JPH11258772A - Halftone phase shift mask blank and halftone phase shift mask - Google Patents
Halftone phase shift mask blank and halftone phase shift maskInfo
- Publication number
- JPH11258772A JPH11258772A JP6577598A JP6577598A JPH11258772A JP H11258772 A JPH11258772 A JP H11258772A JP 6577598 A JP6577598 A JP 6577598A JP 6577598 A JP6577598 A JP 6577598A JP H11258772 A JPH11258772 A JP H11258772A
- Authority
- JP
- Japan
- Prior art keywords
- phase shift
- shift mask
- halftone phase
- halftone
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000010363 phase shift Effects 0.000 title claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 230000003287 optical effect Effects 0.000 abstract description 12
- 230000008033 biological extinction Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 5
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004544 sputter deposition Methods 0.000 abstract description 4
- 229910021355 zirconium silicide Inorganic materials 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 56
- 239000010410 layer Substances 0.000 description 24
- 238000002834 transmittance Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 150000003755 zirconium compounds Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体製造プロセ
ス中のフォトリソグラフィ工程においてパターンを形成
する際の露光転写用フォトマスクに関し、特に位相シフ
トフォトマスク及びこの位相シフトフォトマスクを製造
するための位相シフトフォトマスクブランクスに関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photomask for exposing and transferring when forming a pattern in a photolithography step in a semiconductor manufacturing process, and more particularly to a phase shift photomask and a phase shift mask for manufacturing the phase shift photomask. It relates to shift photomask blanks.
【０００２】[0002]
【従来の技術】近年の半導体の配線パターンの微細化に
伴い、Ｓｉウエハ上にパターンを転写する際に解像度を
向上させる技術を施したフォトマスクの利用は盛んにな
りつつある。位相シフト法はこの解像度向上技術の１つ
であり、隣接する開口部の片側に位相シフト部を設け隣
接するパターンを透過する投影光の位相差を互いに１８
０度とすることにより、透過光が回折し干渉し合う際に
境界部の光強度を弱め、その結果として転写パターンの
解像度を向上させるものである。2. Description of the Related Art With the recent miniaturization of semiconductor wiring patterns, the use of photomasks provided with a technique for improving resolution when transferring a pattern onto a Si wafer is increasing. The phase shift method is one of the resolution improving techniques, in which a phase shift portion is provided on one side of an adjacent opening to make the phase difference between projection lights transmitted through an adjacent pattern equal to each other.
By setting the angle to 0 degree, when the transmitted light is diffracted and interferes with each other, the light intensity at the boundary is reduced, and as a result, the resolution of the transfer pattern is improved.
【０００３】上記のような位相シフト法はＩＢＭのＬｅ
ｖｅｎｓｏｎらによって提唱され、特開昭５８−１７３
７４４号公報や、原理では特公昭６２−５０８１１号公
報に記載されており、レベンソン型やハーフトーン型な
どが公知となっている。レベンソン型はパターンを遮光
層で形成し、遮光パターンに隣接する開孔部の片側に位
相シフト部を設けて位相反転させるもので解像性能と焦
点深度は大きく向上する。[0003] The phase shift method described above is based on IBM's Le.
proposed by Venson et al.
No. 744 and, in principle, Japanese Patent Publication No. 62-50811, and a Levenson type and a halftone type are known. In the Levenson type, a pattern is formed by a light-shielding layer, and a phase shift portion is provided on one side of an opening portion adjacent to the light-shielding pattern to invert the phase, so that the resolution performance and the depth of focus are greatly improved.
【０００４】また、遮光層に完全な遮光性を持たせず、
この半透明遮光層によって露光光をレジスト感度以下で
透過させると共に、且つ位相を反転させるものをハーフ
トーン型と呼び、同様な解像度向上効果を得ることが可
能となる。この場合は特に孤立パターンの解像度向上に
有効である。Further, the light-shielding layer does not have complete light-shielding properties,
The translucent light-shielding layer that transmits the exposure light at a resist sensitivity or lower and also inverts the phase is called a halftone type, and it is possible to obtain the same resolution improving effect. This case is particularly effective for improving the resolution of an isolated pattern.
