TWI823862B - Reflective mask base and reflective mask - Google Patents
Reflective mask base and reflective mask Download PDFInfo
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- TWI823862B TWI823862B TW107127398A TW107127398A TWI823862B TW I823862 B TWI823862 B TW I823862B TW 107127398 A TW107127398 A TW 107127398A TW 107127398 A TW107127398 A TW 107127398A TW I823862 B TWI823862 B TW I823862B
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- 239000000463 material Substances 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 238000005530 etching Methods 0.000 claims abstract description 51
- 238000010521 absorption reaction Methods 0.000 claims abstract description 50
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 38
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 35
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- 238000001312 dry etching Methods 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical group [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 238000000059 patterning Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 67
- 239000007789 gas Substances 0.000 description 37
- 230000007547 defect Effects 0.000 description 26
- 238000001755 magnetron sputter deposition Methods 0.000 description 18
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- 230000015572 biosynthetic process Effects 0.000 description 13
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- 239000011521 glass Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000007689 inspection Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229910052743 krypton Inorganic materials 0.000 description 7
- 238000002310 reflectometry Methods 0.000 description 7
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- 238000002156 mixing Methods 0.000 description 6
- 238000000206 photolithography Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
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- 239000011651 chromium Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
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- 239000011135 tin Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910003071 TaON Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
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- 229910052726 zirconium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019895 RuSi Inorganic materials 0.000 description 1
- -1 Si 3 N 4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 238000001020 plasma etching Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
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- Preparing Plates And Mask In Photomechanical Process (AREA)
- Drying Of Semiconductors (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
本發明提供一種具備於蝕刻處理時具有充分之蝕刻速度之吸收膜之反射型遮罩基底。本發明之反射型遮罩基底之特徵在於：其係於基板上依序具備反射EUV光之多層反射膜、及吸收EUV光之吸收膜者，且上述吸收膜為包含鉭系材料之鉭系材料膜，上述吸收膜係於X射線繞射之圖案中源自鉭系材料之峰之峰繞射角2θ為36.8deg以上，源自該鉭系材料之峰之半值寬為1.5deg以上。 The present invention provides a reflective mask substrate having an absorbing film with sufficient etching speed during etching. The characteristic of the reflective mask substrate of the present invention is that it is provided with a multi-layer reflective film that reflects EUV light and an absorption film that absorbs EUV light in sequence on the substrate, and the above-mentioned absorption film is a tantalum-based material including a tantalum-based material. Film, the above-mentioned absorption film is such that the peak diffraction angle 2θ of the peak derived from the tantalum-based material in the X-ray diffraction pattern is 36.8deg or more, and the half-maximum width of the peak derived from the tantalum-based material is 1.5deg or more.
Description
本發明係關於一種半導體製造等中所使用之反射型遮罩基底、及於該反射型遮罩基底之吸收膜形成遮罩圖案而成之反射型遮罩。The present invention relates to a reflective mask substrate used in semiconductor manufacturing and the like, and a reflective mask in which a mask pattern is formed on an absorption film of the reflective mask substrate.
先前，於半導體產業中，作為於Si基板等上形成包含微細之圖案之積體電路時所需之微細圖案之轉印技術，可利用使用可見光或紫外光之光微影法。然而，半導體裝置之微細化加速，另一方面，不斷接近先前之光微影法之極限。於光微影法之情形時，圖案之解析極限為曝光波長之1/2左右，即便使用液浸法，亦稱為曝光波長之1/4左右，即便使用ArF雷射(193 nm)之液浸法，亦預測45 nm左右為極限。因此，作為45 nm以下之曝光技術，認為作為與ArF雷射相比進而使用短波長之EUV(Extreme Ultraviolet，極紫外線)光之曝光技術之EUV光微影法有希望。於本說明書中，所謂EUV光，係指軟X射線區域或真空紫外線區域之波長之光線，具體而言，係指波長10～20 nm左右，尤其係指13.5 nm±0.3 nm左右之光線。Previously, in the semiconductor industry, photolithography using visible light or ultraviolet light was used as a transfer technology for forming fine patterns on integrated circuits including fine patterns on Si substrates and the like. However, the miniaturization of semiconductor devices is accelerating. On the other hand, the limits of previous photolithography methods are constantly approaching. In the case of photolithography, the resolution limit of the pattern is about 1/2 of the exposure wavelength. Even if the liquid immersion method is used, it is also called about 1/4 of the exposure wavelength. Even if the liquid of ArF laser (193 nm) is used. According to the immersion method, it is also predicted that around 45 nm will be the limit. Therefore, as an exposure technology below 45 nm, EUV photolithography is considered to be promising as an exposure technology that uses short-wavelength EUV (Extreme Ultraviolet, extreme ultraviolet) light compared to ArF laser. In this specification, EUV light refers to light with a wavelength in the soft X-ray region or vacuum ultraviolet region. Specifically, it refers to light with a wavelength of about 10 to 20 nm, especially light of about 13.5 nm±0.3 nm.
EUV光係容易被多數之物質吸收，且於該波長下物質之折射率接近於1，故而無法使用如先前之使用可見光或紫外光之光微影法之折射光學系統。因此，於EUV光微影法中，可使用反射光學系統即反射型光罩與鏡。EUV light is easily absorbed by most materials, and the refractive index of materials at this wavelength is close to 1. Therefore, it is impossible to use refractive optical systems such as the previous photolithography method using visible light or ultraviolet light. Therefore, in EUV photolithography, a reflective optical system, that is, a reflective mask and mirror, can be used.
反射型遮罩基底係用於反射型光罩製造用途之圖案化前之積層體，具有依序形成於玻璃等基板上反射EUV光之反射層、及吸收EUV光之吸收膜之構造。 作為反射層，通常使用藉由使對於EUV光成為低折射率之低折射率層、與對於EUV光成為高折射率之高折射率層交替地積層，而提高使EUV光照射至層表面時之光線反射率之多層反射膜。作為多層反射膜之低折射率層，通常使用鉬(Mo)層，作為高折射率層，通常使用矽(Si)層。 吸收膜可使用對於EUV光之吸收係數較高之材料具體而言例如以鉭(Ta)作為主成分之材料(參照專利文獻1～5)。 [先前技術文獻] [專利文獻]The reflective mask substrate is a pre-patterned laminate used for manufacturing reflective masks. It has a structure in which a reflective layer that reflects EUV light and an absorbing film that absorbs EUV light are sequentially formed on a substrate such as glass. As the reflective layer, a low refractive index layer having a low refractive index for EUV light and a high refractive index layer having a high refractive index for EUV light are usually stacked alternately to increase the resistance when EUV light is irradiated to the layer surface. Multi-layer reflective film for light reflectivity. As the low refractive index layer of the multilayer reflective film, a molybdenum (Mo) layer is usually used, and as the high refractive index layer, a silicon (Si) layer is usually used. As the absorption film, a material having a high absorption coefficient for EUV light, specifically, a material containing tantalum (Ta) as a main component can be used (see Patent Documents 1 to 5). [Prior art documents] [Patent documents]
[專利文獻1]日本專利第5507876號說明書 [專利文獻2]日本專利特開2012-33715號公報 [專利文獻3]日本專利特開2015-84447號公報 [專利文獻4]日本專利特開2010-206156號公報 [專利文獻5]日本專利第3806702號說明書[Patent Document 1] Specification of Japanese Patent No. 5507876 [Patent Document 2] Japanese Patent Laid-Open No. 2012-33715 [Patent Document 3] Japanese Patent Laid-Open No. 2015-84447 [Patent Document 4] Japanese Patent Laid-Open No. 2010- Publication No. 206156 [Patent Document 5] Japanese Patent No. 3806702 Specification
[發明所欲解決之問題][Problem to be solved by the invention]
於由遮罩基底製造反射型光罩時，於遮罩基底之吸收膜形成所需之圖案。於在吸收膜形成圖案時，可使用蝕刻處理，通常可使用乾式蝕刻處理。只要於乾式蝕刻處理時具有充分之蝕刻速度，則圖案形成時之蝕刻選擇比提高，故而較佳。若蝕刻選擇比提高，則可縮短圖案化所需之時間，提高生產性，減輕因蝕刻處理對多層反射膜造成之損傷。When manufacturing a reflective mask from a mask base, a desired pattern is formed on the absorption film of the mask base. When forming a pattern on the absorbing film, an etching process may be used, and generally a dry etching process may be used. It is preferable to have a sufficient etching speed during dry etching because the etching selectivity during pattern formation can be improved. If the etching selectivity is increased, the time required for patterning can be shortened, productivity can be improved, and damage to the multilayer reflective film caused by the etching process can be reduced.
