WO2012062059A1 - 高k栅介质/金属栅叠层栅结构刻蚀后聚合物去除方法 - Google Patents
高k栅介质/金属栅叠层栅结构刻蚀后聚合物去除方法 Download PDFInfo
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- WO2012062059A1 WO2012062059A1 PCT/CN2011/070996 CN2011070996W WO2012062059A1 WO 2012062059 A1 WO2012062059 A1 WO 2012062059A1 CN 2011070996 W CN2011070996 W CN 2011070996W WO 2012062059 A1 WO2012062059 A1 WO 2012062059A1
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- Prior art keywords
- gate
- etching
- metal
- gate dielectric
- polymer
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005530 etching Methods 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 10
- 229920005591 polysilicon Polymers 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000002955 isolation Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 claims description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910004129 HfSiO Inorganic materials 0.000 claims description 3
- DUMHRFXBHXIRTD-UHFFFAOYSA-N Tantalum carbide Chemical compound [Ta+]#[C-] DUMHRFXBHXIRTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910010037 TiAlN Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 239000003870 refractory metal Substances 0.000 claims description 3
- 229940028300 tigan Drugs 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000000206 photolithography Methods 0.000 claims description 2
- 238000001020 plasma etching Methods 0.000 claims description 2
- 240000006394 Sorghum bicolor Species 0.000 claims 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims 1
- 238000000992 sputter etching Methods 0.000 claims 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract 1
- 238000001259 photo etching Methods 0.000 abstract 1
- 229920002120 photoresistant polymer Polymers 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000001039 wet etching Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000003756 stirring Methods 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
Definitions
- the invention belongs to the field of nano-semiconductor technology, and particularly relates to a method for removing a polymer after etching in a high-kappa (high dielectric constant) gate dielectric/metal gate stack structure in a prior gate process.
- the present invention is suitable for applications in the fabrication of 45 nm and below complementary metal oxide semiconductor devices and circuits. Background technique
- An object of the present invention is to provide a method for removing a polymer after etching in a high-k gate dielectric/metal gate stack structure. It not only maintains the steep stack gate etch profile, but also removes the polymer remaining on both sides of the stack gate and the surface of the silicon substrate, and does not cause damage to the silicon substrate. It has good compatibility with CMOS process and low cost.
- Step 2) photolithography to form a glue pattern
- Step 3) etching the stacked gate structure
- Step 4) The product of step 3) is immersed in the etching solution to remove the polymer.
- the ratio of the corrosive solution is 0.2 ⁇ 1% of hydrofluoric acid, 5 ⁇ 15% of hydrochloric acid, and the rest is water.
- the method, wherein the high-k gate dielectric in step 1) is an Hf-based doped oxide, such as Hf0 2 , HfSiON, HfSiO, HfSiON, HfLaO, HfLaON, HfAlON or HfSiAlON.
- Hf-based doped oxide such as Hf0 2 , HfSiON, HfSiO, HfSiON, HfLaO, HfLaON, HfAlON or HfSiAlON.
- the method, wherein the metal gate in the step 1) is a metal nitride or a doped refractory metal such as TaN, TiN, TaC, TaCN, ⁇ 1 ⁇ , TiAlN, TiGaN or MoAlN.
- the method, wherein the hard mask in step 1) is SiO 2 , Si 3 N 4 or a combination thereof.
- step 3 the hard mask is etched by a fluorine-based gas CF 4 /CHF 3 , the polysilicon is etched by a Cl 2 /HBr mixed gas, and the metal gate is etched by a C1 -based reactive ion, such as BCl 3 Mixed gas etching such as /Cl 2 /Ar or BCl 3 /Cl 2 /SF 6 /Ar; high-k gate dielectric etched with BC1 3 -based gas.
- a fluorine-based gas CF 4 /CHF 3 the polysilicon is etched by a Cl 2 /HBr mixed gas
- the metal gate is etched by a C1 -based reactive ion, such as BCl 3 Mixed gas etching such as /Cl 2 /Ar or BCl 3 /Cl 2 /SF 6 /Ar; high-k gate dielectric etched with BC1 3 -based gas.