【０００５】[0005]
【発明が解決しようとする課題】然しながら、ハーフト
ーン型位相シフトマスクは透明基板上に半透明膜パター
ンを設け、半透明膜パターン領域で位相差および透過率
が適切な値で無いと十分な転写効果は得られない。However, in the halftone type phase shift mask, a translucent film pattern is provided on a transparent substrate, and if the phase difference and transmittance in the translucent film pattern area are not appropriate values, sufficient transfer is performed. No effect.
【０００６】通常半透明膜はスパッタリングを用いて成
膜を行い、そのとき酸素や窒素ガス等の添加ガスの分量
を調節することにより所望の屈折率や消衰係数を得る
が、成膜後の膜は概して中間的な組成すなわち半結合状
態である場合が多い。そのため成膜後の自然酸化等の経
時的な変化やマスク製造工程内での加熱処理、もしくは
露光時の露光光吸収により生ずる熱の影響で透過率、屈
折率及び消衰係数等の光学定数が変化することはよく指
摘されており、この結果として露光時のパターン転写精
度に悪影響を及ぼすことが問題点として挙げられてい
る。Usually, a semi-transparent film is formed by sputtering, and a desired refractive index or extinction coefficient is obtained by adjusting the amount of an additional gas such as oxygen or nitrogen gas. Films are often of an intermediate composition or semi-bonded state. Therefore, the optical constants such as transmittance, refractive index, and extinction coefficient are affected by the temporal change such as natural oxidation after film formation, the heat treatment in the mask manufacturing process, or the heat generated by the absorption of exposure light during exposure. It is often pointed out that the change occurs, and as a result, it is pointed out that a problem is exerted on the pattern transfer accuracy at the time of exposure.
【０００７】本発明は上記問題点に鑑みなされたもの
で、熱処理工程及び特定の薬液処理工程を経ても透過
率、屈折率及び消衰係数等の光学定数の変化を起こさな
いハーフトーン型位相シフトマスク用ブランクス及びハ
ーフトーン型位相シフトマスクを提供することを目的と
する。The present invention has been made in view of the above-mentioned problems, and has a halftone phase shift which does not cause a change in optical constants such as transmittance, refractive index and extinction coefficient even after a heat treatment step and a specific chemical treatment step. It is an object to provide a mask blank and a halftone type phase shift mask.
【０００８】[0008]
【課題を解決するための手段】本発明に於いて上記課題
を解決するために、まず請求項１においては、透明基板
上に半透明膜が形成されたハーフトーン型位相シフトマ
スク用ブランクスにおいて、該半透明膜の最表面に８０
Å以上の厚さの酸化膜層を設けたことを特徴とするハー
フトーン型位相シフトマスク用ブランクスとしたもので
ある。Means for Solving the Problems In order to solve the above problems in the present invention, first, in a blank for a halftone type phase shift mask in which a translucent film is formed on a transparent substrate, 80 on the outermost surface of the translucent film
ブ ラ ン ク This is a blank for a halftone type phase shift mask, which is provided with an oxide film layer having a thickness of not less than.
【０００９】また、請求項２においては、前記半透明膜
はジルコニウムもしくはジルコニウム及び珪素を含んだ
化合物であることを特徴とする請求項１に記載のハーフ
トーン型位相シフトマスク用ブランクスとしたものであ
る。According to a second aspect of the present invention, the translucent film is made of zirconium or a compound containing zirconium and silicon. is there.
【００１０】さらにまた、請求項３においては、前記酸
化膜層は前記半透明膜の成膜工程後２００℃以上の加熱
処理により熱酸化されたものであることを特徴とする請
求項１又は２に記載のハーフトーン型位相シフトマスク
用ブランクスとしたものである。Further, according to claim 3, the oxide film layer is thermally oxidized by a heat treatment at 200 ° C. or more after the step of forming the translucent film. And a blank for a halftone type phase shift mask described in (1).
【００１１】さらにまた、請求項４においては、前記酸
化膜層は金属と酸素の元素比率が金属１に対して酸素が
２以上であることを特徴とする請求項１ないし３のうち
いずれか一項に記載のハーフトーン型位相シフトマスク
用ブランクスとしたものである。Further, according to claim 4, the oxide film layer has an element ratio of metal to oxygen of 2 or more with respect to metal 1. The blanks for a halftone type phase shift mask described in the section were used.