本發明之目的在於提供一種具備於乾式蝕刻處理時具有充分之蝕刻速度之吸收膜之反射型遮罩基底、及反射型遮罩。 [解決問題之技術手段]An object of the present invention is to provide a reflective mask substrate and a reflective mask provided with an absorbing film having a sufficient etching speed during dry etching. [Technical means to solve problems]
本發明者等為了達成上述目的而努力研究，結果發現：於對含有Ta與氮(N)之吸收膜，將其結晶狀態設為特定之狀態之情形時，於乾式蝕刻處理時，可達成充分之蝕刻速度。 本案發明係基於上述見解而完成者，提供一種反射型遮罩基底，其特徵在於：其係於基板上自基板側依序具備反射EUV光之多層反射膜、及吸收EUV光之吸收膜者，且上述吸收膜為包含鉭系材料之鉭系材料膜， 上述吸收膜係於X射線繞射之圖案中源自鉭系材料之峰之峰繞射角2θ為36.8 deg以上，源自該鉭系材料之峰之半值寬為1.5 deg以上。The inventors of the present invention have worked hard to achieve the above object, and have found that when the crystallization state of the absorption film containing Ta and nitrogen (N) is set to a specific state, sufficient performance can be achieved during dry etching. The etching speed. The present invention is based on the above knowledge and provides a reflective mask substrate, which is characterized in that it has a multi-layer reflective film that reflects EUV light and an absorbing film that absorbs EUV light in order from the substrate side. And the above-mentioned absorption film is a tantalum-based material film containing a tantalum-based material. The above-mentioned absorption film is derived from the peak diffraction angle 2θ of the tantalum-based material in the X-ray diffraction pattern of 36.8 deg or more, which is derived from the tantalum-based material. The half value width of the peak is more than 1.5 deg.
於本發明之反射型遮罩基底中，較佳為上述鉭系材料膜含有10.0～35.0 at%之氮原子。In the reflective mask substrate of the present invention, it is preferred that the tantalum-based material film contains 10.0 to 35.0 at% nitrogen atoms.
於本發明之反射型遮罩基底中，較佳為上述鉭系材料膜含有0.05 at%以上之氪原子。In the reflective mask substrate of the present invention, it is preferable that the tantalum-based material film contains more than 0.05 at% of krypton atoms.
於本發明之反射型遮罩基底中，較佳為於上述多層反射膜上具備保護膜，於利用氯氣之乾式蝕刻處理中，上述吸收膜與上述保護膜之蝕刻選擇比為45以上。In the reflective mask substrate of the present invention, it is preferable that a protective film is provided on the multilayer reflective film, and in a dry etching process using chlorine gas, the etching selectivity ratio between the absorbing film and the protective film is 45 or more.
於本發明之反射型遮罩基底中，較佳為上述保護膜為包含釕系材料之釕系材料膜。In the reflective mask substrate of the present invention, it is preferable that the protective film is a ruthenium-based material film containing a ruthenium-based material.
又，本發明提供一種藉由於本發明之反射型遮罩基底之上述吸收膜形成圖案而獲得之反射型遮罩。 [發明之效果]Furthermore, the present invention provides a reflective mask obtained by patterning the above-mentioned absorption film of the reflective mask base of the present invention. [Effects of the invention]
本發明之反射型遮罩基底係具備於乾式蝕刻處理時具有充分之蝕刻速度之吸收膜，故而圖案形成時之蝕刻選擇比較高。The reflective mask substrate of the present invention is equipped with an absorbing film with sufficient etching speed during dry etching, so the etching selectivity during pattern formation is relatively high.
以下，參照圖式說明本發明之反射型遮罩基底。 圖1係表示本發明之反射型遮罩基底之一實施形態之概略剖視圖。圖1所示之反射型遮罩基底1係依序形成於基板11上反射EUV光之多層反射膜12、及吸收EUV光之吸收膜14。於多層反射膜12與吸收膜14之間，形成用以於在吸收膜14形成圖案時保護多層反射膜12之保護膜13。對基板11之背面側即相對於形成有多層反射膜12、保護膜13及吸收膜14之面之背面側形成背面導電膜15。 以下，對本發明之遮罩基底之各個構成元件進行說明。 再者，於本發明之反射型遮罩基底中，於圖1所示之構成中，基板11、多層反射膜12、及吸收膜14僅為必需，保護膜13及背面導電膜15為任意之構成元件。 以下，對反射型遮罩基底1之各個構成元件進行說明。Hereinafter, the reflective mask substrate of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of the reflective mask substrate of the present invention. The reflective mask substrate 1 shown in FIG. 1 is formed sequentially on the substrate 11 with a multi-layer reflective film 12 that reflects EUV light and an absorbing film 14 that absorbs EUV light. A protective film 13 is formed between the multilayer reflective film 12 and the absorbing film 14 to protect the multilayer reflective film 12 when the absorbing film 14 is patterned. The back conductive film 15 is formed on the back side of the substrate 11 , that is, on the back side of the surface on which the multilayer reflective film 12 , the protective film 13 and the absorption film 14 are formed. Each component of the mask base of the present invention will be described below. Furthermore, in the reflective mask substrate of the present invention, in the structure shown in FIG. 1 , the substrate 11, the multilayer reflective film 12, and the absorption film 14 are only necessary, and the protective film 13 and the back conductive film 15 are optional. Components. Each component of the reflective mask base 1 will be described below.
基板11要求滿足作為反射型遮罩基底用之基板之特性。因此，基板11較佳為具有低熱膨脹係數(具體而言，20℃下之熱膨脹係數較佳為0±0.05×10-7 /℃，尤佳為0±0.03×10-7 /℃)，平滑性、平坦度、及對用於遮罩基底或圖案形成後之光罩之洗淨等之洗淨液之耐受性優異者。作為基板11，具體而言，使用具有低熱膨脹係數之玻璃例如SiO2 -TiO2 系玻璃等，但並不限定於其，可使用使β石英固溶體析出而成之結晶化玻璃或石英玻璃或矽或金屬等基板。 基板11具有表面粗糙度(rms)0.15 nm以下之平滑之表面與100 nm以下之平坦度之情況可使圖案形成後之反射型光罩獲得高反射率及轉印精度，故而較佳。 基板11之大小或厚度等係由遮罩之設計值等而適宜決定者。於以下所示之實施例中，使用外形6英吋(152 mm)見方且厚度0.25英吋(6.3 mm)之SiO2 -TiO2 系玻璃。 較佳為於基板11之形成有多層反射膜12之側之表面不存在缺點。然而，即便於存在之情形時，為了不因凹狀缺點及/或凸狀缺點而產生相位缺點，較佳為凹狀缺點之深度及凸狀缺點之高度為2 nm以下，且該等凹狀缺點及凸狀缺點之半值寬為60 nm以下。The substrate 11 is required to satisfy the characteristics of a substrate used as a reflective mask substrate. Therefore, the substrate 11 preferably has a low thermal expansion coefficient (specifically, the thermal expansion coefficient at 20°C is preferably 0±0.05×10 -7 /°C, especially 0±0.03×10 -7 /°C), smooth and Those with excellent properties, flatness, and resistance to cleaning solutions used for masking substrates or photomasks after pattern formation, etc. As the substrate 11 , specifically, glass having a low thermal expansion coefficient such as SiO 2 -TiO 2 based glass is used, but it is not limited thereto. Crystallized glass or quartz glass obtained by precipitating β quartz solid solution may be used. Or substrates such as silicon or metal. It is preferable that the substrate 11 has a smooth surface with a surface roughness (rms) of 0.15 nm or less and a flatness of 100 nm or less, so that the reflective mask after pattern formation can obtain high reflectivity and transfer accuracy. The size, thickness, etc. of the substrate 11 are appropriately determined based on the design value of the mask, etc. In the embodiment shown below, SiO 2 -TiO 2 glass with an outer shape of 6 inches (152 mm) square and a thickness of 0.25 inches (6.3 mm) is used. It is preferable that there is no defect on the surface of the substrate 11 on the side where the multilayer reflective film 12 is formed. However, even if it exists, in order to prevent phase defects from occurring due to concave defects and/or convex defects, it is preferable that the depth of the concave defects and the height of the convex defects be 2 nm or less, and the concave defects The half-value width of defects and convex defects is 60 nm or less.
