JPH0414339B2 - - Google Patents
Info
- Publication number
- JPH0414339B2 JPH0414339B2 JP22122585A JP22122585A JPH0414339B2 JP H0414339 B2 JPH0414339 B2 JP H0414339B2 JP 22122585 A JP22122585 A JP 22122585A JP 22122585 A JP22122585 A JP 22122585A JP H0414339 B2 JPH0414339 B2 JP H0414339B2
- Authority
- JP
- Japan
- Prior art keywords
- light
- thin film
- film
- photomask
- taox
- 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.)
- Expired - Lifetime
Links
- 239000010408 film Substances 0.000 claims description 34
- 239000010409 thin film Substances 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 15
- 229910003070 TaOx Inorganic materials 0.000 claims description 10
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 10
- 229910000423 chromium oxide Inorganic materials 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/40—Electrostatic discharge [ESD] related features, e.g. antistatic coatings or a conductive metal layer around the periphery of the mask substrate
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、半導体、IC，LSI等の製造に用いら
れるフオトマスクブランクおよびフオトマスクに
関する。さらに詳しくは、本発明は、フオトマス
ク、とくにハードマスクと一般に呼ばれる、透明
基板表面に金属またはそれに代わる遮光性物質の
薄膜を蒸着またはスパツタによつて形成し、フオ
トリングラフイ、エツチング技術を経て、前記薄
膜からなるIC，LSI用パターンを形成されるフオ
トマスクブランクおよびフオトマスクに関するも
のである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photomask blank and a photomask used for manufacturing semiconductors, ICs, LSIs, etc. More specifically, the present invention involves forming a thin film of a metal or a light-shielding material in place of it on the surface of a transparent substrate, generally called a photomask, especially a hard mask, by vapor deposition or sputtering, and then using photolithography and etching techniques. The present invention relates to a photomask blank and a photomask on which IC and LSI patterns made of the thin film are formed.
（従来の技術）
従来この種のフオトマスクは、半導体基板上に
重ねられて転写露光用に用いられるが、フオトマ
スクの遮光パターンはガラス基板上に点在する金
属クロムまたは酸化クロムなどの被膜から構成さ
れている。しかし、その被膜はすべてが連続して
いるとは限らず、ガラス基板上に島状に孤立して
存在している部分もある。しかるにこのハードマ
スクの遮光パターンを他に転写しようとして、銀
乳剤被膜を有する基板やレジストコートされた半
導体基板上に接触させた場合、密着、剥離によつ
て静電気が発生し、ハードマスクのパターン間あ
るいは他の部品と放電現象が起こり、とくに上記
したパターンの島状部分の金属クロムまたは酸化
クロムなどからなる被膜の周辺部に欠落が生じる
という現象がみられる。この現象は、フオトマス
クが大形サイズになればなるほど顕著であり、最
近の半導体技術のパターン微細化からすると、こ
のような部分のわずかな欠落はフオトマスクとし
ての機能を全く失なわせるものであり致命的な欠
陥となる。(Prior Art) Conventionally, this type of photomask is used for transfer exposure by being superimposed on a semiconductor substrate, but the light-shielding pattern of the photomask is composed of a film of metallic chromium or chromium oxide dotted on a glass substrate. ing. However, not all of the coating is continuous, and some portions exist isolated in the form of islands on the glass substrate. However, when trying to transfer the light-shielding pattern of this hard mask onto another substrate and bringing it into contact with a substrate with a silver emulsion coating or a resist-coated semiconductor substrate, static electricity is generated due to adhesion and peeling, and the gaps between the patterns of the hard mask are generated. Alternatively, a phenomenon in which a discharge occurs with other parts occurs, and a phenomenon is observed in which chipping occurs particularly in the peripheral portion of the coating made of metallic chromium or chromium oxide in the island-like portion of the pattern described above. This phenomenon becomes more pronounced as the photomask becomes larger, and given the miniaturization of patterns in recent semiconductor technology, even the slightest omission of such a part can completely destroy the function of the photomask, making it fatal. It becomes a defect.
また、静電気を帯びることは、ゴミを吸着しや
すく、ゴミによる不良パターンの発生等の原因に
もなる。 Furthermore, being charged with static electricity tends to attract dust, which may cause the generation of defective patterns due to dust.