【００１２】さらにまた、請求項５においては、前記酸
化膜層はその下部に形成された前記半透明膜の酸化度の
高い膜であることを特徴とする請求項１ないし４のうち
いずれか一項に記載のハーフトーン型位相シフトマスク
用ブランクスとしたものである。Further, in claim 5, the oxide film layer is a film having a high degree of oxidation of the translucent film formed thereunder, wherein the oxide film layer has a high degree of oxidation. The blanks for a halftone type phase shift mask described in the section were used.
【００１３】さらにまた、請求項６においては、請求項
１ないし５のうちいずれか一項に記載のハーフトーン型
位相シフトマスク用ブランクスを用いて、位相シフトマ
スクを形成したことを特徴とするハーフトーン型位相シ
フトマスクとしたものである。According to a sixth aspect of the present invention, a halftone phase shift mask is formed by using the blank for a halftone type phase shift mask according to any one of the first to fifth aspects. This is a tone type phase shift mask.
【００１４】本発明が提供するものは、透明基板上に形
成された半透明膜の最表面に加熱処理して８０Å以上の
厚さで酸化膜層を形成することにより、マスク作製プロ
セスでの熱処理工程や薬液洗浄工程により生ずる半透明
膜の透過率等の光学定数の変化を抑えることができるよ
うにしたものである。An object of the present invention is to provide a heat treatment in a mask manufacturing process by heating the outermost surface of a translucent film formed on a transparent substrate to form an oxide film layer having a thickness of 80 ° or more. It is possible to suppress a change in an optical constant such as a transmittance of a translucent film caused by a process or a chemical cleaning process.
【００１５】[0015]
【発明の実施の形態】本発明のハーフトーン型位相シフ
トマスクブランクス及びハーフトーン型位相シフトマス
クは図１（ｂ）及び図１（ｄ）に示すような構成をして
おり、透明基板１１上に形成された半透明膜１２の最表
面に加熱処理して酸化膜層１３を設けることにより、マ
スク作成工程中での加熱処理又は露光時の露光光吸収に
より生ずる熱の影響による半透明膜パターン１２ａの透
過率、屈折率及び消衰係数等の光学定数の変化を抑える
ことができ、位相シフトマスクとしての光学特性が維持
されて、露光転写時のパターン解像度の向上を図るよう
にしたものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS A halftone type phase shift mask blank and a halftone type phase shift mask of the present invention have a structure as shown in FIGS. 1 (b) and 1 (d). By providing a heat treatment on the outermost surface of the translucent film 12 formed on the substrate to provide the oxide film layer 13, a translucent film pattern due to the influence of heat generated during the heat treatment during the mask making process or the exposure light absorption at the time of exposure. A change in optical constants such as transmittance, refractive index, and extinction coefficient of 12a can be suppressed, and optical characteristics as a phase shift mask are maintained to improve pattern resolution during exposure transfer. is there.
【００１６】まず、窒素、酸素、ハロゲンガス等の雰囲
気中でジルコニウム又はジルコニウムシリサイドターゲ
ットを使用したスパッタリングにて、石英ガラスからな
る透明基板１１上に屈折率、消衰係数及び膜厚を調節し
たジルコニウム又はジルコニウム化合物膜からなる半透
明膜１２を成膜する（図１（ａ）参照）。ここで、半透
明膜１２はジルコニウム又はジルコニウム化合物膜の単
層膜か、２層以上の多層膜のいずれでも良い。First, zirconium whose refractive index, extinction coefficient and film thickness are adjusted on a transparent substrate 11 made of quartz glass by sputtering using a zirconium or zirconium silicide target in an atmosphere of nitrogen, oxygen, halogen gas or the like. Alternatively, a translucent film 12 made of a zirconium compound film is formed (see FIG. 1A). Here, the translucent film 12 may be a single layer film of zirconium or a zirconium compound film or a multilayer film of two or more layers.
【００１７】次に、半透明膜１２が形成された透明基板
１１を大気又は酸化性雰囲気中で、オーブン又はホット
プレートにて２００℃以上の温度にて加熱して、半透明
膜１２上に酸化膜層１３を形成し、本発明のハーフトー
ン型位相シフトマスクブランクス１０を作製する（図１
（ｂ）参照）。Next, the transparent substrate 11 on which the translucent film 12 is formed is heated in an air or an oxidizing atmosphere at a temperature of 200 ° C. or more in an oven or a hot plate to oxidize the translucent film 12. The film layer 13 is formed, and the halftone type phase shift mask blank 10 of the present invention is manufactured.