多層反射膜12係藉由使高折射層與低折射率層交替地積層複數次而達成高EUV光線反射率。於多層反射膜12中，於低折射率層中廣泛使用Mo，於高折射率層中廣泛使用Si。即，最通常為Mo/Si多層反射膜。然而，多層反射膜並不限定於此，亦可使用Ru/Si多層反射膜、Mo/Be多層反射膜、Mo化合物/Si化合物多層反射膜、Si/Mo/Ru多層反射膜、Si/Mo/Ru/Mo多層反射膜、Si/Ru/Mo/Ru多層反射膜。The multilayer reflective film 12 achieves high EUV light reflectivity by alternately stacking high refractive index layers and low refractive index layers a plurality of times. In the multilayer reflective film 12, Mo is widely used in the low refractive index layer, and Si is widely used in the high refractive index layer. That is, the most common one is a Mo/Si multilayer reflective film. However, the multilayer reflective film is not limited to this, and Ru/Si multilayer reflective film, Mo/Be multilayer reflective film, Mo compound/Si compound multilayer reflective film, Si/Mo/Ru multilayer reflective film, Si/Mo/ Ru/Mo multilayer reflective film, Si/Ru/Mo/Ru multilayer reflective film.
多層反射膜12只要為具有作為反射型遮罩基底之多層反射膜所需之特性者，則並無特別限定。此處，對多層反射膜12尤其要求之特性係高EUV光線反射率。具體而言，於使EUV光之波長區域之光線以入射角6度照射至多層反射膜12表面時，波長13.5 nm附近之光線反射率之最大值較佳為60%以上，更佳為65%以上。又，即便於在多層反射膜12之上設置保護膜13之情形時，波長13.5 nm附近之光線反射率之最大值較佳為60%以上，更佳為65%以上。The multilayer reflective film 12 is not particularly limited as long as it has characteristics required for a multilayer reflective film serving as a reflective mask base. Here, a particularly required characteristic of the multilayer reflective film 12 is high EUV light reflectivity. Specifically, when light in the wavelength range of EUV light is irradiated onto the surface of the multilayer reflective film 12 at an incident angle of 6 degrees, the maximum reflectivity of light with a wavelength near 13.5 nm is preferably more than 60%, and more preferably 65%. above. In addition, even when the protective film 13 is provided on the multilayer reflective film 12, the maximum value of the reflectivity of light near a wavelength of 13.5 nm is preferably 60% or more, more preferably 65% or more.
構成多層反射膜12之各層之膜厚及層之重複單元之數量可根據使用之膜材料及多層反射膜所要求之EUV光線反射率而適宜選擇。若列舉Mo/Si反射膜為例，於製作EUV光線反射率之最大值為60%以上之反射層12時，多層反射膜只要將膜厚2.3±0.1 nm之Mo層、與膜厚4.5±0.1 nm之Si層以重複單元數成為30～60之方式積層即可。The film thickness of each layer constituting the multi-layer reflective film 12 and the number of repeating units of the layers can be appropriately selected according to the film material used and the EUV light reflectivity required of the multi-layer reflective film. Taking the Mo/Si reflective film as an example, when producing the reflective layer 12 with a maximum EUV light reflectivity of more than 60%, the multilayer reflective film only needs to combine a Mo layer with a thickness of 2.3±0.1 nm and a thickness of 4.5±0.1 nm. The nm Si layer may be stacked so that the number of repeating units is 30 to 60.
再者，構成多層反射膜12之各層只要使用磁控濺鍍法、離子束濺鍍法等周知之成膜方法以成為所需之厚度之方式成膜即可。例如於使用離子束濺鍍法形成Si/Mo多層反射膜之情形時，較佳為使用Si靶作為靶，使用氬氣(氣壓1.3×10-2 Pa～2.7×10-2 Pa)作為濺鍍氣體，以離子加速電壓300～1500 V、成膜速度1.8～18 nm/min，以成為厚度4.5 nm之方式將Si膜成膜，繼而，使用Mo靶作為靶，使用氬氣(氣壓1.3×10-2 Pa～2.7×10-2 Pa)作為濺鍍氣體，以離子加速電壓300～1500 V、成膜速度1.8～18 nm/min，以成為厚度2.3 nm之方式將Mo膜成膜。將其設為1個週期，並藉由將Si膜及Mo膜積層40～50個週期而使Si/Mo多層反射膜成膜。In addition, each layer constituting the multilayer reflective film 12 may be formed to a desired thickness using a well-known film forming method such as magnetron sputtering or ion beam sputtering. For example, when forming a Si/Mo multilayer reflective film using ion beam sputtering, it is preferable to use a Si target as the target and argon gas (gas pressure 1.3×10 -2 Pa to 2.7×10 -2 Pa) as the sputtering Gas, use an ion acceleration voltage of 300 to 1500 V and a film formation speed of 1.8 to 18 nm/min to form a Si film to a thickness of 4.5 nm. Then, use a Mo target as the target and use argon gas (gas pressure 1.3×10 -2 Pa ~ 2.7 × 10 -2 Pa) was used as the sputtering gas, using an ion acceleration voltage of 300 to 1500 V, a film formation speed of 1.8 to 18 nm/min, and a Mo film to a thickness of 2.3 nm. Let this be one cycle, and stack the Si film and the Mo film for 40 to 50 cycles to form a Si/Mo multilayer reflective film.
為了防止多層反射膜12表面氧化，較佳為將多層反射膜12之最上層設為不易氧化之材料之層。不易氧化之材料之層係作為多層反射膜12之蓋層發揮功能。至於作為蓋層發揮功能之不易氧化之材料之層之具體例，可例示Si層。於多層反射膜12為Si/Mo膜之情形時，可藉由將最上層設為Si層，而使該最上層作為蓋層發揮功能。該情形蓋層之膜厚較佳為11±2 nm。In order to prevent the surface of the multi-layer reflective film 12 from being oxidized, it is preferable that the uppermost layer of the multi-layer reflective film 12 is made of a material that is not easily oxidized. The layer of material that is not easily oxidized functions as a cover layer of the multilayer reflective film 12 . As a specific example of the layer of a material that is not easily oxidized and functions as a capping layer, a Si layer can be exemplified. When the multilayer reflective film 12 is a Si/Mo film, the uppermost layer can be made into a Si layer so that the uppermost layer can function as a capping layer. In this case, the film thickness of the capping layer is preferably 11±2 nm.
保護膜13係於藉由蝕刻處理通常為乾式蝕刻處理而於吸收膜14形成圖案時，以不使多層反射膜12因蝕刻處理而受到損傷之方式且以保護多層反射膜12之目的所設置之任意之構成元件。然而，就保護多層反射膜12之觀點而言，較佳為於多層反射膜12上形成保護膜13。The protective film 13 is provided for the purpose of protecting the multilayer reflective film 12 so as not to damage the multilayer reflective film 12 due to the etching process when the absorption film 14 is patterned by an etching process, usually a dry etching process. Any component. However, from the viewpoint of protecting the multilayer reflective film 12 , it is preferable to form the protective film 13 on the multilayer reflective film 12 .
作為保護膜13之材質，選擇不易受到因吸收膜14之蝕刻處理造成之影響即該蝕刻速度小於吸收膜14，並且不易受到因該蝕刻處理造成之損傷之物質。 又，保護膜13為了即便於形成保護膜13後亦無損多層反射膜12上之EUV反射率，較佳為選擇保護膜13本身亦為EUV反射率較高之物質。 作為保護膜13，較佳為包含釕系材料之釕系材料膜。於本說明書中，於稱為釕系材料之情形時，係指Ru及Ru化合物(RuB、RuSi等)。釕系材料膜中之Ru之含有率較佳為50 at%以上，更佳為70 at%以上，進而較佳為90 at%以上，尤佳為95 at%以上。As the material of the protective film 13, a material is selected that is not easily affected by the etching process of the absorbing film 14, that is, the etching speed is lower than that of the absorbing film 14, and is not easily damaged by the etching process. In addition, in order for the protective film 13 not to damage the EUV reflectivity of the multilayer reflective film 12 even after the protective film 13 is formed, it is preferable to select the protective film 13 itself to be a material with a high EUV reflectivity. As the protective film 13, a ruthenium-based material film containing a ruthenium-based material is preferred. In this specification, when it is called a ruthenium-based material, it refers to Ru and Ru compounds (RuB, RuSi, etc.). The Ru content rate in the ruthenium-based material film is preferably 50 at% or more, more preferably 70 at% or more, further preferably 90 at% or more, particularly preferably 95 at% or more.