- Figure 1 is a cross-sectional photograph of the stacked gate structure after etching and before depolymerization. Residual of the polymer (a thin layer of white deposit referred to by arrow A) is clearly visible on both sides of the laminate gate and on the surface of the silicon substrate.
- Figure 2 is a cross-sectional photograph of the stacked gate structure after etching followed by polymer removal. detailed description
- Step 1) After the device isolation is formed, sequentially formed on the silicon substrate: interface 310 2 / high 1 ⁇ gate dielectric / metal gate / polysilicon / hard mask laminated structure, wherein the high K gate dielectric is H can doped oxide , such as Hf0 2 , HfSiON, HfSiO, HfSiON, HfLaO, HfLaON, HfAlON or HfSiAlON; etc.; metal gate is metal nitride or miscellaneous refractory metal, such as TaN, TiN, TaC, TaCN, ⁇ 1 ⁇ , TiAlN, TiGaN or MoAlN Etc.
- the hard mask is Si0 2 , Si 3 N 4 or a combination thereof.
- Step 3) Reactive ion etching stacked gate structure The hard mask is etched by CF 4 /CHF 3 fluorine-based gas, the polysilicon is etched with Cl 2 /HBr mixed gas, and the metal gate is etched by C1 -based reactive ion, such as BCl 3 /Cl 2 /Ar or
- Step 4) Removal of polymer The wet chemical removal method, the volume ratio of the etching solution: hydrofluoric acid (HF) 0.2-0.5%, hydrochloric acid (HC1) 8 ⁇ 12%, the rest is water (3 ⁇ 40), at constant temperature Immerse 10" ⁇ 60" in the solution and stir the solution to obtain good uniformity.
- HF hydrofluoric acid
- HC1 hydrochloric acid
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Insulated Gate Type Field-Effect Transistor (AREA)
- Drying Of Semiconductors (AREA)
- Electrodes Of Semiconductors (AREA)
Description
高 K栅介质 /金属栅叠层栅结构刻蚀后聚合物去除方法
技术领域
' 本发明属于纳米半导体技术领域,特别是指一种在先栅工艺中高 κ (高介电常数) 栅介质 /金属栅叠层结构刻蚀后聚合物的去除方法。本发明适合 45nm及以下技术代互 补型金属氧化物半导体器件和电路制备的应用。 背景技术
当器件特征尺寸缩小到 45nm及以下时采用高 K栅介质 /金属栅叠层结构代替常规 的 Si02/多晶硅栅结构已势在必行, 同为高 K栅介质 /金属栅叠层结构大幅度降低了传 统的 Si02/多晶硅栅结构的大的栅漏电流, 消除了多晶硅栅耗尽效应, 降低了栅电阻。 但研究发现在先栅工艺中当高 K栅介质 /金属栅叠层结构刻蚀后, 叠层栅两侧及硅衬 底表面往往残留一层聚合物, 为消除这层聚合物对器件和电路特性的影响必须把它去 掉。 但关于先栅工艺中叠层栅结构刻蚀后聚合物的去除没见到有公开报道。 发明内容