(B)).
【００１８】上記ジルコニウム又はジルコニウム化合物
からなる半透明膜１２は成膜後自然酸化により５０〜８
０Åの表面酸化膜層が形成されるが、この状態ではまだ
熱に対して安定した膜になっておらず、加熱処理して熱
酸化することにより半透明膜１２上に８０Å以上の酸化
膜層が形成されて、半透明膜１２は安定した膜になる。
熱酸化のための加熱温度は２００℃以上が必要で、好ま
しくは２５０℃前後である。この表面酸化膜層をＥＳＣ
Ａにて分析した結果金属（この場合にはＺｒ及びＳｉ）
と酸素の組成比は金属１に対し酸素が２以上であった。
ここで、加熱処理により半透明膜の光学定数（特に透過
率）が変化するため、あらかじめ加熱処理による変化を
見込んで、初期の半透明膜の光学定数を設計する必要が
ある。The translucent film 12 made of zirconium or a zirconium compound is formed to a thickness of 50 to 8 by natural oxidation after film formation.
Although a surface oxide film layer of 0 ° is formed, in this state, the film is not yet stable against heat. Is formed, and the translucent film 12 becomes a stable film.
The heating temperature for thermal oxidation needs to be 200 ° C. or higher, and preferably around 250 ° C. This surface oxide layer is
As a result of analysis in A, metals (in this case, Zr and Si)
The composition ratio of oxygen to oxygen was 2 or more with respect to 1 metal.
Here, since the optical constant (particularly, transmittance) of the translucent film changes due to the heat treatment, it is necessary to design the optical constant of the initial translucent film in advance in consideration of the change due to the heat treatment.
【００１９】上記ハーフトーン型位相シフトマスクブラ
ンクス１０にレジストを塗布し、電子線描画、現像、ベ
ーク等の一連のパターニング処理を施して開口部１５を
有するレジストパターン１４を形成する（図１（ｃ）参
照）。さらに、レジストパターン１４をマスクにしてド
ライエッチングにて半透明膜１２及び酸化膜層１３を除
去して半透明膜パターン１２ａ及び酸化膜層パターン１
３ａを形成し、レジスト剥離、洗浄の工程を経てマスク
パターン１６を有する本発明のハーフトーン型位相シフ
トマスク２０を得る（図１（ｄ）参照）。A resist is applied to the halftone phase shift mask blank 10 and subjected to a series of patterning processes such as electron beam drawing, development, and baking to form a resist pattern 14 having an opening 15 (FIG. 1C). )reference). Further, the translucent film 12 and the oxide film layer 13 are removed by dry etching using the resist pattern 14 as a mask to remove the translucent film pattern 12a and the oxide film layer pattern 1.
3a is formed, and the halftone type phase shift mask 20 of the present invention having the mask pattern 16 is obtained through the steps of resist stripping and cleaning (see FIG. 1D).
【００２０】[0020]
【実施例】本発明のハーフトーン型位相シフトマスク用
ブランクス及びハーフトーン型位相シフトマスクを実施
例により詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS A blank for a halftone type phase shift mask and a halftone type phase shift mask according to the present invention will be described in detail with reference to examples.
【００２１】まず、ＤＣスパッタ装置を用いて、チャン
バー内にアルゴン（Ａｒ）ガス及び酸素（Ｏ2 ）ガスを
導入し、ジルコニウムシリサイド（ＺｒＳｉ2 ）ターゲ
ットを用いた反応性スパッタにより、合成石英ガラスか
らなる透明基板１１上にシフタとなる２層膜構成の半透
明膜１２を成膜した。成膜条件は電力４００Ｗで１層目
成膜時のガス条件をＡｒ／Ｏ2 ＝２８／２ＳＣＣＭ、 ２
層目のガス条件をＡｒ／Ｏ2 ＝２５／５ＳＣＣＭ とし
た。また、このとき得られた膜のｎ（屈折率）及びｋ
（消衰係数）はそれぞれ１層目の膜がｎ＝１．９２、ｋ
＝１．０６、２層目の膜がｎ＝１．９５、ｋ＝０．２０
４であった。First, an Argon (Ar) gas and an Oxygen (O 2 ) gas are introduced into a chamber by using a DC sputtering apparatus, and the synthetic quartz glass is formed by reactive sputtering using a zirconium silicide (ZrSi 2 ) target. A translucent film 12 having a two-layer film structure serving as a shifter was formed on a transparent substrate 11. The film formation conditions were as follows: gas conditions at the time of forming the first layer at a power of 400 W were Ar / O 2 = 28/2 SCCM;
The gas condition of the layer was set to Ar / O 2 = 25/5 SCCM. Further, n (refractive index) and k of the film obtained at this time are
(Extinction coefficient) is n = 1.92, k
= 1.06, n = 1.95 for the second layer, k = 0.20
It was 4.