於在多層反射膜12上形成保護膜13之情形時，保護膜13之厚度就提高EUV反射率，且可獲得耐蝕刻特性之理由而言，較佳為1～10 nm。保護膜13之厚度更佳為1～5 nm，進而較佳為2～4 nm。When the protective film 13 is formed on the multilayer reflective film 12, the thickness of the protective film 13 is preferably 1 to 10 nm in order to increase EUV reflectivity and obtain etching resistance. The thickness of the protective film 13 is preferably 1 to 5 nm, and further preferably 2 to 4 nm.
於在多層反射膜12上形成保護膜13之情形時，保護膜13可使用磁控濺鍍法、離子束濺鍍法等周知成膜方法而形成。 於使用離子束濺鍍法形成Ru膜作為保護膜13之情形時，只要使用Ru靶作為靶，於氬(Ar)氛圍中進行放電即可。具體而言，只要利用以下之條件實施離子束濺鍍即可。 濺鍍氣體：Ar(氣壓：1.3×10-2 Pa～2.7×10-2 Pa) 離子加速電壓：300～1500 V 成膜速度：1.8～18.0 nm/minWhen forming the protective film 13 on the multilayer reflective film 12, the protective film 13 can be formed using a known film forming method such as magnetron sputtering or ion beam sputtering. When the ion beam sputtering method is used to form a Ru film as the protective film 13, a Ru target is used as the target and discharge is performed in an argon (Ar) atmosphere. Specifically, ion beam sputtering may be performed using the following conditions. Sputtering gas: Ar (gas pressure: 1.3×10 -2 Pa～2.7×10 -2 Pa) Ion acceleration voltage: 300～1500 V Film formation speed: 1.8～18.0 nm/min
對吸收膜14尤其要求之特性係EUV反射率極低。具體而言，於將EUV光之波長區域之光線照射至吸收膜14表面時，較佳為波長13.5 nm附近之最大光線反射率為2.0%以下，更佳為1.0%以下，進而較佳為0.5%以下，尤佳為0.1%以下。A particularly required characteristic of the absorbing film 14 is extremely low EUV reflectivity. Specifically, when light in the wavelength range of EUV light is irradiated to the surface of the absorbing film 14, the maximum light reflectance near the wavelength of 13.5 nm is preferably 2.0% or less, more preferably 1.0% or less, and further preferably 0.5 % or less, preferably less than 0.1%.
為了達成上述特性，吸收膜14係由EUV光之吸收係數較高之材料構成。於本發明之反射型遮罩基底1中，作為構成吸收膜14之EUV光之吸收係數高之材料，乃使用包含鉭系材料之鉭系材料膜。使用鉭系材料膜之理由在於：於化學上穩定之吸收膜之圖案形成時容易蝕刻等。再者，於本說明書中，於稱鉭系材料之情形時，係指鉭(Ta)及Ta化合物。In order to achieve the above characteristics, the absorption film 14 is made of a material with a high absorption coefficient of EUV light. In the reflective mask substrate 1 of the present invention, a tantalum-based material film containing a tantalum-based material is used as a material constituting the absorbing film 14 with a high EUV light absorption coefficient. The reason for using a tantalum-based material film is that it is easy to etch during pattern formation of a chemically stable absorbing film. In this specification, when a tantalum-based material is referred to, it refers to tantalum (Ta) and Ta compounds.
鉭系材料膜含有Ta及氮(N)可抑制Ta之結晶化，防止結晶增大而使表面粗糙度提高，故而較佳。 於鉭系材料膜含有Ta及N之情形時，N原子之含有率為10.0～35.0 at%之情況於達成吸收膜14之X射線繞射圖案之下述條件，且提高蝕刻選擇比之方面較佳，更佳為10.0～25.0 at%，進而較佳為10.5～18.0 at%，尤佳為11.0～16.0 at%。It is preferable that the tantalum-based material film contains Ta and nitrogen (N), which can inhibit the crystallization of Ta and prevent the increase in crystallization and increase in surface roughness. When the tantalum-based material film contains Ta and N, the following conditions are achieved for the X-ray diffraction pattern of the absorbing film 14 and the etching selectivity is improved when the content rate of N atoms is 10.0 to 35.0 at%. Preferably, it is 10.0-25.0 at%, more preferably 10.5-18.0 at%, especially 11.0-16.0 at%.
於鉭系材料膜含有Ta及N之情形時，鉭系材料膜亦可進而包含選自鉿(Hf)、矽(Si)、鋯(Zr)、鈦(Ti)、鍺(Ge)、硼(B)、錫(Sn)、鎳(Ni)、鈷(Co)及氫(H)中之至少一種之元素。於包含該等元素之情形時，較佳為鉭系材料膜中之該等元素之合計含有率為10 at%以下。When the tantalum-based material film contains Ta and N, the tantalum-based material film may further include hafnium (Hf), silicon (Si), zirconium (Zr), titanium (Ti), germanium (Ge), boron ( B), at least one element selected from tin (Sn), nickel (Ni), cobalt (Co) and hydrogen (H). When these elements are included, the total content of these elements in the tantalum-based material film is preferably 10 at% or less.
作為鉭系材料膜之吸收膜14係於X射線繞射之圖案中具有源自鉭系材料之峰。於本發明之反射型遮罩基底1中，藉由使源自鉭系材料之峰滿足以下所示之1、2之條件，而於乾式蝕刻處理時具有充分之蝕刻速度。 條件1：該峰之峰繞射角2θ為36.8 deg以上。 條件2：該峰之半值寬為1.5 deg以上。 於本說明書中，半值寬亦稱為FWHM。The absorption film 14 which is a tantalum-based material film has a peak originating from the tantalum-based material in the X-ray diffraction pattern. In the reflective mask substrate 1 of the present invention, the peak derived from the tantalum-based material satisfies the following conditions 1 and 2, thereby achieving a sufficient etching speed during dry etching. Condition 1: The peak diffraction angle 2θ of this peak is 36.8 deg or more. Condition 2: The half-width of the peak is more than 1.5 deg. In this specification, the half-maximum width is also called FWHM.
於該峰之峰繞射角2θ未達36.8 deg之情形時，結晶相中之非晶相之比率提高，乾式蝕刻處理時之蝕刻速度降低。另一方面，若峰繞射角2θ為36.8 deg以上，則結晶相中之非晶相與微結晶相之混相狀態變得合適，於相界面蝕刻容易進行，故而蝕刻速度提高。 該峰之峰繞射角2θ較佳為36.8 deg～40.0 deg之範圍，更佳為37.0 deg～39.0 deg之範圍。When the peak diffraction angle 2θ of this peak does not reach 36.8 deg, the ratio of the amorphous phase in the crystalline phase increases, and the etching rate during dry etching process decreases. On the other hand, if the peak diffraction angle 2θ is 36.8 deg or more, the mixed phase state of the amorphous phase and the microcrystalline phase in the crystal phase becomes suitable, and etching at the phase interface is easy to proceed, so the etching rate is increased. The peak diffraction angle 2θ of this peak is preferably in the range of 36.8 deg to 40.0 deg, more preferably in the range of 37.0 deg to 39.0 deg.
於該峰之半值寬未達1.5 deg之情形時，鉭系材料膜之結晶性提高，故而於鉭系材料膜之表面產生粗大之結晶粒。鉭系材料膜之表面之粗大之結晶粒係於缺陷檢查時以附著異物之形式被檢測出，有與本來應被檢查之附著異物之區別變得困難，而使缺陷檢查精度降低之虞。又，亦有難以對吸收膜均勻地蝕刻，而蝕刻後之表面粗糙度變粗之虞。 該峰之半值寬較佳為2.5 deg～6.0 deg，更佳為3.0 deg～5.0 deg。When the half-maximum width of the peak is less than 1.5 deg, the crystallinity of the tantalum-based material film increases, so coarse crystal grains are generated on the surface of the tantalum-based material film. Coarse crystal grains on the surface of the tantalum-based material film are detected as adhering foreign matter during defect inspection, which may make it difficult to distinguish them from the adhering foreign matter that should be inspected, and may reduce the accuracy of defect inspection. Furthermore, it may be difficult to uniformly etch the absorption film, and the surface roughness may become rough after etching. The half-maximum width of the peak is preferably 2.5 deg to 6.0 deg, more preferably 3.0 deg to 5.0 deg.
