Process for producing a phase shift layer-containing photomask

Abstract: A photomask blank for preparing a reticle for use in the production of integrated circuits comprises a substrate 30, an electrically conductive layer 31, a light-shielding thin film 32 and an ionizing radiation resist 33 formed of a coated spin-on-glass layer. A pattern is directly formed on the layer 33 by electron beam exposure. After development with a solvent to give a resist pattern 35 (Fig 1c) exposed portions of the light-shielding layer 32 are etched by an etching glass plasma 36 (Fig 1d) to form a light-shielding pattern 37. The remaining resist 33 is incinerated by oxygen plasma 38 (Fig 1e) to form a photomask (Fig 1f). Next, a transparent film 39 is spin-coated over the pattern 37 (Fig 1g), and pattern-exposed to electron beam radiation 40 (Fig 1h), baked (Fig 1i) and developed to form a reticle bearing a phase shift pattern 41 (Fig 1j). The correction of defects in the phase shift layer is also disclosed.

Description: The present invention relates generally to photomasks used for producing high-density integrated circuits such as LSIs and VLSIs and more specifically to phase shift layer-containing photomasks used for forming fine patterns with high accuracy,as well as their production and correction. So far, semiconductor integrated circuits such as ICs, LSIs and VLSIs have been produced by repeating a so-called lithographic cycle wherein resists are applied on substrates to be processed, like Si wafers, and the substrates are then exposed to light through steppers to form the desired patterns, followed by development and etching. The photomasks used in such a lithographic step and called "reticles" are now increasingly required to have much higher accuracy as current semiconductor integrated circuits become higher in performance and integration than ever before. Referring to a DRAM that is a typical LSI as an example, a dimensional variation of a five-fold reticle for a 1 megabit DRAM, i.e., of a reticle five-fold greater in size than the pattern to be exposed to light is required to have an accuracy of 0.15 µm even where the mean value = ± 3 σ ( σ is standard deviation). Likewise, five-fold reticles for 4- and 16-megabit DRAMs are required to have an accuracy of 0.1-0.15 µm and 0.05-0.1 µm, respectively. Furthermore, the line widths of device patterns formed with these reticles must be much finer, say, 1.2 µm for 1-megabit DRAMs and 0.8 µm for 16-megabit DRAMs, and various exposure processes are now being studied to meet such demand. With the next generation device patterns of, e.g. the 64 megabit DRAM class, however, stepper exposure systems using conventional reticles have been found to place some limitation on the resolution of resist patterns. Thus, a version of reticle based on a new idea, such as set forth in Japanese Provisional Patent Publication No. 58(1983)-173744, Japanese Patent Publication No. 62(1987)-59296, etc. and referred to as a phase shift mask, has been proposed in the art. Phase shift lithography using this reticle is a technique designed to improve the resolving power and contrast of projected images by operating the phase of light transmitted through the reticle. Photomasks such as those set forth in EP-A-0,090,924 also use a phase shift pattern to improve resolution and contrast, however, when the phase shift pattern is drawn on a resist layer with ionizing radiation there is no means of grounding the charges that build up and therefore a charging-up phenomenon occurs, which causes positional deviation or accuracy deterioration in the pattern produced. EP-A-0,440,467 discloses a process for producing a phase shift photomask, the phase shift layer itself being an electrically conducting thin film formed below the resist. JP-A-2,211,450 discloses a process for producing a phase shift mask, the mask having a conductive film which is of a lower shifter type than the photomask of the present invention, and EP-A-0,464,492 discloses a process for producing a phase shift photomask having an electrically conducting ITO layer applied between the substrate and the phase shift layer. In both publications the conducting layer is formed below the resist layer. It is an object of the present invention to provide an improved process for producing a phase shift layer-containing photomask with a phase shift pattern of improved position and accuracy. It is a further object of the present invention to provide a process for producing a phase shift