PHOTOMASK BLANK AND PHOTOMASK

Abstract: A photomask (B) is fabricated by forming, in a photo­ mask (hard mask) produced by forming a patternized film (3a) of a masking material such as metallic chromium, a chromium oxide, a chromium nitride, metallic silicon, a silicon oxide or a mixture thereof on a transparent substrate (1), a metallic film (2) of a translucent and electroconductive material selected from Mo, Nb, Ta, Ti, V, W, Cr, Au and Zr between the masking film (3a) and the transparent substrate (1). At the time of pattern transferring by photolithography, dropping off of parts of the pattern of this photomask does not occur even when it includes isolated island-like parts, and, at the time of inspection by electron-beam exposure, the precision of inspection does not lower. The photomask, by further comprising a chemically resistant and translucent protective film (5) between the electroconductive film (2) and the masking film (3a), is free of destruction of the electrocon­ ductive film (2) during the repeated washing between the repeated use of the photomask.

Description: PHOTOMASK BLANK AND PHOTOMASK This invention relates generally to photomask blanks and photomasks for use in the production of semiconductors, integrated circuits (IC), large-scale integrated circuits (LSI), and like electronic components. More specifically, this invention relates to photomasks of the type generally called hard masks and to their blanks. In general, a photomask blank is fabricated by forming on an outer surface of a transparent substrate a thin metal film or, in place thereof, a thin film of a masking material by a process such as vacuum evaporation or sputtering. By applying a photolithographic process including the steps of forming a photoresist film, pattern exposure to light, and etching to this photomask blank, a film of the above mentioned metal or masking material is left in the form of a pattern such as a pattern of a circuit for an IC or an LSI on the transparent substrate thereby to produce a photomask. This photomask is superposed on a semiconductor wafer and thus used for pattern transfer exposure, but since the photomask is actually an expendable article, the common practice at present is to fabricate beforehand a master mask or, further, a sub-master mask and, with the use of this master mask or sub-master mask, to fabricate masks for transferring patterns onto semiconductor wafers. For reasons of cost, photomasks having a silver emulsion film as a light-screening or masking film are frequently used as photomasks for pattern transfer. A circuit pattern on the above mentioned hard mask comprises a film of a material such as metallic chromium or chromium oxide in scattered state on a glass plate. This film is not necessarily continuous over its entire expanse, there being parts existing in isolated island-like state on the glass plate. A problem arises in the following two cases as described below. The first case is that wherein this hard mask is used as a master mask or a sub-master mask and caused to contact a mask blank having a silver emulsion film, onto which the circuit pattern of the master mask is transferred. The second case is that wherein the circuit pattern of a mask is caused to contact a semiconductor wafer which has been coated with a resist thereby to transfer the circuit pattern. In each of these cases, static electricity is generated by friction at the time of intimate contact and peeling off, and a discharge phenomenon occurs between the pattern parts of the hard mask. Consequently, particularly at the peripheral parts of the film comprising metallic chromium, a chromium oxide, or the like of the above mentioned island-like parts of the pattern, portions of the film are observed to have dropped off and are missing. Even small portions which are thus missing give rise to a complete loss of the function of the master mask, whereby this result is a fatal defect. Furthermore, photomasks known in the prior art have exposed portions of the substrate outer surface. These exposed portions have lower surface strength than film portions and are subject to so-called staining during storage. Portions in which staining has occurred are easily damaged, in general, and lead to a lowering of the resolution of the mask. Another problem is that, when the photomask is brought into intimate contact with a semiconductor wafer for exposure to light, the portions in which staining has occurred are very easily scratched or scored by the concavities and convexities of the semiconductor surface, dust, and other causes. Consequently, in spite of the use of the film of metallic chromium, chromium oxide, or the like for the light-screening film especially for their high value of surface hardness, the strength and durability of the entire hard mask is determined by those of the transparent substrate. Still another difficulty is that, because of the accumulation of electrostatic charge during use as a result of repeated use, dust readily adheres to give rise to problems such as impairment of the intimate contact with the wafer and scratching of surfaces due to the dust. Furthermore, together with miniaturization and denser arrangement of semiconductor devices, extremely high degrees of image quality and dimensional precision of the photomasks therefor become