さらに近年、半導体素子の微細化、高密度化に
伴い、フオトリングラフイにかわり電子線露光法
が使用されるに至つているが、上述したマスク
は、ガラス基板が絶縁性のため、電子線露光に際
して照射部が帯電し画像の歪み、位置ずれ等を生
ずる欠点がある。 Furthermore, in recent years, with the miniaturization and higher density of semiconductor devices, electron beam exposure has come to be used instead of photolithography. There is a drawback that the irradiation section is charged during exposure, causing image distortion, positional shift, etc.
このような欠点を解決する手段として、フオト
マスクに透明な導電膜を設け、フオトマスクの帯
電現象を解消することが提案されている。しか
し、問題は、透明な導電膜に用いる材料にあるの
であつて、例えば、酸化インジウムや酸化スズ
は、透明性に優れるが、所望の導電度を得るには
相当な厚さの膜が必要であり、その上に遮光膜と
してミクロンオーダーの微細パターンを形成する
ことは、パターンとしての荒れの問題が生じる惧
れがある。それに前者酸化インジウムは、化学的
耐久性に劣り遮光用薄膜の金属クロムや酸化クロ
ムをパターン化する際のエツチング剤に侵されて
しまうということがある。、このほか透明な導電
膜の材料として、モリブデン（Mo）、タングス
テン（Ｗ）、タンタル（Ta）等の比較的侵されに
くい金属を薄く蒸着して透明導電膜とすることも
提案されているが、これらの材料は、本質的に金
属であるから、透明性に劣り、またエツチング剤
に侵されやすく、さらに言えば、ガラス基板との
接着性および遮光薄膜である金属クロムや酸化ク
ロムとの接着性にも問題が無いとは言えない。 As a means to solve these drawbacks, it has been proposed to provide a transparent conductive film on a photomask to eliminate the charging phenomenon of the photomask. However, the problem lies in the materials used for the transparent conductive film; for example, indium oxide and tin oxide have excellent transparency, but require a fairly thick film to achieve the desired conductivity. However, forming a fine pattern on the order of microns as a light-shielding film thereon may cause the problem of roughness of the pattern. In addition, the former indium oxide has poor chemical durability and may be attacked by the etching agent used when patterning the metal chromium or chromium oxide of the light-shielding thin film. In addition, as a material for transparent conductive films, it has also been proposed to make transparent conductive films by thinly vapor-depositing metals that are relatively resistant to corrosion, such as molybdenum (Mo), tungsten (W), and tantalum (Ta). Since these materials are essentially metal, they have poor transparency and are easily attacked by etching agents.Furthermore, they have poor adhesion to glass substrates and to metal chromium and chromium oxide, which are light-shielding thin films. It cannot be said that there are no problems with sexuality.
（発明が解決しようとする問題点）
本発明は、大形サイズのフオトマスクに特に起
こりがちな静電気の放電現象の発生を防止し、透
明性および隣接する層との接着性を向上させるこ
と、成膜が容易でかつ耐薬品性等の化学的耐久性
が高いこと、等を実現するフオトマスクブランク
およびフオトマスクを提供するものである。(Problems to be Solved by the Invention) The present invention aims to prevent the occurrence of electrostatic discharge phenomenon that tends to occur particularly in large-sized photomasks, improve transparency and adhesion with adjacent layers, and improve transparency and adhesion with adjacent layers. The present invention provides a photomask blank and a photomask that are easy to form and have high chemical durability such as chemical resistance.
（発明の構成）
すなわち、本発明は透明基板上に感光性樹脂の
感光領域の光に対して75％以上の透過率を有し膜
厚30〜80Åの酸化タンタル（TaOx：Ｘ≦２）の
導電性薄膜を設け、さらに感光性樹脂の感光領域
の光に対して遮光性の薄膜を設けたことを特徴と
するフオトマスクブランクであり、かつ透明基板
上に感光性樹脂の感光領域の光に対して75％以上
の透過率を有し膜厚30〜80Åの酸化タンタル
（TaOx：Ｘ≦２）からなる導電性薄膜を設け、
さらに感光性樹脂の感光領域の光に対して遮光性
のパターン化された薄膜を設けたことを特徴とす
るフオトマスクである。(Structure of the Invention) In other words, the present invention provides a film of tantalum oxide (TaOx: This is a photomask blank characterized by providing a conductive thin film and further providing a thin film that blocks light from the photosensitive area of the photosensitive resin, and which is provided on a transparent substrate from the light from the photosensitive area of the photosensitive resin. A conductive thin film made of tantalum oxide (TaOx:
The photomask is further characterized by being provided with a patterned thin film that blocks light from the photosensitive area of the photosensitive resin.