【００２２】次に、オーブンにて２５０℃１時間の熱処
理を行い酸化膜層１３を形成し、本発明のハーフトーン
型位相シフトマスクブランクス１０を得た。Next, heat treatment was performed at 250 ° C. for 1 hour in an oven to form an oxide film layer 13, thereby obtaining a halftone type phase shift mask blank 10 of the present invention.
【００２３】次に、上記ハーフトーン型位相シフトマス
クブランクス１０上に電子線レジストをスピナーにより
塗布してレジスト層を形成し、電子線描画、現像して開
口部１５を有するレジストパターン１４を形成した。Next, a resist layer was formed on the halftone type phase shift mask blanks 10 by applying an electron beam resist by a spinner, and electron beam drawing and development were performed to form a resist pattern 14 having openings 15. .
【００２４】次に、レジストパターン１４をマスクにし
てドライエッチングにて半透明膜１２及び酸化膜層１３
をパターニングした後レジストパターン１４を剥膜処理
して、マスクパターン１６からなるハーフトーン型位相
シフトマスク２０を得た。Next, the translucent film 12 and the oxide film layer 13 are dry-etched using the resist pattern 14 as a mask.
After patterning the resist pattern 14, the resist pattern 14 was subjected to a film removing process to obtain a halftone type phase shift mask 20 including the mask pattern 16.
【００２５】上記ハーフトーン型位相シフトマスクブラ
ンクス１０及びハーフトーン型位相シフトマスク２０の
耐熱性及び耐薬品性試験を行った。耐熱性については、
２５０℃１時間の熱処理に対して透過率、屈折率及び消
衰係数等の光学定数の変化は認められなかった。The halftone type phase shift mask blanks 10 and the halftone type phase shift mask 20 were tested for heat resistance and chemical resistance. Regarding heat resistance,
No change in optical constants such as transmittance, refractive index, and extinction coefficient was observed with the heat treatment at 250 ° C. for 1 hour.
【００２６】耐薬品性試験については、次の手順で行っ
た。 酸処理として７０℃の濃硫酸に１時間浸漬する。 アルカリ処理として５０℃に加熱された３０ｗｔ％の
ＫＯＨ溶液に１時間浸漬する。 洗浄液処理として３５℃に加熱されたＡＰＭ洗浄液
（ＮＨ4 ＯＨ：Ｈ2 Ｏ2 ：Ｈ2 ０＝１：３：５）に１時
間浸漬する。 上記〜の処理を行った前後の分光透過率変化を測定
した結果、測定波長１９３ｎｍ〜３６５ｎｍの範囲で、
０．２％未満の変化しかなく、実用上問題のない値であ
った。The chemical resistance test was performed according to the following procedure. It is immersed in concentrated sulfuric acid at 70 ° C. for one hour as an acid treatment. As an alkali treatment, it is immersed in a 30 wt% KOH solution heated to 50 ° C. for one hour. As a cleaning liquid treatment, it is immersed in an APM cleaning liquid (NH 4 OH: H 2 O 2 : H 2 0 = 1: 3: 5) heated to 35 ° C. for 1 hour. As a result of measuring a change in spectral transmittance before and after performing the above-mentioned processes, the measurement wavelength was in the range of 193 nm to 365 nm.
There was only a change of less than 0.2%, which was a value with no practical problem.