necessary. For this reason, in place of the ordinary photographic inspection, the electron beam inspection is coming into use. However, since photomasks after patterning are generally insulative along the expanse thereof, the parts irradiated by electron beam are charged and the accuracy of inspection is lowered to an impractical level. In order to avoid the above difficulties, it has been proposed to use a photomask wherein an electroconductive film made of an oxide such as indium oxide and tin oxide is interposed between a transparent substrate and a masking film (U.S. Patent No. 4178403). According to this mask, the above mentioned difficulties resulting from the insulative property of photomasks can be obviated. However, electroconductive photomasks of this type accompany the following other difficulties and are not practically satisfactory. Firstly, the oxide electroconductive films as mentioned above do not have a sufficient chemical resistance and are readily attacked by a chromic acid mixture solution, a mixture solution of H2SO4 + H202 and a mixture solution of benzenesulfonic acid and a phenol which are generally used as cleaning solutions for photomasks, whereby not only the transparency of parts not covered by the masking film is considerably changed but also the oxide electroconductive films are caused to dissolve in a relatively short time and lose their conductivity. These oxide films, of course, have a sufficient resistance to organic solvent, whereas it is, as is well-known in the art, extremely difficult to remove various kinds of stains adhering to photomasks with organic solvent. Secondly, these electroconductive oxide films have poor adhesiveness or stickiness to both glass substrates and masking films such as chromium films and are liable to form defects such as pin-holes. Furthermore, for the same reason, they generally have a poor scratch-resistance. Because of these difficulties, this type of photomasks having an oxide electroconductive film generally fails to give an improved durability which hard masks are expected to provide for. It is an object of this invention to overcome the problems encountered with respect to known hard masks as described above and thereby to provide photomask blanks and photomasks having high durability and, moreover, excellent applicability to the electron-beam inspection. This invention contemplates the achievement of the above stated object by a multilayer construction produced by forming, on a transparent substrate as used in the prior art, a translucent film having electroconductivity by vacuum evaporation, sputtering, or electroless plating and further forming thereon a film of a material used heretofore as a material for mask such as metallic chromium, chromium oxide, metallic silicon, iron oxide, metallic tantalum, or tantalum oxide. According to this invention in one aspect thereof, briefly summarized, there is provided a photomask blank comprising a transparent substrate, a metallic film of a translucent and electroconductive material selected from the group consisting of Mo, Nb, Ta, Ti, V, W, Cr, Zr and Au on the substrate, and a masking film comprising at least one layer of a masking material selected from the group consisting of metallic chromium, chromium oxide, chromium nitride, metallic silicon, iron oxide, metallic tantalum, tantalum oxide, tantalum nitride and combinations thereof on the first film. According to this invention in another aspect thereof, there is provided a photomask of a general construction as described above in which the masking film is patternized. Throughout this specification, the terms "translucent" (or "light-transmittancy" or "light-transmissive") and "masking" (or "light-screening") are intended to mean these characteristics with respect to light used in photolithography in a broad sense. The nature, utility, and further features of this invention will be more clearly apparent from the following detailed description when read in conjunction with the accompanying drawing, briefly described below. In the drawings: FIGS. 1 and 5 are schematic sectional views, respectively showing laminated structures of one example of the photomask blank according to this invention and one example of a photomask prepared from that photomask blank; FIGS. 2, 3 and 4 are schematic sectional views illustrating the steps for preparation of a photomask from a photomask blank; and FIGS. 6 and 7 are schematic sectional views, similar to FIGS. 1 and 5, respectively showing the laminated structure of another example of the photomask blank and another example of the photomask prepared therefrom. As shown in FIG. 1, a photomask blank A according to the present invention has an electroconductive metallic film 2 having translucency, and a masking film 3 laminated successively on a transparent substrate 1. The transparent substrate 1 in the photomask blank A of this invention is made of any optically transparent material such as, for example, soda-lime glass, quartz glass, or sapphire. While there are essentially no limits to the thickness of this substrate, substrates of thicknesses of 0.2 to 6 mm are ordinarily used. Next, the translucent metallic film having electroconductivity 2 formed on the transparent substrate must be one having the property of readily transmitting light therethrough and the property