（発明の詳述）
以下さらに、本発明を詳細に説明すれば、第１
図から第３図は、本発明のフオトマスクブランク
の種々の形状を示すものであるが、透明基板１
は、たとえば、ソーダライムガラス、硼硅酸ガラ
ス、石英ガラス、水晶、サフアイヤ等、光学的に
透明な任意材料からなり、その厚みには本質的な
制約はないが、通常0.2〜６mmのものが用いられ
る。(Detailed Description of the Invention) The present invention will be described in more detail below.
FIG. 3 shows various shapes of photomask blanks of the present invention.
is made of any optically transparent material such as soda lime glass, borosilicate glass, quartz glass, crystal, sapphire, etc. There is no essential restriction on its thickness, but it is usually 0.2 to 6 mm. used.
第１図のものは、酸化タンタル（TaOx：Ｘ≦
２）の透明導電膜２を透明基板１の表面に積層
し、その上に遮光性薄膜３としての金属クロムが
設けられている。ここで、透明導電膜２は、他の
実施例でも共通であるので説明すると、酸化数Ｘ
は２以下とする。もしもこの値が2.5となると、
それは、五酸化タンタル（Ta2O5）を意味し、全
くの絶縁物となり、導電性を示さない。膜厚は30
〜80Å（オングストローム）とする。30Åより薄
い膜では、導電性が不足気味であり、80Åより厚
い膜では感光性樹脂の感光領域の光に対して75％
以上の光透過率を示さないからまずい。膜厚の最
適値は、、40〜60Åであり、この時の面抵抗値は
10〜20KΩ／cm2を示し良好である。（但し、透明
導電膜２を成膜した直後の値である。）
第２図は、酸化タンタル（TaOx：Ｘ≦２）の
透明導電膜２の上に遮光性薄膜３として金属クロ
ム膜３ａと酸化クロム膜３ｂとからなる二層構成
を採用している。上層の酸化クロム膜３ｂは、表
面の光反射を防止する役目を荷つている。 The one in Figure 1 is tantalum oxide (TaOx:
The transparent conductive film 2 of 2) is laminated on the surface of the transparent substrate 1, and metal chromium as the light-shielding thin film 3 is provided thereon. Here, since the transparent conductive film 2 is common to other embodiments, the oxidation number
shall be 2 or less. If this value becomes 2.5,
It stands for tantalum pentoxide (Ta 2 O 5 ), which is completely insulating and does not exhibit electrical conductivity. Film thickness is 30
~80 Å (Angstrom). A film thinner than 30 Å lacks conductivity, and a film thicker than 80 Å has 75% of the light in the photosensitive area of the photosensitive resin.
It's bad because it doesn't show a higher light transmittance. The optimal value for the film thickness is 40 to 60 Å, and the sheet resistance value at this time is
It shows a good value of 10 to 20KΩ/cm 2 . (However, this is the value immediately after forming the transparent conductive film 2.) Figure 2 shows a metal chromium film 3a as a light-shielding thin film 3 on the transparent conductive film 2 of tantalum oxide (TaOx: X≦2). A two-layer structure consisting of a chromium oxide film 3b is adopted. The upper layer chromium oxide film 3b has the role of preventing light reflection on the surface.
第３図は、遮光性薄膜３として、下側にも酸化
クロムの薄膜３ｃを設けたものである。薄膜３ｃ
は、裏面の光反射を防止することと、隣接する上
下の層の接着性を補強させる役目も荷つている。 In FIG. 3, a chromium oxide thin film 3c is also provided on the lower side as the light-shielding thin film 3. thin film 3c
It also has the role of preventing light reflection on the back surface and reinforcing the adhesion between the adjacent upper and lower layers.