滿足上述條件1、2之吸收膜14係於乾式蝕刻處理時具有充分之蝕刻速度，與多層反射膜(於多層反射膜上未形成保護膜之情形)、或保護膜(於多層反射膜上形成保護膜之情形)之蝕刻選擇比提高。例如，於使用氯系氣體作為蝕刻氣體之乾式蝕刻處理時之蝕刻速度加快，與保護膜13之蝕刻選擇比成為45以上。於本說明書中，蝕刻選擇比例如可使用下述式進行計算。 蝕刻選擇比 ＝(吸收膜14之蝕刻速度)/(保護膜13之蝕刻速度) 使用氯系氣體作為蝕刻氣體之乾式蝕刻處理時之蝕刻選擇比較佳為45以上，更佳為50以上，進而較佳為55以上，尤佳為60以上。又，蝕刻選擇比較佳為250以下，更佳為100以下。The absorption film 14 that satisfies the above conditions 1 and 2 has a sufficient etching speed during dry etching, and is different from the multilayer reflective film (when no protective film is formed on the multilayer reflective film) or the protective film (when the multilayer reflective film is formed on the multilayer reflective film). In the case of protective film), the etching selectivity is improved. For example, in a dry etching process using a chlorine-based gas as the etching gas, the etching speed increases, and the etching selectivity ratio to the protective film 13 becomes 45 or more. In this specification, the etching selection ratio can be calculated using the following formula, for example. Etching selectivity ratio = (etching speed of the absorption film 14 )/(etching speed of the protective film 13 ) When dry etching using a chlorine-based gas as the etching gas, the etching selectivity ratio is preferably 45 or more, more preferably 50 or more, and further preferably 45 or more, and more preferably 50 or more. The best is 55 or above, and the best is 60 or above. Moreover, the etching selectivity ratio is preferably 250 or less, more preferably 100 or less.
吸收膜14之膜厚較佳為5 nm以上，更佳為20 nm以上，進而較佳為30 nm以上，尤佳為35 nm以上。 另一方面，若吸收膜14之膜厚過大，則有形成於該吸收膜14之圖案之精度降低之虞，故而較佳為100 nm以下，更佳為90 nm以下，進而較佳為80 nm以下。 再者，藉由利用相位偏移之原理，於吸收膜14中包含吸收係數較高之元素例如Sn、Ni、Co等，可減小吸收膜14之膜厚。The film thickness of the absorption film 14 is preferably 5 nm or more, more preferably 20 nm or more, further preferably 30 nm or more, particularly preferably 35 nm or more. On the other hand, if the film thickness of the absorption film 14 is too large, the accuracy of the pattern formed on the absorption film 14 may decrease. Therefore, it is preferably 100 nm or less, more preferably 90 nm or less, and still more preferably 80 nm. the following. Furthermore, by utilizing the principle of phase shift and including elements with higher absorption coefficients such as Sn, Ni, Co, etc. in the absorption film 14 , the film thickness of the absorption film 14 can be reduced.
吸收膜14可使用如磁控濺鍍法或離子束濺鍍法之濺鍍法等周知之成膜方法。 於形成TaN層作為吸收膜14之情形、使用磁控濺鍍法之情形時，藉由使用Ta靶，於利用Ar所稀釋之氮氣(N2 )氛圍中對靶進行放電，可形成TaN層。The absorption film 14 can be formed by a known film-forming method such as magnetron sputtering or ion beam sputtering. When the TaN layer is formed as the absorber film 14 or when the magnetron sputtering method is used, the TaN layer can be formed by using a Ta target and discharging the target in a nitrogen (N 2 ) atmosphere diluted with Ar.
於利用上述所例示之方法形成作為吸收膜14之TaN層時，具體而言，只要利用以下之成膜條件實施即可。 濺鍍氣體：稀有氣體與N2 之混合氣體(氮氣濃度3～80 vol%，較佳為5～30 vol%，更佳為8～15 vol%；氣壓0.5×10-1 Pa～10×10-1 Pa，較佳為0.5×10-1 Pa～5×10-1 Pa，更佳為0.5×10-1 Pa～3×10-1 Pa。) 投入電力(對各靶)：30～2000 W、較佳為50～1500 W、更佳為80～1000 W 成膜速度：2.0～60 nm/min、較佳為3.5～45 nm/min、更佳為5～30 nm/minWhen the TaN layer as the absorption film 14 is formed using the method illustrated above, specifically, the following film formation conditions may be used. Sputtering gas: mixed gas of rare gas and N2 (nitrogen concentration 3~80 vol%, preferably 5~30 vol%, more preferably 8~15 vol%; gas pressure 0.5×10 -1 Pa~10×10 -1 Pa, preferably 0.5×10 -1 Pa to 5×10 -1 Pa, more preferably 0.5×10 -1 Pa to 3×10 -1 Pa.) Input power (for each target): 30 to 2000 W, preferably 50 to 1500 W, more preferably 80 to 1000 W. Film formation speed: 2.0 to 60 nm/min, preferably 3.5 to 45 nm/min, more preferably 5 to 30 nm/min.
於上述中，使用氪(Kr)作為濺鍍氣體中之稀有氣體可防止吸收膜14形成時之膜變形，抑制基板變形，故而較佳。 使用氪(Kr)作為濺鍍氣體中之稀有氣體所形成之吸收膜14含有0.05 at%以上之Kr原子。Kr原子之含量之上限較佳為1%，更佳為0.3%。Among the above, it is preferable to use krypton (Kr) as the rare gas in the sputtering gas because it can prevent film deformation when the absorption film 14 is formed and suppress deformation of the substrate. The absorption film 14 formed by using krypton (Kr) as a rare gas in the sputtering gas contains more than 0.05 at% of Kr atoms. The upper limit of the content of Kr atoms is preferably 1%, more preferably 0.3%.
背面導電膜15係以薄片電阻成為100 Ω/□以下之方式選擇構成材料之導電率與厚度。作為背面導電膜15之構成材料，可自公知之文獻中記載者廣泛地選擇。例如可列舉：日本專利特表2003-501823號公報或日本專利再表2008/072706中記載之高介電常數物質層具體而言為選自由矽、TiN、鉬、鉻(Cr)、CrN、TaSi所組成之群中之物質層。背面導電膜可藉由乾式成膜法具體而言為磁控濺鍍法、離子束濺鍍法等濺鍍法、CVD(Chemical Vapor Deposition，化學氣相沈積)法、及真空蒸鍍法等乾式成膜法而形成。例如於利用磁控濺鍍法形成CrN膜之情形時，只要將靶設為Cr靶，將濺鍍氣體設為Ar與N2 之混合氣體，而實施磁控濺鍍即可，具體而言，只要利用以下之成膜條件實施即可。 靶：Cr靶 濺鍍氣體：Ar與N2 之混合氣體(氮氣濃度10～80 vol%；氣壓0.02 Pa～5 Pa) 投入電力：30～2000 W 成膜速度：2.0～60 nm/mimThe conductivity and thickness of the constituent material of the back conductive film 15 are selected so that the sheet resistance becomes 100 Ω/□ or less. As a constituent material of the back surface conductive film 15, a wide range of materials can be selected from those described in known literature. For example, the high dielectric constant material layer described in Japanese Patent Publication No. 2003-501823 or Japanese Patent Publication No. 2008/072706 is specifically selected from the group consisting of silicon, TiN, molybdenum, chromium (Cr), CrN, and TaSi. The material layer in the group composed of. The backside conductive film can be formed by dry film formation methods, specifically sputtering methods such as magnetron sputtering, ion beam sputtering, CVD (Chemical Vapor Deposition), and vacuum evaporation. Formed by film forming method. For example, when forming a CrN film by magnetron sputtering, it is sufficient to set the target to a Cr target, set the sputtering gas to a mixed gas of Ar and N2 , and perform magnetron sputtering. Specifically, Just use the following film forming conditions. Target: Cr target Sputtering gas: Mixed gas of Ar and N2 (nitrogen concentration 10~80 vol%; gas pressure 0.02 Pa~5 Pa) Input power: 30~2000 W Film formation speed: 2.0~60 nm/mim
本發明之反射型遮罩基底亦可具有上述以外之構成元件。例如亦可於吸收膜上形成用於檢查遮罩圖案之檢查光中之低反射層或硬質遮罩。 作為低反射層，可列舉：含有Ta、Hf、Si、Zr、Ti、Ge、B、Sn、Ni、Co、N、H、及O中之至少一種以上之元素之材料。例如可列舉：TaO、TaON、TaONH、TaHfO、TaHfON等。 作為硬質遮罩層之材料，可列舉：含有Cr、Ru、Zr、In、Si、N、H、及O中之至少一種以上之元素之材料。例如可列舉：CrN、CrON、Ru、SiO2 、SiON、Si3 N4 、SiC等。 [實施例]The reflective mask base of the present invention may also have components other than those mentioned above. For example, a low-reflection layer or a hard mask in inspection light used to inspect the mask pattern may be formed on the absorbing film. Examples of the low-reflective layer include materials containing at least one element selected from Ta, Hf, Si, Zr, Ti, Ge, B, Sn, Ni, Co, N, H, and O. Examples include: TaO, TaON, TaONH, TaHfO, TaHfON, etc. Examples of materials for the hard mask layer include materials containing at least one element among Cr, Ru, Zr, In, Si, N, H, and O. Examples include: CrN, CrON, Ru, SiO 2 , SiON, Si 3 N 4 , SiC, etc. [Example]
以下，使用實施例進一步說明本發明。 例1～例5為實施例，例6及例7為比較例。Hereinafter, the present invention will be further explained using examples. Examples 1 to 5 are examples, and Examples 6 and 7 are comparative examples.