of readily conducting electricity therethrough. As for its transmittancy, a film having a transmittance of 60 percent or more with respect to light of a wavelel;gth of 200 to 550 nm, particularly 400 to 550 nm, is preferable. An electrical resistivity of the film in terms of sheet resistivity of 50 RQ per square or lower, specially 10 KQ per square or lower, is desirable. Further, the thickness of this film is preferably 10 to 1,000 A and more preferably 10 to 200 A. It is also necessary that the adhesiveness of this film relative to the masking film 3 which will be described in detail hereinafter and to the transparent substrate 1 be good. Another requirement is that, since the photomask is washed and repeatedly used, this film have a high chemical resistance with respect to acids, alkalis, and solvents to be used in the washing. Still another requirement is that this electroconductive film 2 have chemical resistance with respect also to etching agents for the masking film 3. As a material for the electroconductive film 2 having the above described characteristics, a material selected from the group consisting of Mo, Nb, Ta, Ti, V, W, Zr, Cr and Au is used. Among these materials, Ta is most preferable. Ordinarily, these materials are used singly,but it is possible to use two or more thereof in combination. Considering now the masking film 3, it comprises at least one layer of one or more materials selected from chromium, chromium oxide, chromium nitride, silicon, silicon oxide, tantalum, tantalum nitride, tantalum oxide and iron oxide. This film may itself be a laminated product having a low reflection layer such as a chromium oxide layer laminated on a layer of chromium. The thick ness of the masking film 4 is, for example, 300 A to 200 o A and more preferably 600 to 2,000 A. FIGS. 2 through 5 indicate the steps for production of a photomask of this invention with the use of a photomask blank of this invention. As shown in FIG. 2, a resist 4 is coated on the masking film 3. Then, exposure to light and development are carried out to form a resist pattern 4a as shown in FIG. 3. This step is followed by etching of the exposed portions of the masking film 3 as shown in FIG. 4. Finally, the resist 4a is peeled off to obtain a desired photomask B as shown in FIG. 5. The etching of the masking film may be conducted by either the wet etching method or the dry etching method. In the case of wet etching, it is possible to use an etchant which will etch the masking film without erosion of the electro-conductive film. Some examples of such an etchant are as follows. Composition of etchant when the masking film is metallic chromium or chromium oxide (NH4) 2Ce (NO3)4 165.0 g HC104(70%) 43.0 ml pure water 1,000 ml Composition of etchant when the masking film is silicon AgNO3 1.0 g NH4F 0.5 g HNO3 100 ml pure water 100 ml Composition of etchant when the masking film is iron oxide HC1 300 ml pure water 100 ml Next, in the case of dry etching, it can be conducted by means of a parallel-plate type plasma-etching device under the conditions corresponding to the masking film as specified below. Conditions when the masking film is metallic chromium or chromium oxide Etching gas: mixture of CC14 and air Gas pressure: 0.3 Torr High-frequency power applied: 200 W Etching time: 5 minutes Conditions when the masking film is silicon Etching gas: CF4 Gas pressure: 0.02 Torr High-frequency power applied: 250 W Etching time: 1 minute Conditions when the masking film is metallic tantalum or tantalum oxide Etching gas: CF 4 Gas pressure: 0.01 Torr High-frequency power applied: 300 W Etching time: 2 minutes In the foregoing part of the disclosure, a basic example of each of the photomask blank and the photomask according to this invention has been described along with the method for production thereof. A photomask thus obtained is, however, subjected to repeated washing many times with a cleaning agent such as an acid or an alkali between the repeated use thereof, and it is therefore possible that the electroconductive film will be attacked by the cleaning agent, whereby the photomask will no longer be capable of performing as an electroconductive photomask. The corrosion of the electroconductive film 2 can be caused by its contact with the masking film 3 even if the chemical resistance of the electroconductive film 2 itself is large. Moreover, the surface hardness of the electroconductive film may be small, and the durability of the entire photomask can be restricted by that of the electroconductive film 2. In order to overcome these difficulties, according to preferred embodiments of this invention, there is inserted a translucent and chemically resistant protective film 5 made of one or more materials selected from aluminum oxide, calcium oxide, magnesium oxide, silicon oxide, cerium oxide, tantalum oxide, chromium oxide and titanium oxide, as shown in FIGS. 6 and 7. Among these materials, silicon dioxide is the most preferable as a single material. This film has a transmittance desirably of 80 percent or more with respect to light of a wavelength of 200 to 600 nm, particularly 400 to 600 nm. This film is highly resistant to chemicals and protects the aforesaid electroconductive film, thus functioning to prevent the electroconductive film from being destroyed by repeated washing