遮光性薄膜３としては、上記のほか酸化クロム
の単層膜もありうる。 In addition to the above, the light-shielding thin film 3 may also be a single layer film of chromium oxide.
これらの膜は、公知のエツチング液例えば硝酸
セリウムと過酸化水素の混合液やドライエツチン
グ法でパターン化が可能であり、しかも下層の
TaOxの導電性薄膜が耐薬品性に富むので、エツ
チングされない。 These films can be patterned using a known etching solution, such as a mixture of cerium nitrate and hydrogen peroxide, or by dry etching.
The conductive thin film of TaOx has high chemical resistance, so it will not be etched.
導電性薄膜（TaOx）の成膜方法としては、反
応性のスパツタ蒸着法が良く、例えば、モル比で
アルゴンガス（Ar）10に対して炭酸ガスを0.5〜
２の割合でスパツター室へ導入し、スパツター室
の圧力を10-4〜10-3Torr程度に設定したDCマグ
ネトロン方式でターゲツトを金属タンタルとした
スパツター蒸着法があげられる。 A good method for forming a conductive thin film (TaOx) is a reactive sputter deposition method. For example, the molar ratio of argon gas (Ar) to 10 to 10 carbon dioxide gas is
One example is a sputter vapor deposition method using tantalum metal as a target using a DC magnetron system in which tantalum is introduced into a sputter chamber at a ratio of 2:2 and the pressure in the sputter chamber is set at about 10 -4 to 10 -3 Torr.
酸素源として炭酸ガスを用いず酸素ガスを用い
ても良い。その際はアルゴンガスに対してモル比
で0.3〜1.0程度の酸素ガスを用いる。。しかし、
酸素ガスは酸化力が強すぎる傾向があり、酸素ガ
スよりも炭酸ガスを用いたほうが、金属タンタル
の酸化度（TaOxのＸの値）の制御がやりやすい
ので奨められる。酸化が進みすぎてTa2O5になる
と、全くの絶縁膜となつてしまい、本発明の目的
に反するから注意を要する。 Oxygen gas may be used as the oxygen source instead of carbon dioxide gas. At that time, oxygen gas is used at a molar ratio of about 0.3 to 1.0 to argon gas. . but,
Oxygen gas tends to have too strong oxidizing power, and it is recommended to use carbon dioxide gas rather than oxygen gas because it is easier to control the degree of oxidation of tantalum metal (value of X of TaOx). If the oxidation progresses too much and becomes Ta 2 O 5 , it will become a complete insulating film, which is contrary to the purpose of the present invention, so care must be taken.
以下に本発明の酸化タンタル導電膜つきのフオ
トマスクの製造方法の一例を、図面の第４図ａ〜
ｄに基いて述べる。 An example of the method for manufacturing a photomask with a tantalum oxide conductive film of the present invention is shown below in Figures 4a to 4 of the drawings.
I will explain based on d.
（実施例）
石英ガラス、硼ケイ酸系ガラス、ソーダライム
ガラス等の透明基板１に対して、直流マグネトロ
ンスパツタ装置を用いて、ターゲツトとして金属
タンタルを用い、アルゴンガス流量30SCCM、炭
酸ガス（CO2）流量3SCCMに設定し、ターゲツ
ト電流0.5A，ターゲツト電圧400〜450V、スパツ
タ放電時の圧力が5.8〜6.2×10-4Torrの条件で、
透明基板１の上に透明導電膜２のTaOx（Ｘ≦２）
を50〜60Å厚に成膜した。得られた透明導電膜２
の感光性樹脂の感光領域（300〜500nm）の光透
過率は80〜90％で、表面電気抵抗値は、10〜
20KΩ／cm2であつた。この上に、遮光性薄膜３と
して金属クロム800Åおよび酸化クロム200Åの二
層構成の膜を成膜して、表面の光反射率を低減し
たフオトマスクブランクを得た。(Example) A transparent substrate 1 made of quartz glass, borosilicate glass, soda lime glass, etc. was coated with a DC magnetron sputtering device using tantalum metal as a target, an argon gas flow rate of 30 SCCM, and carbon dioxide gas (CO 2 ) Set the flow rate to 3SCCM, target current 0.5A, target voltage 400 to 450V, and sputter discharge pressure of 5.8 to 6.2×10 -4 Torr.