pattern without occurence of the charging-up phenomenon. According to the present invention there is provided a process for producing a phase shift layer-containing photomask by forming a thin resist film on a layer of phase-shift layer forming material on a substrate, forming a pattern on the thin resist film with ionizing radiation, developing the thin resist film to form a resist pattern, etching an exposed portion of the phase-shift layer using the resist pattern as a mask and removing the remainder of the resist after the completion of etching, characterized in that said pattern formation is carried out with the ionizing radiation after an electrically conductive thin film has been formed above said thin resist film. Preferably, the electrically conductive thin film is obtained by spreading and depositing a Langmuir-Blodgett film. There now follows a brief description of the drawings accompanying the specification; the Figures are not necessarily referred to in sequence in the text. Fig. 1 is a series of sketches illustrating a phase shift process, Fig. 2 is a series of sketches illustrating the principles of a conventional process, Fig. 3 is diagrams illustrating examples of SOGs after they have been formed by heating, Fig. 4 is a series of sectional sketches for illustrating a production process according to the invention, Fig. 5 is a view showing the structure of one example of the electrically conductive compound used with the inventive process, Fig. 6 is a series of sketches for illustrating how to build up an LB film by the vertical dipping technique, Fig. 7 is a series of sketches for illustrating how to build up an LB film by the horizontal deposition technique, Fig. 8 is a series of sectional views for illustrating a conventional process for producing phase shift masks. Phase shift lithography will now be explained with reference to Figs. 1 and 2. Fig. 1 is a diagrammatical sketch showing the principium of the phase shift process and Fig. 2 is a diagrammatical sketch illustrating a conventional process. Figs. 1a and 2a are sectional views of reticles; Figs. 1b and 2b show the amplitude of light on the reticles; Figs. 1c and 2c depict the amplitude of light on wafers; and Figs. 1d and 2d illustrate the intensity of light on the wafers. In Figs. 1 or 2, reference numeral 1 stands for a substrate, 2 a light-shielding film, 3 a phase shifter and 4 incident light. In the conventional process, as illustrated in Fig. 2a, the substrate 1 formed of glass, etc. is provided thereon with the light-shielding film 2 formed of chromium, etc., only to form a given pattern of light-transmitting regions. In phase shift lithography, however, the phase shifter 3 to cause phase reversal (with a phase difference of 180°) is mounted on one pair of adjacent light-transmitting regions on a reticle, as sketched in Fig. 1a. According to the conventional process, therefore, the amplitude of light on the reticle is in the same phase, as illustrated in Fig. 2b, as is the amplitude of light on the wafer, as depicted in Fig. 2c, with the result that the patterns on the wafer cannot be separated from each other, as sketched in Fig. 2d. By contrast, the phase shift lithography enables the adjacent patterns to be distinctly separated from each other, as illustrated in Fig. 1d, because the light transmitting through the phase shifter is reversed in phase between the adjacent patterns, as depicted in Fig. 1b, so that the intensity of light on the pattern boundary can be reduced to zero. With the phase shift lithography, even patterns which cannot heretofore be separated from each other are thus made separable from each other, thereby achieving high resolution. Now, one example of conventional processes of producing phase shift reticles will be explained with reference to Fig. 8 which is a series of sectional views illustrating the steps of producing a typical phase shift reticle. As illustrated in Fig. 8a, a chromium film 12 is first formed on an optically polished substrate 11, and an ionizing radiation resist is uniformly coated and heated for drying thereon in conventional manner to form a resist layer 13. Then, a pattern is drawn on the resist layer 13 with ionizing radiation 14, as shown in Fig. 8b, followed by development and rinsing, thereby forming such a resist pattern 15 as sketched in Fig. 8c. If required, the edges, etc. of the resist pattern 15 are then cleared of such unnecessary matters as resist scums and whiskers by heating and descumming. Afterwards, portions