treatment with acids or alkalis. This film also functions as a barrier, by which the masking film can be effectively protected from deleterious effects due to sodium ions precipitated from a transparent substrate such as that of glass. Further, this film has chemical resistance with respect to an etching solution or an etching gas employed for etching of a masking film to be provided on the film. The thickness of this film is o o preferably 10 to 1,000 A, particularly 50 to 100 A. With a thickness within such a range, surface electroconductivity can be retained after formation of the protective film 3. As described in detail above, the photomask blank of this invention can produce a photomask having ample electroconductivity to prevent destruction of silicon wafer elements and occurrence of pattern defects of the photomask caused by electrostatic charges at the time of pattern printing, for which dimensional measurement and evaluation of registration by an electron-beam system are possible. Further, with use of the photomask blank according to this invention, a photomask can be prepared not only by a wet etching system but also by a dry etching system. The photomask thus obtained has an electroconductive film and therefore has ample electroconductivity to avoid destruction of the silicon wafer elements and occurrence of pattern defects in the photomask caused by electrostatic charges at the time of pattern printing. Further, dimensional measurement by an electron-beam system and evaluation of registration of the photomask of this invention are possible. Furthermore, where the electroconductive film is covered by a chemically resistant protective film, a photomask protected against damage during repeated washing with an acid, alkali or the like is obtained. In order to indicate more fully the nature and utility of this invention, the following examples are set forth, it being understood that these examples are presented as illustrative only and are not intended to limit the scope of the invention. Example 1 On a transparent substrate made of soda lime glass of a thickness of 2.3 mm, a Ta film of a thickness of o 50 A was formed by sputtering to constitute a translucent electroconductive film. It should be mentioned that this electroconductive film can also be formed, in general, by a process such as vacuum evaporation or electroless plating. Then, on this Ta film, a masking film made of a thin film of metallic chromium of a thick o ness of 1,000 A was formed in accordance with the sputtering process. Thus, a photomask blank of the construction as indicated in FIG. 1 was fabricated. Then, on the Ta film of the photomask blank thus fabricated, a photoresist (AZ-1350 mfd. by Shipley Co., Inc.) of a thickness of 0.5 micron was formed. After exposure to light of the photoresist through a circuit pattern, the photoresist was developed by using a developer prescribed therefor thereby to obtain a resist pattern. Then, with an etching liquid comprising 165.0 g of (NH4)2Ce(NO3)6, 43.0 g of HC104 (70%) and 1,000 ml of pure water, etching of the Cr layer was carried out without essentially any corrosion of the Ta film thereby to form a pattern. Then, by peeling off and removing the resist film, a photomask (hard mask) of this invention as shown in FIG. 5 was obtained. In the photomask thus obtained, the light-transmittance of the electroconductive film with respect to light of wavelengths of 400 to 550 nm was found to be 80 percent or more, and the sheet resistivity was found to be less than 50 KQ per square. Ten of these hard mask materials were fabricated and subjected to a durability test. In this test, pattern transfer onto a photomask blank having a silver emulsion film was carried out 100 times in an atmosphere at a temperature of 220C and a humidity of 40 percent. As a result, it was found that there was no occurrence of dropping off of the Cr film parts in island-like state in all ten hard mask materials, and there were no defects whatsoever on also the glass substrate surfaces without Cr films. For comparison, ten hard mask samples of known type obtained by the procedure described above except that the electroconductive film was not formed were subjected to the same test described above. As a result, dropping off of the Cr film pattern occurred in all ten samples with 10 transfers. Example 2 Furthermore, the procedure of the above Example 1 was carried out except for the forming of a silicon film o of a thickness of 1,000 A in place of the Cr film thereby to obtain a photomask blank as indicated in FIG. 1. The silicon film of this blank was coated with an electronbeam resist (PBS mfd. by Mead Chemical Corp.) of a thickness of 0.4 micron. This blank was used to carry out electron-beam exposure. As a result, a parallel pattern of 0.5-u width was obtained without distortion. Example 3 On a glass plate, a film of tantalum was formed to o a thickness of 50 A according to the electron-beam heated vacuum evaporation method, and then a film of silicon o oxide was formed to a thickness of 200 A according to the electron-beam heated vacuum evaporation method. Further, on the silicon oxide film, a chromium film was o formed to a thickness of 1,000 A according to the electronbeam heated vacuum evaporation method to produce a photomask blank of this invention. On the chromium film of the blank as prepared above, a resist (AZ-1350, produced by Shipley Co.) was coated, and then a resist pattern was formed thereon by exposure to light and then developing of the resist. Thereafter, with the use of an etchant having the composition shown below, etching was carried out at a liquid temperature of 200C for 40 seconds to remove the exposed chromium film portions by etching to produce a desired photomask. Composition of etchant (NH4)2Ce(NO3)6 165.0 g He104(708) 43.0 ml Pure water 1,000 ml The following durability tests were conducted on ten sheets of the thus prepared photomask. The test for chemical resistance was carried out by immersing the photomask in a mixture of conc. sulfuric acid with 20 vol.