【００２７】さらに、参考までに熱処理を施していない
従来のブランクス及びマスクの耐熱性及び耐薬品性試験
を行った。耐熱性については、２５０℃１時間の熱処理
で半透明膜の透過率が１９３ｎｍの波長で０．４％、２
４８ｎｍ波長で１．７％変化した。耐薬品性試験につい
ては、上記〜の条件で処理した前後の波長１９３、
２４８及び３６５ｎｍでの分光透過率の変化率を測定し
た結果を表１に示す。Further, for reference, heat resistance and chemical resistance tests were performed on conventional blanks and masks that were not heat-treated. Regarding the heat resistance, the transmittance of the translucent film was 0.4% at a wavelength of 193 nm by heat treatment at 250 ° C. for 1 hour.
It changed 1.7% at the wavelength of 48 nm. For the chemical resistance test, the wavelength 193 before and after the treatment under the above conditions 1 to 3 was performed.
Table 1 shows the results of measuring the rates of change in the spectral transmittance at 248 and 365 nm.
【００２８】[0028]
【表１】 [Table 1]
【００２９】表１の結果から明らかなように、アルカ
リ、洗浄液処理で２．４〜４．６％とかなり大きな分光
透過率変化を示した。このように、本発明の実施例の方
法によれば、熱処理及び薬品処理しても透過率、屈折率
及び消衰係数等の光学定数が変化しない安定したハーフ
トーン型位相シフトマスク及びマスク用ブランクスを得
ることができる。本発明のハーフトーン型位相シフトマ
スクブランクス１０及びハーフトーン型位相シフトマス
ク２０の半透明膜はジルコニウムシリサイド等のジルコ
ニウム化合物以外にも、クロムやその化合物、モリブデ
ンシリサイドといった薄膜にも適用可能である。As is clear from the results shown in Table 1, the treatment with alkali and the cleaning solution showed a considerably large change in spectral transmittance of 2.4 to 4.6%. As described above, according to the method of the embodiment of the present invention, a stable halftone type phase shift mask and a blank for a mask in which optical constants such as transmittance, refractive index, and extinction coefficient do not change even after heat treatment and chemical treatment. Can be obtained. The translucent films of the halftone type phase shift mask blanks 10 and the halftone type phase shift mask 20 of the present invention can be applied not only to zirconium compounds such as zirconium silicide but also to thin films such as chromium, its compounds, and molybdenum silicide.
【００３０】[0030]
【発明の効果】本発明のハーフトーン型位相シフトマス
ク用ブランクスを使ってハーフトーン型位相シフトマス
クを作製する際作製工程中の熱処理、薬液処理に対して
透過率、屈折率及び消衰係数等の光学定数の変化を起こ
さない、安定したハーフトーン型位相シフトマスクマス
クを得ることができる。さらに、本発明のハーフトーン
型位相シフトマスクマスクを使って、半導体製造プロセ
ス中のフォトリソグラフィ工程に適用した際、位相シフ
トマスクとしての光学特性が維持されて、露光転写時の
パターン解像度の向上を図ることができる。When the halftone phase shift mask is manufactured using the blank for the halftone phase shift mask of the present invention, the transmittance, the refractive index, the extinction coefficient, etc. for the heat treatment and the chemical solution treatment during the manufacturing process. A stable halftone type phase shift mask that does not cause a change in the optical constant. Furthermore, when the halftone type phase shift mask of the present invention is applied to a photolithography step in a semiconductor manufacturing process, the optical characteristics of the phase shift mask are maintained, and the pattern resolution during exposure transfer is improved. Can be planned.
【図１】（ａ）〜（ｂ）は、本発明のハーフトーン型位
相シフトマスク用ブランクスの製造方法の一例を工程順
に示す模式断面図である。（ｂ）は、本発明のハーフト
ーン型位相シフトマスク用ブランクスの構成を示す模式
断面図である。（ｃ）〜（ｄ）は、本発明のハーフトー
ン型位相シフトマスクの製造方法の一例を工程順に示す
模式断面図である。（ｄ）は、本発明のハーフトーン型
位相シフトマスクの構成を示す模式断面図である。FIGS. 1A and 1B are schematic cross-sectional views illustrating an example of a method for manufacturing a blank for a halftone phase shift mask of the present invention in the order of steps. (B) is a schematic sectional view showing a configuration of a blank for a halftone phase shift mask of the present invention. 4C to 4D are schematic cross-sectional views illustrating an example of a method for manufacturing a halftone phase shift mask of the present invention in the order of steps. (D) is a schematic sectional view showing the configuration of the halftone phase shift mask of the present invention.