TaOx (X≦2) of transparent conductive film 2 on transparent substrate 1
was deposited to a thickness of 50 to 60 Å. Obtained transparent conductive film 2
The light transmittance of the photosensitive resin in the photosensitive region (300-500 nm) is 80-90%, and the surface electrical resistance value is 10-90%.
It was 20KΩ/ cm2 . A two-layer film of 800 Å of metal chromium and 200 Å of chromium oxide was formed thereon as a light-shielding thin film 3 to obtain a photomask blank with reduced surface light reflectance.
これにAZ−1350（米国シツプレー社製ポジ型感
光性樹脂）を1.2μ厚にスピンナー塗布してフオト
レジスト層４とし、所望のパターンを部分露光し
た（第４図ａ参照）。しかる後、AZ−1350の指定
現像液を用いて露光部のフオトレジスト層４を除
去し（第４図ｂ参照）、続いて硝酸セリウムアン
モンと過酸化水素からなる酸化クロム〜金属クロ
ム用腐食液を用いて露出した遮光性薄膜３を選択
的に腐食除去し（第４図ｃ参照）、しかる後、残
存していたフオトレジスト層４′を剥離液にて除
去し、フオトマスクとした（第４図ｄ参照）。得
られたマスクの接着性をテストするため、鉄筆や
カミソリ刃による摩擦試験を行なつたが、膜の剥
がれ等の欠陥は生じなかつた。 This was coated with AZ-1350 (a positive photosensitive resin manufactured by Shippley, USA) to a thickness of 1.2 μm using a spinner to form a photoresist layer 4, and a desired pattern was partially exposed (see FIG. 4a). After that, the photoresist layer 4 in the exposed area was removed using a specified developer of AZ-1350 (see Figure 4b), and then a chromium oxide to metal chromium corrosive solution consisting of cerium ammonium nitrate and hydrogen peroxide was applied. The exposed light-shielding thin film 3 was selectively etched away using a solvent (see Figure 4c), and the remaining photoresist layer 4' was then removed using a stripping solution to form a photomask (see Figure 4c). (see figure d). In order to test the adhesion of the obtained mask, a friction test was performed using a steel pen or a razor blade, but no defects such as peeling of the film occurred.
（発明の効果）
本発明のフオトマスクブランクおよびフオトマ
スクは以上のようなものであり、本発明によれ
ば、フオトマスクに導電膜を付したので、静電気
が帯電せず、放電現象による遮光パターンの欠落
あるいは静電気によるゴミ吸着などを防止でき
る。本発明による透明導電膜の材料は酸化物であ
り、金属のように遮光性に富むものではないか
ら、感光性樹脂の感光領域での光透過率も75％以
上（実際には80〜90％にもなる）とすることが容
易で、しかも酸化タンタルとして低酸化度のもの
を用いるから、導電率も所期の高い値が得られ
る。そのほか、金属と異なり、耐薬品性が高く、
遮光性薄膜をエツチングする際にも下層の透明導
電膜は侵されにくく、エツチング剤の選定幅も広
くなる。そのほか、酸化タンタルの透明導電膜
は、金属タンタル等の金属の透明導電膜に比べ
て、隣接する上下の層との接着性が強固であり、
実施例に述べたように、遮光性薄膜を鉄筆やカミ
ソリ刃で摩擦する試験でも剥離が起こらず、良好
であつた。(Effects of the Invention) The photomask blank and photomask of the present invention are as described above, and according to the present invention, since a conductive film is attached to the photomask, static electricity is not charged, and the light-shielding pattern is not missing due to a discharge phenomenon. Alternatively, it is possible to prevent dust from being attracted by static electricity. The material of the transparent conductive film according to the present invention is an oxide and does not have a high light-shielding property like metal, so the light transmittance in the photosensitive area of the photosensitive resin is 75% or more (actually 80 to 90%). Moreover, since tantalum oxide with a low oxidation degree is used, the desired high value of electrical conductivity can be obtained. In addition, unlike metals, it has high chemical resistance,
Even when etching a light-shielding thin film, the underlying transparent conductive film is not easily attacked, and the selection range of etching agents is widened. In addition, transparent conductive films made of tantalum oxide have stronger adhesion with adjacent upper and lower layers compared to transparent conductive films made of metals such as tantalum metal.