% of a hydrogen peroxide (30%) aqueous solution under heating at 1100C. As a result, no failure occurred in the electroconductive film with no change whatsoever in electroconductivity. The test with respect to electrostatic charges was carried out by repeating 100 times pattern transfer onto photomask blanks having silver emulsion coatings in an atmosphere at 220C at a humidity of 40%. No failure occurred in the photomask. Example 4 On a glass plate, a film of tantalum was formed to o a thickness of 50 A according to the electron-beam heated vacuum evaporation method, and then a film of silicon oxide was formed to a thickness of 200 A according to the same deposition method. Further, on the silicon oxide film, a silicon film was formed to a thickness of o 1,000 A according to the same deposition method to produce a photomask blank of this invention. On the silicon film of the blank as prepared above, an electron-beam resist (COP, produced by Mead Chemical Co.) was coated. This step was followed by exposure to an electron beam and development of the image formed to form a resist pattern. Thereafter, with the use of an etchant having the composition shown below, etching was carried out at a liquid temperature of 200C for 2 minutes to remove the exposed silicon film portions to obtain a desired photomask. Composition of etchant AgNO3 1.0 g NH4F 0.5 g HNO3 100 ml Pure water 100 ml The chemical resistance test and the test with respect to electrostatic charges were conducted similarly as described in Example 3 for ten sheets of the thus prepared photomask. As a result of the chemical resistance test, no defect was found to occur in the electroconductive film and there was observed no change in electroconductivity. No defect caused by electrostatic charges was observed, either. For the photomask as prepared above, it was also possible to effect registration of the mask with the use of an electron beam with good precision. Example 5 A part of the chromium film in the photomask blank as prepared in Example 1 was removed by the dry etching method under the etching conditions shown below to produce a desired photomask. Etching conditions Etching gas: mixture of CC14 and air Gas pressure: 0.3 Torr High-frequency power applied: 200 W Etching time: 5 minutes Example 6 On a glass plate, a film of chromium was formed to o a thickness of 50 A according to the electron-beam heated vacuum evaporation method, and then a film of silicon oxide was formed to a thickness of 200 A according to the same method. Further, a tantalum film was formed on the silicon oxide film to a thickness of 1,000 A according to the electron-beam heated vacuum evaporation method to obtain a desired photomask blank. A part of the tantalum film in the blank as prepared above was removed by etching according to the dry etching method under the following etching conditions to obtain a desired photomask. Etching conditions Etching gas: CF4 Gas pressure: 0.01 Torr High-frequency power applied: 300 W Etching time 2 minutes Example 7 A part of the silicon film in the photomask blank as prepared in Example 4 was removed by etching according to the dry etching method under the following etching conditions to obtain a desired photomask. Etching conditions Etching gas: CCl4 Gas pressure: 0.02 Torr High-frequency power applied: 250 W Etching time: one minute Example 8 On a glass plate, a chromium film was formed to a o thickness of 50 A according to the electron-beam heating system vapor deposition method, and then a film of silicon oxide was formed thereon to a thickness of 200 o A according to the same method. Further, on the silicon oxide film, a silicon film was formed to a thickness of o 1,000 A to obtain a photomask blank. Following the procedures as described in Example 4, a part of the silicon film in the blank as prepared above was removed by etching to produce a desired photomask. Example 9 A part of the silicon film in the blank as prepared in Example 8 was removed by etching according to the dry etching method under the following conditions. Etching conditions Etching gas: CCl4 Gas pressure: 0.02 Torr High-frequency power applied: 250 W Etching time one minute With the use of ten sheets for each of the photomasks as prepared in Examples 5 to 9, the chemical resistance test and the test with respect to electrostatic charges were conducted similarly as described in Example 3. As a result of the chemical resistance tests, no defect was found to have developed in any of the photomasks, without change in electroconductivity. Further, no defect was observed to be caused by electrostatic charges.