本发明的目的在于提供一种高 K栅介质 /金属栅叠层结构刻蚀后聚合物的去除方 法。不仅保持陡直的叠栅刻蚀剖面,而且能去净叠栅两侧及硅衬底表面残留的聚合物, 并对硅衬底不造成损伤, 与 CMOS工艺兼容性好, 成本低。
为实现上述目的, 本发明提供了一种高 K栅介质 /金属栅叠层结构刻蚀后聚合物 的去除方法,在稀 HF中加入 HC1抑制对场区 Si02的侵蚀,提高对聚合物的去除效果; 其主要的步骤如下- 步骤 1 ) 在器件隔离形成后, 在硅衬底上依次形成界面 Si02/高 K栅介质 /金属栅 / 多晶硅 /硬掩膜叠层栅结构;
步骤 2) 光刻形成胶图形;
步骤 3 ) 刻蚀叠层栅结构;
步骤 4) 将步骤 3 ) 的产品浸没于腐蚀溶液中去除聚合物, 腐蚀溶液配比为氢氟 酸 0.2~1%, 盐酸 5~15%, 其余为水。
所述的方法,其中,步骤 1 )中的高 K栅介质为 Hf基掺杂氧化物,如 Hf02、HfSiON、
HfSiO、 HfSiON、 HfLaO、 HfLaON、 HfAlON或 HfSiAlON等。
所述的方法,其中,步骤 1 )中的金属栅为金属氮化物或揍杂的耐熔金属,如 TaN、 TiN、 TaC、 TaCN、 ΜοΑ1Ν、 TiAlN、 TiGaN或 MoAlN等。
所述的方法, 其中, 步骤 1 ) 中的硬掩膜为 Si02、 Si3N4或及其组合。
所述的方法, 其中, 步骤 3 ) 中硬掩膜采用氟基气体 CF4/CHF3刻蚀, 多晶硅采用 Cl2/HBr 混合气体刻蚀, 金属栅采用 C1 基反应离子刻蚀, 如 BCl3/Cl2/Ar 或 BCl3/Cl2/SF6/Ar等混合气体刻蚀; 高 K栅介质釆用 BC13基气体刻蚀。
所述的方法, 其中, 步骤 4)是在室温下于溶液中浸没 10~120秒, 并搅动腐蚀溶 液。 附图说明
图 1为叠层栅结构刻蚀后、 去聚合物前的剖面照片。 在叠层栅两侧和硅衬底表面 明显可见聚合物的残留 (箭头 A所指的白色沉积物薄层)。
图 2为叠层栅结构刻蚀后接着去除聚合物处理后的剖面照片。 具体实施方式
所举实例只用于解释本发明并非用于限定本发明的范围。
步骤 1 ) 在器件隔离形成后在硅衬底上依次形成: 界面 3102/高1^栅介质 /金属栅 /多 晶硅 /硬掩膜叠层结构, 其中高 K栅介质为 H堪掺杂氧化物, 如 Hf02、 HfSiON, HfSiO、 HfSiON、 HfLaO、 HfLaON、 HfAlON或 HfSiAlON等; 金属栅为金属氮化物或惨杂的 耐熔金属, 如 TaN、 TiN、 TaC、 TaCN、 ΜοΑ1Ν、 TiAlN、 TiGaN或 MoAlN等; 硬掩膜 为 Si02、 Si3N4或及其组合。
步骤 2) 电子束光刻形成胶图形;
步骤 3 ) 反应离子刻蚀叠层栅结构: 硬掩膜采用 CF4/CHF3氟基气体刻蚀, 多晶硅 釆用 Cl2/HBr混合气体刻蚀, 金属栅采用 C1基反应离子刻蚀, 如 BCl3/Cl2/Ar或
BCl3/Cl2/SF6/Ar等混合气体刻蚀; 高 K栅介质采用 BC13基气体刻蚀。
步骤 4) 去除聚合物: 采用湿法化学去除方法, 腐蚀溶液的体积比: 氢氟酸 (HF) 0.2-0.5%, 盐酸 (HC1) 8~12%, 其余为水 (¾0), 在定温下于溶液中浸没 10"~60", 并不 断搅动溶液以获得好的均匀性。
本发明去除聚合物残留的效果可比较参阅图 1和图 2, 从图 2中可见叠层栅两侧和
硅衬底表面的聚合物已去除干净, 剖面仍保持陡直, 硅表面光滑, 没引起损伤 t
Claims
权 利 要 求
. 1. 一种高 K栅介质 /金属栅叠层栅结构刻蚀后聚合物去除方法, 主要步骤如下- 步骤 1 ) 在器件隔离形成后, 在硅衬底上依次形成界面 Si02/高 Κ栅介质 /金属栅 / 多晶硅 /硬掩膜叠层栅结构;
步骤 2 ) 光刻形成胶图形;
步骤 3 ) 刻蚀叠层栅结构;
步骤 4 ) 将步骤 3 ) 的产品浸没于腐蚀溶液中去除聚合物, 腐蚀溶液体积配比为 氢氟酸 0.2~1%, 盐酸 5〜15%, 其余为水。
2. 根据权利要求 1所述的方法, 其中, 步骤 1 ) 中的高 K栅介质为 Hf基掺杂氧 化物。
3. 根据权利要求 1或 2所述的方法,其中,高 K栅介质为 Hf02、HfSiON、HfSiO、 HfSiON, HfLaO、 HfLaON、 HfAlON或 HfSiA10N。
4. 根据权利要求 1所述的方法, 其中, 步骤 1 ) 中的金属栅为金属氮化物或掺杂 的耐熔金属。
5. 根据权利要求 1或 4所述的方法, 其中, 金属栅为 TaN、 TiN、 TaC、 TaCN、 ΜοΑ1Ν、 TiAlN、 TiGaN或 MoAlN。
6. 根据权利要求 1所述的方法, 其中, 步骤 1 ) 中的硬掩膜为 Si02、 Si3N4或及 其组合。