(例1) 利用以下之方法，製造反射型遮罩基底。 首先，作為基板，準備縱152.4 mm×橫152.4 mm×厚度6.3 mm之玻璃基板(SiO2 -TiO2 系)。 該玻璃基板之熱膨脹率為0.2×10-7 /℃，楊氏模數為67G Pa，泊松比為0.17，比剛性為3.07×107 m2 /s2 。玻璃基板係以主面之表面粗糙度(均方根高度Sq)成為0.15 nm以下、平坦度成為100 nm以下之方式研磨而使用。 其次，於玻璃基板之一面(第2主面)形成背面導電膜。背面導電膜係設為CrN膜，利用磁控濺鍍法以厚度成為約100 nm之方式成膜。背面導電膜之薄片電阻為100 Ω/□。 繼而，使用靜電吸盤，藉由經由背面導電膜之靜電吸附方式，將玻璃基板固定於成膜室內。於該狀態下，於玻璃基板之第1主面將多層反射膜成膜。 於成膜時，使用離子束濺鍍法，以將厚度2.3 nm之Mo層與厚度4.5 nm之Si層交替地各成膜50次，而形成Mo/Si多層反射膜。 於Mo層之成膜時，使用Mo，於氬氣氛圍下實施離子束濺鍍(氣壓：0.02 Pa)。施加電壓係設為700 V，成膜速度係設為3.84 nm/min。 另一方面，於Si層之成膜時，使用摻雜有硼之Si靶，於氬氣氛圍下實施離子束濺鍍(氣壓：0.02 Pa)。施加電壓係設為700 V，成膜速度係設為4.62 nm/min。 多層反射膜之總厚度(目標值)係(2.3 nm＋4.5 nm)×50次＝340 nm。再者，多層反射膜之最上層係設為Si層。 繼而，藉由離子束濺鍍法，於多層反射膜上形成保護膜。 保護膜係設為Ru層，使用Ru靶，於氬氣氛圍下實施離子束濺鍍(氣壓：0.02 Pa)。施加電壓係設為700 V，成膜速度係設為3.12 nm/min。保護膜之膜厚係設為2.5 nm。 繼而，於保護膜上，利用磁控濺鍍法形成吸收膜。 吸收膜係設為TaN層，使用Ta靶，於Kr與N2 之混合氣體(Kr＝95 vol%、N2 ＝5 vol%)氛圍下，實施磁控濺鍍。成膜速度係設為7.7 nm/min，膜厚係設為75 nm。 藉此，獲得評價例1之反射型遮罩基底之吸收膜之特性之樣品1。 繼而，於吸收膜上，利用磁控濺鍍法形成低反射層。 低反射層係設為TaON層，使用Ta靶，於Ar、O2 、及N2 之混合氣體(Ar＝60 vol%、O2 ＝30 vol%、N2 ＝10 vol%)氛圍下，實施磁控濺鍍。成膜速度係設為1.32 nm/min。低反射層之膜厚係設為5 nm。 繼而，製造例1之反射型遮罩基底。(Example 1) Use the following method to manufacture a reflective mask substrate. First, as a substrate, a glass substrate (SiO 2 -TiO 2 system) with a length of 152.4 mm, a width of 152.4 mm, and a thickness of 6.3 mm is prepared. The thermal expansion rate of the glass substrate is 0.2×10 -7 /℃, the Young's modulus is 67G Pa, the Poisson's ratio is 0.17, and the specific rigidity is 3.07×10 7 m 2 /s 2 . The glass substrate is polished and used so that the surface roughness (root mean square height Sq) of the main surface becomes 0.15 nm or less and the flatness becomes 100 nm or less. Next, a back conductive film is formed on one side (the second main surface) of the glass substrate. The back conductive film is a CrN film, which is formed by magnetron sputtering to a thickness of approximately 100 nm. The sheet resistance of the back conductive film is 100 Ω/□. Then, an electrostatic chuck is used to fix the glass substrate in the film-forming chamber by electrostatic adsorption through the back conductive film. In this state, a multilayer reflective film is formed on the first main surface of the glass substrate. During film formation, an ion beam sputtering method was used to alternately form a Mo layer with a thickness of 2.3 nm and a Si layer with a thickness of 4.5 nm 50 times each to form a Mo/Si multilayer reflective film. When forming the Mo layer, Mo was used and ion beam sputtering was performed in an argon atmosphere (air pressure: 0.02 Pa). The applied voltage was set to 700 V, and the film formation speed was set to 3.84 nm/min. On the other hand, when forming the Si layer, a Si target doped with boron was used, and ion beam sputtering was performed in an argon atmosphere (gas pressure: 0.02 Pa). The applied voltage was set to 700 V, and the film formation speed was set to 4.62 nm/min. The total thickness (target value) of the multi-layer reflective film is (2.3 nm + 4.5 nm) × 50 times = 340 nm. Furthermore, the uppermost layer of the multilayer reflective film is a Si layer. Then, a protective film is formed on the multi-layer reflective film by ion beam sputtering. The protective film was a Ru layer, and ion beam sputtering was performed in an argon atmosphere using a Ru target (air pressure: 0.02 Pa). The applied voltage was set to 700 V, and the film formation speed was set to 3.12 nm/min. The film thickness of the protective film is set to 2.5 nm. Then, an absorption film is formed on the protective film using magnetron sputtering. The absorption film was a TaN layer, and magnetron sputtering was performed using a Ta target in an atmosphere of a mixed gas of Kr and N 2 (Kr = 95 vol%, N 2 = 5 vol%). The film formation speed was set to 7.7 nm/min, and the film thickness was set to 75 nm. Thereby, Sample 1 for evaluating the characteristics of the absorbing film of the reflective mask base of Example 1 was obtained. Then, a low-reflective layer is formed on the absorbing film using magnetron sputtering. The low-reflection layer is a TaON layer, and a Ta target is used in an atmosphere of a mixed gas of Ar, O 2 , and N 2 (Ar=60 vol%, O 2 =30 vol%, N 2 =10 vol%). Magnetron sputtering. The film formation speed was set to 1.32 nm/min. The film thickness of the low-reflective layer is set to 5 nm. Next, the reflective mask substrate of Example 1 was manufactured.