Claims: CLAIMS: 1. A photomask blank comprising a transparent substrate (1), a metallic film (2) of a translucent and electroconductive material selected from the group consisting of Mo, Nb, Ta, Ti, V, W, Cr, Zr and Au on the substrate, and a masking film (3) comprising at least one layer of a masking material selected from the group consisting of metallic chromium, chromium oxide, chromium nitride, metallic silicon, iron oxide, metallic tantalum, tantalum oxide, tantalum nitride and combinations thereof on the metallic film (2). 2. A photomask blank according to claim 1 in which the film has a transmittance of at least 60 percent with respect to light of a wavelength of 400 to 550 nm and a sheet resistivity of at most 50 KQ per square and o has a thickness of 10 to 200 A. 3. A photomask blank according to claim 1 or 2 in which a chemically resistant and translucent protective film of a material selected from the group consisting of aluminum oxide, calcium oxide, magnesium oxide, silicon oxide, silicon nitride, cerium oxide, tantalum oxide, chromium oxide, and titanium oxide is interposed between the metallic film and the masking film. 4. A photomask blank according to claim 3 in which the protective film has a thickness of 10 to 1,000 A and a transmittance of 80% or more with respect to light of a wavelength of 400 to 600 nm. 5. A photomask blank according to claim 3 or 4 in which the protective film is made of silicon oxide. 6. A photomask comprising a transparent substrate (1), a metallic film (2) of a translucent and electroconductive material selected from the group consisting of Mo, Nb, Ta, Ti, V, W, Cr, Zr and Au on the substrate, and a patternized masking film (3a) comprising at least one layer of a masking material selected from the group consisting of metallic chromium, chromium oxides, metallic silicon, chromium nitrides, silicon oxides, iron oxides, metallic tantalum, tantalum oxides, tantalum nitrides and combinations thereof on the metallic film (2). 7. A photomask according to claim 6 in which the metallic film has a transmittance of at least 60 percent with respect to light of a wavelength of 400 to 550 nm and a sheet resistivity of at most 50 KQ per square and o has a thickness of 10 to 200 A. 8. A photomask according to claim 6 or 7 in which the masking film has been patternized by etching, and the metallic film has a characteristic of undergoing substantially no attack by the etching. 9. A photomask according to claim 6, 7 or 8 in which the masking film includes parts in the state of islands isolated from other parts of the same film. 10. A photomask according to any one of claims 6 to 9 in which a chemically resistant and translucent protective film of a material selected from the group consisting of aluminum oxide, calcium oxide, magnesium oxide, silicon oxide, silicon nitride, cerium oxide, tantalum oxide, chromium oxide, and titanium oxide is interposed between the metallic film and the masking film. 11. A photomask blank according to claim 10 in which the protective film has a thickness of 10 to 1,000 A and a transmittance of 80% or more with respect to light of a wavelength of 400 to 600 nm. 12. A photomask blank according to claim 9 or 10 in which the protective film is made of silicon oxide.

Inventors: KANEKI, SATORU, TABUCHI, KAZUHIRO
Applicants: DAI NIPPON INSATSU KABUSHIKI KAISHA
Application year: 1981
Main classification: G03F1
IPC codes: G03F1