exposed to open view between the resist pattern lines 15 and to be processed, i.e., the chromium layer 12 portions are dry-etched by an etching gas plasma 16, as shown in Fig. 8d, thereby to form a chromium pattern 17. After etching in this manner, the resist pattern 15, viz., the remaining resist is incinerated out by an oxygen plasma 18, as shown in Fig. 8 e, thereby obtaining such a complete photomask as shown in Fig. 8 f. Subsequently, this photomask is inspected to make a correction on the pattern, if required, followed by washing. After that, a transparent film 19 formed of, e.g. SiO 2 is formed on the chromium pattern 17, as depicted in Fig. 8g. Then, as depicted in Fig. 8h, an ionizing radiation resist 20 is formed on the transparent film 19 in similar manner as mentioned above, followed by alignment of the resist patterns 20, as shown in Fig. 8i. Subsequent drawing of a given pattern with ionizing radiations 21, development and rinsing give a resist pattern, as illustrated in Fig. 8j. Then, heating and descumming are effected, if required. After that, portions of the transparent film 19 exposed to open view between the resist pattern lines 22 are dry-etched by means of an etching gas plasma 23, as shown in Fig. 8k, to form a phase shifter pattern 24. Finally, the remainder of the resist is incinerated out by an oxygen plasma 25, as illustrated in Fig. 81. By the foregoing steps, such a phase shift photomask containing phase shifters 24 as shown in Fig. 8m is produced. Before discussing the production process according to this invention, we will now give a brief explanation to spin-on-glass (hereinafter "SOG" for short) that is a film of an organic solvent solution of an organosilicon compound which has been converted into silicon oxide by coating, drying and heating. The starting materials used for SOG are a metal alkoxide such as tetraethoxysilane - Si(OC 2 H 5 ) 4 , bipolar solvents such as water and methanol and hydrochloric acid. To leave a methyl group (-CH 3 ) in SOG, triethoxymethylsilane - CH 3 Si(OC 2 H 5 ) 3 , diethoxydimethoxysilane - (CH 3 ) 2 Si(OC 2 H 5 ) 3 or trimethylethoxysilane - (CH 3 ) 3 Si(OC 2 H 5 ) may be added to tetraethoxysilane in an amount of a few % to a few tens %. One example of the mixing ratio of these starting materials is: Si(OC 2 H 5 ) 4 :CH 3 Si(OC 2 H 5 ) 3 :H 2 O:C 2 H 5 OH:HCl = 100:2:660:1050:6 Upon mixing together, the starting materials start hydrolysis and polycondensation. These reactions are schematically expressed as follows: Hydrolysis: wherein Et=C 2 H 5 Polycondensation: ≡Si-OH + HO-Si≡→≡Si-O-Si≡+H 2 O Total Reaction: Through such hydrolysis and polycondensation, an Si-O polymer (polysilicate) having a low molecular weight is obtained. To obtain a methyl group-containing SOG, a mixture of Si(OC 2 H 5 ) 4 with CH 3 Si(OCH 5 ) 3 is used as one of the starting materials. The reaction scheme is then expressed as follows: Hydrolysis: Polycondensation: ≡Si-OH + HO-Si≡→≡Si-O-Si≡ + H 2 O Total Reaction: This low-molecular-weight SOG is spin-coated and softbaked (at 80-120°C) on a substrate, whereby the molecular weight of SOG is slightly increased. Heating [(CH 3 ) n/2 Si(OEt) a (OH) b O c ] n [(CH 3 ) n*/2 Si((OEt) a* (OH) b* O c* ] n* wherein a*<a, b*<b, c*>c, and n*>n Upon this substrate being further heated at 400-500°C, dehydration and dealcoholization proceed to cause a drastic increase in molecular weight, giving an intimate SOG film. [(CH 3 ) n*/2 Si(OEt) a* (OH) b* O c* ] n [(CH 3 ) n'/2 Si(OH) x O y ] n' wherein n', x and y approximate to infinity, zero and two, respectively. The methyl group-containing SOG allows the methyl group in the film to be left behind, even after heating at 400-500°C 3 One example of the SOG structure after heating at 400-500°C is illustrated in Fig. 3. When SOG is irradiated with electron beams, ion beams, radiation light such as X rays, r rays and SOR or laser light - all hereinafter called the energy beams - after the above-mentioned soft baking, polymerization takes place at the irradiated region, resulting in an increase in molecular weight. Due to a difference in molecular weight, this SOG has the property of leaving its irradiated region intact, when it is developed with a solvent like an alcohol after irradiation. By the way, when SOG which contains an acid generator such as halogenoacid onium salt and other compounds like triphenyl-sulfonium-trifrate, tetrabromobisphenol, 1,1-bis-parachlorophenyl-2,2,2-trichloroethane, etc. is irradiated