(例2) 藉由與例1相同之方法，製造反射型遮罩基底。 其中，於該例2中，與例1之情形相比，係將利用磁控濺鍍法而將作為吸收膜之TaN層成膜時之條件進行變化。更具體而言，將混合氣體中之Kr與N2 之混合比(體積比)設為93：7。其他條件係與例1相同。 與例1同樣地，製作評價成膜至吸收膜之反射型遮罩基底之吸收膜之特性。將其稱為「樣品2」(以下，相同)。(Example 2) A reflective mask substrate was manufactured by the same method as Example 1. In this Example 2, compared with the case of Example 1, the conditions for forming a TaN layer as an absorbing film using the magnetron sputtering method were changed. More specifically, the mixing ratio (volume ratio) of Kr and N2 in the mixed gas was set to 93:7. Other conditions are the same as Example 1. In the same manner as in Example 1, the characteristics of the absorbing film formed into the reflective mask base were evaluated. This is called "sample 2" (hereinafter, the same).
(例3) 藉由與例1相同之方法，而製造反射型遮罩基底。 其中，於該實施例3中，與實施例1之情形相比，係將利用磁控濺鍍法而將作為吸收膜之TaN層成膜時之條件進行變化。更具體而言，將混合氣體中之Kr與N2 之混合比(體積比)設為91：9。其他條件係與例1相同。(Example 3) A reflective mask substrate was manufactured by the same method as Example 1. In this Example 3, compared with the case of Example 1, the conditions for forming a TaN layer as an absorption film using the magnetron sputtering method were changed. More specifically, the mixing ratio (volume ratio) of Kr and N2 in the mixed gas was set to 91:9. Other conditions are the same as Example 1.
(例4) 藉由與例1相同之方法，而製造反射型遮罩基底。 其中，於該例4中，與實施例1之情形相比，係將利用磁控濺鍍法而將作為吸收膜之TaN層成膜時之條件進行變化。更具體而言，將混合氣體中之Kr與N2 之混合比(體積比)設為89：11。其他條件係與例1相同。(Example 4) A reflective mask substrate was manufactured by the same method as Example 1. In this Example 4, compared with the case of Example 1, the conditions for forming a TaN layer as an absorbing film using the magnetron sputtering method were changed. More specifically, the mixing ratio (volume ratio) of Kr and N2 in the mixed gas was set to 89:11. Other conditions are the same as Example 1.
(例5) 藉由與例1相同之方法，而製造反射型遮罩基底。 其中，於該例5中，與例1之情形相比，係將利用磁控濺鍍法而將作為吸收膜之TaN層成膜時之條件進行變化。更具體而言，作為混合氣體，使用Ar、Kr、及N2 之混合氣體。Ar、Kr、及N2 之混合比(體積比)係設為54：38：8。其他條件係與例1相同。(Example 5) A reflective mask substrate was manufactured by the same method as Example 1. In this Example 5, compared with the case of Example 1, the conditions for forming a TaN layer as an absorbing film using the magnetron sputtering method were changed. More specifically, as the mixed gas, a mixed gas of Ar, Kr, and N2 is used. The mixing ratio (volume ratio) of Ar, Kr, and N 2 is set to 54:38:8. Other conditions are the same as Example 1.
(例6) 藉由與例1相同之方法，而製造反射型遮罩基底。 其中，於該例6中，與例1之情形相比，係將利用磁控濺鍍法而將作為吸收膜之TaN層成膜時之條件進行變化。更具體而言，作為混合氣體，使用Ar、Kr、及N2 之混合氣體。Ar、Kr、及N2 之混合比(體積比)係設為67：17：16。其他條件係與例1相同。(Example 6) A reflective mask substrate was manufactured by the same method as Example 1. However, in Example 6, compared with the case of Example 1, the conditions for forming a TaN layer as an absorbing film using the magnetron sputtering method were changed. More specifically, as the mixed gas, a mixed gas of Ar, Kr, and N2 is used. The mixing ratio (volume ratio) of Ar, Kr, and N 2 is set to 67:17:16. Other conditions are the same as Example 1.
(例7) 藉由與例1相同之方法，而製造反射型遮罩基底。 其中，於該例7中，與例1之情形相比，係將利用磁控濺鍍法而將作為吸收膜之TaN層成膜時之條件進行變化。更具體而言，將混合氣體中之Kr與N2 之混合比(體積比)設為94：6。其他條件係與例1相同。(Example 7) A reflective mask substrate was manufactured by the same method as Example 1. However, in Example 7, compared with the case of Example 1, the conditions for forming a TaN layer as an absorption film using the magnetron sputtering method were changed. More specifically, the mixing ratio (volume ratio) of Kr and N2 in the mixed gas was set to 94:6. Other conditions are the same as Example 1.
(評價) 使用以上述之方式所製造之各樣品，進行以下之評價。(Evaluation) Using each sample produced in the above manner, the following evaluation was performed.
(XRD測定) 使用X射線繞射裝置(型號：ATX-G，製造商：RIGAKU股份有限公司製造)，進行共平面(In-plane)XRD測定。測定時，自X射線之入射側將使寬度限制狹縫1 mm與縱制限狹縫10 mm重疊者與使寬度限制狹縫0.1 mm與縱制限狹縫10 mm重疊者配置於兩處，於其間配置發散角0.48°之索勒狹縫。於受光側配置發散角0.41°之索勒狹縫。X射線源使用輸出50 kV-300 mA之CuKα射線(波長：1.5418 Å)，以入射角0.6°、步驟幅度0.05°、掃描速度1°/min之條件進行測定，獲得資料。 測定資料之解析係使用X射線解析軟體(型號：PDXL2，製造商：RIGAKU股份有限公司製造)。資料處理係藉由利用B-Spline之平滑化(X閾值：1.50)、基底去除(擬合方式)、Kα2之去除(強度比0.497)、峰檢索(二次微分法，σ截止值：3.00)、剖面擬合(對測定資料進行擬合，峰形狀：分割型Voigt函數)而進行，獲得繞射2θ與半值寬。 圖2係表示樣品1～4、樣品6、7之X射線繞射之圖案之圖。再者，於圖2中，用各樣品之X射線繞射峰之強度(cps)之值加上固定值，使各樣品之X射線繞射峰之強度偏移而容易觀察峰形狀。因此，縱軸之刻度並非強度之絕對值，僅為強度(cps)。(XRD measurement) In-plane XRD measurement was performed using an X-ray diffraction device (model: ATX-G, manufacturer: RIGAKU Co., Ltd.). When measuring, from the incident side of the Equipped with a Soler slit with a divergence angle of 0.48°. A Soller slit with a divergence angle of 0.41° is installed on the light-receiving side. The X-ray source uses CuKα rays (wavelength: 1.5418 Å) with an output of 50 kV-300 mA, and the data is measured under the conditions of an incident angle of 0.6°, a step width of 0.05°, and a scanning speed of 1°/min. The measurement data was analyzed using X-ray analysis software (model: PDXL2, manufacturer: RIGAKU Co., Ltd.). Data processing is by using B-Spline smoothing (X threshold: 1.50), base removal (fitting method), Kα2 removal (intensity ratio 0.497), peak search (second differential method, σ cutoff: 3.00) , profile fitting (fitting the measurement data, peak shape: split Voigt function), and obtaining the diffraction 2θ and half-value width. FIG. 2 is a diagram showing the X-ray diffraction patterns of Samples 1 to 4, and Samples 6 and 7. Furthermore, in Figure 2, a fixed value is added to the intensity (cps) of the X-ray diffraction peak of each sample to shift the intensity of the X-ray diffraction peak of each sample and make it easier to observe the peak shape. Therefore, the scale on the vertical axis is not the absolute value of intensity, but only intensity (cps).
(蝕刻速度評價) 使用蝕刻裝置(型號：CE-300R，製造商：ULVAC股份有限公司製造)，於Cl2 與He之混合氣體(Cl2 ＝20 vol%、He＝80 vol%)氛圍下，進行反應性離子蝕刻。其後，使用X射線反射率測定裝置(型號：SmartLab HTP，製造商：RIGAKU股份有限公司製造)，進行蝕刻後之吸收膜、保護膜之膜厚(nm)之測定，獲得吸收膜、保護膜之蝕刻速度(nm/min)。蝕刻選擇比係由吸收膜之蝕刻速度相對於保護膜之蝕刻速度(吸收膜蝕刻速度/保護膜蝕刻速度)求出。再者，保護膜之蝕刻速度均為0.047 nm/sec。(Etching speed evaluation) Using an etching device (model: CE-300R, manufacturer: ULVAC Co., Ltd.), in an atmosphere of a mixed gas of Cl 2 and He (Cl 2 =20 vol%, He = 80 vol%), Perform reactive ion etching. Thereafter, an X-ray reflectance measuring device (model: SmartLab HTP, manufacturer: RIGAKU Co., Ltd.) was used to measure the film thickness (nm) of the absorption film and protective film after etching, and the absorption film and protective film were obtained. The etching speed (nm/min). The etching selectivity ratio is calculated from the etching rate of the absorbing film relative to the etching rate of the protective film (absorbing film etching rate/protective film etching rate). Furthermore, the etching speed of the protective film is 0.047 nm/sec.