7. 根据权利要求 1所述的方法, 其中, 步骤 3 )中硬掩膜采用氟基气体 CF4/CHF3 刻蚀, 多晶硅釆用 Cl2/HBr混合气体刻蚀, 金属栅采用 C1基反应离子刻蚀, 高 K栅 介质采用 BC13基气体刻蚀。
8. 根据权利要求 7 所述的方法, 其中, C1 基反应离子刻蚀为 BCl3/Cl2/Ar 或 BCl3/Cl2/SF6/Ai-混合气体刻蚀。
9. 根据权利要求 1 所述的方法, 其中, 步骤 4 ) 是在室温下于腐蚀溶液中浸没 10〜120秒, 并搅动腐蚀溶液。
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US13/130,514 US8334205B2 (en) | 2010-11-10 | 2011-02-15 | Method for removing polymer after etching gate stack structure of high-K gate dielectric/metal gate |
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CN201010541134.6A CN102468131B (zh) | 2010-11-10 | 2010-11-10 | 高k栅介质/金属栅叠层栅结构刻蚀后聚合物去除方法 |
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US20070051700A1 (en) * | 2005-09-05 | 2007-03-08 | Lee Hyo-San | Composition for cleaning substrates and method of forming gate using the composition |
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CN101523297A (zh) * | 2006-10-24 | 2009-09-02 | 关东化学株式会社 | 光刻胶残渣及聚合物残渣去除液组合物 |
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2010
- 2010-11-10 CN CN201010541134.6A patent/CN102468131B/zh active Active
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- 2011-02-15 WO PCT/CN2011/070996 patent/WO2012062059A1/zh active Application Filing
Patent Citations (7)
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US6110834A (en) * | 1997-10-29 | 2000-08-29 | Mitsubishi Denki Kabushiki Kaisha | Semiconductor device and manufacturing method thereof for removing reaction products of dry etching |
CN1645259A (zh) * | 2003-12-09 | 2005-07-27 | 关东化学株式会社 | 抗蚀剂残渣去除液组合物及半导体电路元件的制造方法 |
US20070051700A1 (en) * | 2005-09-05 | 2007-03-08 | Lee Hyo-San | Composition for cleaning substrates and method of forming gate using the composition |
US20070184996A1 (en) * | 2006-02-06 | 2007-08-09 | Cheng-Ming Weng | Cleaning agent and method of removing residue left after plasma process |
CN101523297A (zh) * | 2006-10-24 | 2009-09-02 | 关东化学株式会社 | 光刻胶残渣及聚合物残渣去除液组合物 |
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CN102468131B (zh) | 2016-06-01 |
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