１０……ハーフトーン型位相シフトマスク用ブランクス １１……透明基板 １２……半透明膜 １３……酸化膜層 １４……レジストパターン １５……開口部 １６……マスクパターン ２０……ハーフトーン型位相シフトマスク Reference Signs List 10 blanks for halftone phase shift mask 11 transparent substrate 12 translucent film 13 oxide film layer 14 resist pattern 15 opening 16 mask pattern 20 halftone phase Shift mask
Claims (6)
トーン型位相シフトマスク用ブランクスにおいて、該半
透明膜の最表面に８０Å以上の厚さの酸化膜層を設けた
ことを特徴とするハーフトーン型位相シフトマスク用ブ
ランクス。1. A blank for a halftone type phase shift mask having a translucent film formed on a transparent substrate, wherein an oxide film layer having a thickness of 80 ° or more is provided on the outermost surface of the translucent film. For half-tone type phase shift mask.
コニウム及び珪素を含んだ化合物であることを特徴とす
る請求項１に記載のハーフトーン型位相シフトマスク用
ブランクス。2. The blank for a halftone phase shift mask according to claim 1, wherein said translucent film is made of zirconium or a compound containing zirconium and silicon.
２００℃以上の加熱処理により熱酸化されたものである
ことを特徴とする請求項１又は２に記載のハーフトーン
型位相シフトマスク用ブランクス。3. The halftone phase according to claim 1, wherein the oxide film layer is thermally oxidized by a heat treatment at 200 ° C. or more after the step of forming the translucent film. Blanks for shift mask.
属１に対して酸素が２以上であることを特徴とする請求
項１ないし３のうちいずれか一項に記載のハーフトーン
型位相シフトマスク用ブランクス。4. The halftone type according to claim 1, wherein said oxide film layer has an element ratio of metal to oxygen of 2 or more with respect to metal 1. Blanks for phase shift mask.
半透明膜の酸化度の高い膜であることを特徴とする請求
項１ないし４のうちいずれか一項に記載のハーフトーン
型位相シフトマスク用ブランクス。5. The halftone type according to claim 1, wherein said oxide film layer is a film having a high degree of oxidation of said translucent film formed thereunder. Blanks for phase shift mask.
載のハーフトーン型位相シフトマスク用ブランクスを用
いて、位相シフトマスクを形成したことを特徴とするハ
ーフトーン型位相シフトマスク。6. A halftone type phase shift mask, wherein a phase shift mask is formed using the blank for a halftone type phase shift mask according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6577598A JPH11258772A (en) | 1998-03-16 | 1998-03-16 | Halftone phase shift mask blank and halftone phase shift mask |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6577598A JPH11258772A (en) | 1998-03-16 | 1998-03-16 | Halftone phase shift mask blank and halftone phase shift mask |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004061782A Division JP2004199089A (en) | 2004-03-05 | 2004-03-05 | Halftone phase shift mask blank and halftone phase shift mask |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11258772A true JPH11258772A (en) | 1999-09-24 |
Family
ID=13296757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6577598A Pending JPH11258772A (en) | 1998-03-16 | 1998-03-16 | Halftone phase shift mask blank and halftone phase shift mask |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11258772A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001092106A (en) * | 1999-09-21 | 2001-04-06 | Shin Etsu Chem Co Ltd | Phase shift type photomask |
| KR100328448B1 (en) * | 1999-12-29 | 2002-03-16 | 박종섭 | Method of manufacturing a phase shift mask in a semiconductor device |
| JP2002156739A (en) * | 2000-11-21 | 2002-05-31 | Toppan Printing Co Ltd | Phase shift mask blank and phase shift mask |
| JP2005010700A (en) * | 2003-06-23 | 2005-01-13 | Toppan Printing Co Ltd | Inspection apparatus and method for original plate for exposure |
| JP2006507547A (en) * | 2002-11-25 | 2006-03-02 | トッパン、フォウタマスクス、インク | Photomask and method for producing a protective layer thereon |
| WO2006123857A1 (en) * | 2005-05-16 | 2006-11-23 | Pkl Co., Ltd. | Phase shift mask for preventing haze |
| KR100719640B1 (en) * | 2000-04-04 | 2007-05-17 | 다이니폰 인사츠 가부시키가이샤 | Halftone phase-shifting photomask and blanks for halftone phase-shifting photomask therefor and a method for forming pattern by using the halftone phase-shifting photomask |