(膜組成評價) 使用拉塞福背向散射分析裝置(型號：RBS，製造商：KOBELCO科研股份有限公司製造)，獲得樣品1～7之吸收膜中之Ta量(at%)、N量(at%)、Kr量(at%)。又，關於樣品1～3、7，膜中之N量之值較小，故而於拉塞福背向散射分析裝置中，無法精度良好地進行定量評價。因此，使用電子束顯微分析儀(型號：JXA-8500F，製造商：日本電子股份有限公司)，測定Ta量(at%)、N量(at%)。藉由電子束顯微分析儀之測定係設為加速電壓4 kV、照射電流30 nA，將光束直徑設為100 μm，N係將LDE1H進行分光結晶而進行Kα射線之測定，Ta係將PETJ進行分光結晶而進行Mα射線之測定。Ta量(at%)、N量(at%)係藉由校準曲線法進行定量，利用Ta與N以成為100 wt%之方式進行標準化後轉換為at%。作為標準試樣，使用藉由拉塞福背向散射分析而求出N量(at%)之樣品4、與不含N之Ta膜之兩點。(Evaluation of film composition) The Ta amount (at%) and N amount (at%) in the absorption film of samples 1 to 7 were obtained using a Rassef backscattering analyzer (model: RBS, manufacturer: KOBELCO Scientific Research Co., Ltd.) at%), Kr amount (at%). In addition, regarding Samples 1 to 3 and 7, the value of the N amount in the film was small, so it was not possible to perform quantitative evaluation with high accuracy using the Rutherford backscattering analyzer. Therefore, the Ta amount (at%) and the N amount (at%) were measured using an electron beam microanalyzer (model: JXA-8500F, manufacturer: JEOL Ltd.). The measurement by the electron beam microanalyzer was set to an accelerating voltage of 4 kV, an irradiation current of 30 nA, and a beam diameter of 100 μm. N was measured by spectroscopic crystallization of LDE1H and Kα rays were measured. Ta was measured by PETJ. Spectroscopic crystallization to measure Mα rays. Ta amount (at%) and N amount (at%) are quantified by the calibration curve method, and Ta and N are normalized to become 100 wt% and then converted to at%. As a standard sample, two points of sample 4, in which the N amount (at%) was determined by Rutherford backscattering analysis, and a Ta film containing no N were used.
(缺陷檢查) 對各樣品，根據以下之順序實施缺陷檢查。 使用可見光雷射之缺陷檢查裝置(型號：M1350，製造商：Laserte公司製造)，對各樣品之吸收層側之表面實施缺陷檢查。評價區域係設為132 mm×132 m之範圍。 樣品7若利用缺陷檢查裝置進行檢查，則檢測出100 nm以下之缺陷為500個以上，利用掃描型電子顯微鏡(型號：Ultra60，製造商：Carl Zeiss)觀察表面，結果不存在實際之缺陷，未確認到實際缺陷。由此可知，利用缺陷檢查裝置檢測出100 nm以下之缺陷者為因表面粗糙度導致之偽缺陷。此種偽缺陷之存在阻礙正確地評價實際缺陷。 將檢測出大量偽缺陷且正確之缺陷檢查較為困難之樣品之檢查性設為B判定。另一方面，將可實施正確之缺陷檢查之樣品之檢查性設為A判定。(Defect Inspection) For each sample, perform defect inspection according to the following procedure. Using a visible light laser defect inspection device (model: M1350, manufacturer: Laserte Company), defects were inspected on the surface of the absorption layer side of each sample. The evaluation area is set to a range of 132 mm × 132 m. If sample 7 was inspected using a defect inspection device, more than 500 defects below 100 nm were detected. The surface was observed using a scanning electron microscope (model: Ultra60, manufacturer: Carl Zeiss). The result was that there were no actual defects and it was not confirmed. to actual defects. It can be seen from this that defects below 100 nm detected by the defect inspection device are pseudo defects caused by surface roughness. The presence of such pseudo-defects prevents the correct evaluation of actual defects. The inspectionability of samples in which a large number of false defects are detected and for which accurate defect inspection is difficult is judged as B. On the other hand, the inspectionability of a sample that can be accurately inspected for defects is determined as A.
對樣品4與樣品7，觀察根據以下之順序實施TEM(Transmission Electron Microscopy，穿透式電子顯微鏡)。 TEM(以下，亦稱為穿透型電子顯微鏡)觀察用試樣係自形成有吸收膜之基板側不斷進行研磨，製造僅有吸收膜之薄片試樣而獲得。自基板側之研磨係使用機械研磨機(型號：Beta Grinder Polisher，製造商：BUEHLER公司製造)、與離子研磨機(型號：精密離子研磨系統 Model 691，製造商：Gatan公司製造)。使用穿透型電子顯微鏡(型號：JEM-2010F，製造商：日本電子公司製造)，以加速電壓200 kV自吸收膜之平面方向觀察僅有吸收膜之薄片試樣。圖3為樣品7之TEM觀察結果，圖4為樣品4之TEM觀察結果。可知樣品7之表面明顯變粗。Samples 4 and 7 were observed using TEM (Transmission Electron Microscopy) according to the following procedures. A sample for TEM (hereinafter also referred to as a transmission electron microscope) observation is obtained by continuously polishing the substrate side on which the absorption film is formed to produce a thin sample with only the absorption film. The polishing from the substrate side uses a mechanical polisher (Model: Beta Grinder Polisher, manufacturer: BUEHLER Company) and an ion grinder (Model: Precision Ion Grinding System Model 691, manufacturer: Gatan Company). Using a transmission electron microscope (model: JEM-2010F, manufacturer: Japan Electronics Corporation), observe the thin sample with only the absorption film in the plane direction of the self-absorption film at an accelerating voltage of 200 kV. Figure 3 is the TEM observation result of sample 7, and Figure 4 is the TEM observation result of sample 4. It can be seen that the surface of sample 7 is obviously roughened.
又，利用與例1相同之條件，將膜厚設為50 nm、58 nm而製造樣品，並進行評價，結果為與樣品1相同之性能。In addition, samples were produced using the same conditions as Example 1, with film thicknesses of 50 nm and 58 nm, and were evaluated. As a result, the performance was the same as that of Sample 1.
將結果示於下述表。 [表1]
詳細地且參照特定之實施態樣說明了本發明，但對業者明確可於不脫離本發明之精神與範圍之情況下添加各種變更或修正。 本發明案係基於2017年8月10日提出申請之日本專利申請2017-155403及2017年9月22日提出申請之日本專利申請2017-182146者，將其內容作為參照而併入至本文中。The present invention has been described in detail with reference to specific embodiments. However, it is clear to those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the present invention. The present invention is based on Japanese Patent Application No. 2017-155403 filed on August 10, 2017 and Japanese Patent Application No. 2017-182146 filed on September 22, 2017, the contents of which are incorporated herein by reference.
1‧‧‧EUV遮罩基底 11‧‧‧基板 12‧‧‧反射層(多層反射膜) 13‧‧‧保護層 14‧‧‧吸收膜 15‧‧‧背面導電膜 1‧‧‧EUV mask base 11‧‧‧Substrate 12‧‧‧Reflective layer (multilayer reflective film) 13‧‧‧Protective layer 14‧‧‧Absorbent film 15‧‧‧Back conductive film
圖1係表示本發明之反射型遮罩基底之一實施形態之概略剖視圖。 圖2係表示樣品1～4、樣品6、7之X射線繞射之圖案之圖。 圖3係樣品7之TEM觀察結果。 圖4係樣品4之TEM觀察結果。FIG. 1 is a schematic cross-sectional view showing an embodiment of the reflective mask substrate of the present invention. FIG. 2 is a diagram showing the X-ray diffraction patterns of Samples 1 to 4, and Samples 6 and 7. Figure 3 shows the TEM observation results of sample 7. Figure 4 shows the TEM observation results of sample 4.
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