝缘层薄膜。
使用XRR(X射线衍射)测试所得氧化锆薄膜的密度为4.78g/cm3，相比不加入硼酸所得氧化锆薄膜的密度(4.63g/cm3)有较大的提升。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (4)
1.一种溶液法制备高密度ZrO2绝缘层薄膜的方法，其特征在于包括如下制备步骤：
(1)将Zr(NO3)4·5H2O和H3BO3溶于乙二醇单甲醚中，搅拌老化得到前驱体溶液；
(2)在ITO玻璃衬底上旋涂步骤(1)所得前驱体溶液，然后退火处理，得到高密度ZrO2绝缘层薄膜。
2.根据权利要求1所述的一种溶液法制备高密度ZrO2绝缘层薄膜的方法，其特征在于：步骤(1)中所述前驱体溶液中Zr(NO3)4·5H2O的浓度为0.3～0.6mol/L，H3BO3加入的摩尔量为Zr(NO3)4·5H2O的7％～9％。
3.根据权利要求1所述的一种溶液法制备高密度ZrO2绝缘层薄膜的方法，其特征在于步骤(2)中所述旋涂的工艺条件为：转速4000～6000rpm，旋涂次数3～5次，每次旋涂时间30～40s，每次旋涂之间退火温度300℃，时间3～5min。
4.根据权利要求1所述的一种溶液法制备高密度ZrO2绝缘层薄膜的方法，其特征在于：步骤(2)中所述退火处理的温度为300℃，时间为1～2h。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20020072673A (ko) * | 2001-03-12 | 2002-09-18 | 삼성전자 주식회사 | 졸겔공정을 이용한 지르콘산-티탄산 납 후막의 제조방법 |
| CN106431397A (zh) * | 2016-09-14 | 2017-02-22 | 齐鲁工业大学 | 一种高介电氧化锆薄膜的低温溶液制备方法 |
| CN107799415A (zh) * | 2017-10-21 | 2018-03-13 | 河南大学 | 一种化学溶液法制备硼掺杂氧化物介电薄膜的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20020072673A (ko) * | 2001-03-12 | 2002-09-18 | 삼성전자 주식회사 | 졸겔공정을 이용한 지르콘산-티탄산 납 후막의 제조방법 |
| CN106431397A (zh) * | 2016-09-14 | 2017-02-22 | 齐鲁工业大学 | 一种高介电氧化锆薄膜的低温溶液制备方法 |
| CN107799415A (zh) * | 2017-10-21 | 2018-03-13 | 河南大学 | 一种化学溶液法制备硼掺杂氧化物介电薄膜的方法 |
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