| JP2009104174A (en) * | 2000-09-12 | 2009-05-14 | Hoya Corp | Method for manufacturing phase shift mask blank, method for manufacturing phase shift mask, and method for transferring pattern |
| JP2009294568A (en) * | 2008-06-09 | 2009-12-17 | Tsukuba Semi Technology:Kk | Method for forming surface protective film and device for forming surface protective film |
| WO2010092879A1 (en) * | 2009-02-12 | 2010-08-19 | Hoya株式会社 | Method for manufacturing photomask |
| JP2013257544A (en) * | 2012-05-16 | 2013-12-26 | Hoya Corp | Mask blank, transfer mask, and method for manufacturing them |
| JP2015225280A (en) * | 2014-05-29 | 2015-12-14 | Hoya株式会社 | Phase shift mask blank, method for manufacturing the same, and method for manufacturing the phase shift mask |
| CN112015044A (en) * | 2019-05-28 | 2020-12-01 | 爱发科成膜株式会社 | Mask blank, halftone mask, manufacturing method, and manufacturing apparatus |
| TWI841739B (en) * | 2019-05-28 | 2024-05-11 | 日商愛發科成膜股份有限公司 | Mask substrate, half-tone mask, manufacturing method, and manufacturing device |
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|---|---|---|---|---|
| JP2001092106A (en) * | 1999-09-21 | 2001-04-06 | Shin Etsu Chem Co Ltd | Phase shift type photomask |
| KR100328448B1 (en) * | 1999-12-29 | 2002-03-16 | 박종섭 | Method of manufacturing a phase shift mask in a semiconductor device |
| KR100719640B1 (en) * | 2000-04-04 | 2007-05-17 | 다이니폰 인사츠 가부시키가이샤 | Halftone phase-shifting photomask and blanks for halftone phase-shifting photomask therefor and a method for forming pattern by using the halftone phase-shifting photomask |
| JP2009104174A (en) * | 2000-09-12 | 2009-05-14 | Hoya Corp | Method for manufacturing phase shift mask blank, method for manufacturing phase shift mask, and method for transferring pattern |
| JP2002156739A (en) * | 2000-11-21 | 2002-05-31 | Toppan Printing Co Ltd | Phase shift mask blank and phase shift mask |
| JP2006507547A (en) * | 2002-11-25 | 2006-03-02 | トッパン、フォウタマスクス、インク | Photomask and method for producing a protective layer thereon |
| JP2005010700A (en) * | 2003-06-23 | 2005-01-13 | Toppan Printing Co Ltd | Inspection apparatus and method for original plate for exposure |
| WO2006123857A1 (en) * | 2005-05-16 | 2006-11-23 | Pkl Co., Ltd. | Phase shift mask for preventing haze |
| JP2009294568A (en) * | 2008-06-09 | 2009-12-17 | Tsukuba Semi Technology:Kk | Method for forming surface protective film and device for forming surface protective film |
| WO2010092879A1 (en) * | 2009-02-12 | 2010-08-19 | Hoya株式会社 | Method for manufacturing photomask |
| JP2010186069A (en) * | 2009-02-12 | 2010-08-26 | Hoya Corp | Method for manufacturing photomask |
| US8663875B2 (en) | 2009-02-12 | 2014-03-04 | Hoya Corporation | Method of manufacturing a photomask |
| JP2013257544A (en) * | 2012-05-16 | 2013-12-26 | Hoya Corp | Mask blank, transfer mask, and method for manufacturing them |
| US9946153B2 (en) | 2012-05-16 | 2018-04-17 | Hoya Corporation | Mask blank and transfer mask |
| JP2015225280A (en) * | 2014-05-29 | 2015-12-14 | Hoya株式会社 | Phase shift mask blank, method for manufacturing the same, and method for manufacturing the phase shift mask |
| CN112015044A (en) * | 2019-05-28 | 2020-12-01 | 爱发科成膜株式会社 | Mask blank, halftone mask, manufacturing method, and manufacturing apparatus |
| TWI841739B (en) * | 2019-05-28 | 2024-05-11 | 日商愛發科成膜股份有限公司 | Mask substrate, half-tone mask, manufacturing method, and manufacturing device |
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| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20040427 |
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| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20040521 |