As described in the Examples, even in the test in which the light-shielding thin film was rubbed with an iron pen or a razor blade, no peeling occurred and the results were good.
第１図から第３図までは、本発明のフオトマス
クブランクの種々の実施例を示す断面図であり、
第４図ａ〜ｄは、本発明のフオトマスクの製造プ
ロセスの一例を工程順に示す説明図である。
１……透明基板、２……透明導電膜、３……遮
光性薄膜、４……フオトレジスト層。
1 to 3 are cross-sectional views showing various embodiments of photomask blanks of the present invention,
FIGS. 4a to 4d are explanatory diagrams showing an example of the process for manufacturing a photomask of the present invention in the order of steps. 1...Transparent substrate, 2...Transparent conductive film, 3...Light-shielding thin film, 4...Photoresist layer.
Claims (1)
対して75％以上の透過率を有し膜厚30〜80Åの酸
化タンタル（TaOx：Ｘ≦２）からなり反応性の
スパツタ蒸着法により成膜した導電性薄膜を設
け、さらにこの上より感光性樹脂の感光領域の光
に対して遮光性の薄膜を設けたことを特徴とする
フオトマスクブランク。 ２ 透明基板上に、感光性樹脂の感光領域の光に
対して75％以上の透過率を有し膜厚30〜80Åの酸
化タンタル（TaOx：Ｘ≦２）からなり反応性の
スパツタ蒸着法により成膜した導電性薄膜を設
け、さらにこの上より感光性樹脂の感光領域の光
に対して遮光性の薄膜を設けたフオトマスクブラ
ンクの前記遮光性の薄膜がパターン化されたこと
を特徴とするフオトマスク。[Claims] 1. A transparent substrate made of tantalum oxide (TaOx: 1. A photomask blank comprising a conductive thin film formed by a conventional sputter deposition method, and further provided with a thin film that blocks light from a light-sensitive area of a photosensitive resin. 2. On a transparent substrate, a film made of tantalum oxide (TaOx: A photomask blank is provided with a conductive thin film formed thereon and further provided with a thin film that blocks light from the light-sensitive area of a photosensitive resin, and the light-blocking thin film is patterned. Photo mask.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60221225A JPS6280655A (en) | 1985-10-04 | 1985-10-04 | Photomask blank and photomask |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60221225A JPS6280655A (en) | 1985-10-04 | 1985-10-04 | Photomask blank and photomask |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6280655A JPS6280655A (en) | 1987-04-14 |
| JPH0414339B2 true JPH0414339B2 (en) | 1992-03-12 |
Family
ID=16763427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60221225A Granted JPS6280655A (en) | 1985-10-04 | 1985-10-04 | Photomask blank and photomask |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6280655A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07111946B2 (en) * | 1987-05-29 | 1995-11-29 | 株式会社日立製作所 | X-ray exposure mask pattern inspection method |
| JP2788649B2 (en) * | 1989-05-30 | 1998-08-20 | ホーヤ株式会社 | Photomask blank and photomask |
| JP5997530B2 (en) * | 2011-09-07 | 2016-09-28 | Hoya株式会社 | Mask blank, transfer mask, and semiconductor device manufacturing method |
| JP6297321B2 (en) * | 2013-12-09 | 2018-03-20 | Hoya株式会社 | Manufacturing method of substrate with functional film, manufacturing method of substrate with multilayer film, manufacturing method of mask blank, and manufacturing method of transfer mask |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55161240A (en) * | 1979-06-04 | 1980-12-15 | Dainippon Printing Co Ltd | Photomask |
| JPS57205342A (en) * | 1981-06-15 | 1982-12-16 | Seiko Epson Corp | Glass photomask |
-
1985
- 1985-10-04 JP JP60221225A patent/JPS6280655A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55161240A (en) * | 1979-06-04 | 1980-12-15 | Dainippon Printing Co Ltd | Photomask |
| JPS57205342A (en) * | 1981-06-15 | 1982-12-16 | Seiko Epson Corp | Glass photomask |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6280655A (en) | 1987-04-14 |
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| EXPY | Cancellation because of completion of term |