with the energy beams after soft-baking, the oxygen generator gives out an acid which in turn acts on the hydroxyl (-OH) and ethoxy (-OC 2 H 5 ) groups remaining in SOG to allow dehydration or dealcoholization to proceed, resulting in an increase in molecular weight. When compared with the acid generator-free SOG, the acid generator-containing SOG has thus the property of being higher in molecular weight (sensitivity) even at a lower dosage of the energy beams. Reference will now be made in the following Example 1 to a more practical process for producing phase shift layer-containing photomasks, which can effectively prevent a charging-up phenomenon at the time of providing phase shift reticles with phase shifters to eliminate pattern distortions due to the charging-up phenomenon, thereby making it possible to produce highly accurate phase shift reticles. Example 1: Fig. 4 is a series of sectional sketches illustrating the steps of one embodiment of the process for producing such photomasks. As shown in Fig. 4a, an SiO 2 film is first provided on a reticle with SOG or by means of sputtering or other techniques in the form of a shifter layer 54. Subsequently, an ionizing radiation resist is uniformly coated on the phase shifter layer 54 by means of conventional techniques, e.g. spin coating, and is then heated thereon for drying to form a resist layer 55 of about 0.1 to 2.0 µm in thickness, as shown in Fig. 4 b. The heat treatment for drying may usually be carried out at 80 to 200°C for about 20 to 60 minutes, although this depends upon the type of resist used. Then, this resist layer 55 is provided thereon with an electrically conductive layer 56. The conductive layer 56 of about 0.05 to 0.5 µm in thickness, if formed as of a tetracyanoquinodimethane (TCNQ) complex, may be obtained by dissolving it in an organic solvent such as cyclohexane and coating the solution uniformly on the resist layer 55 by means of spin coating or other conventional technique, followed by heating for drying - see Fig. 4b. The heat treatment for drying may be carried out at 50 to 100°C for about 2 to 10 minutes, although this again depends upon the type of TCNQ complexes used. When a metal film is used as the conductive film 56, sufficient electrical conductivity may be obtained by forming such a metal as aluminium, titanium, chromium, gold or copper on the resist layer 55 to a thickness of 200 to 3000Å by means of vapor deposition, sputtering or other technique. Then, as illustrated in Fig. 4c, the resist layer 55 is aligned conventionally, and a pattern is drawn thereon by ionizing radiation 57 with the use of exposure hardware such as an electron beam drawer. In this case, it is possible to draw the pattern with high accuracy, because excessive charges are so grounded through the conductive layer 56 formed on the resist film 55 that alignment marks can be easily detected with no occurrence of the charging-up phenomenon. Subsequently, the pattern is developed with a given developing solution and rinsed with a given rinsing solution to form such a resist pattern 58 as depicted in Fig. 4d. Use of an ordinary alkali development type of resist gives rise to coincident release of the conductive layer 56 at the time of development. Also, when the conductive layer 56 uses a type of resist insoluble in the developer, the pattern may be formed by releasing the conductive layer 56 with an organic solvent and developing it with a predetermined developer. After heating for drying and descumming have been carried out, if required, portions of the transparent film 54 exposed to open view between lines of the resist pattern 58 are dry-etched by an etching gas plasma 59, as shown in Fig. 4d, to form a phase shifter pattern 54 - see Fig. 4e. Then, the remaining resist is incinerated out by an oxygen Plasma 60, as shown in Fig. 4f. Through the above-mentioned steps, such a phase shift mas containing phase shifter 54 as shown in Fig. 4g is completed. The thus formed phase shift pattern provides a high-quality phase shift mask unlikely to suffer a positional deviation or accuracy deterioration, which may otherwise occur due to the charging-up phenomenon at the time of pattern exposure. Incidentally, when the electrically conductive layer 56 of Fig. 4b is coated on the resist layer 55 by means of spin coating or other conventional technique, there is a fear that because the conductive layer has a thickness as great as 100 to 300 nm and has poor thickness uniformity, the resist layer decreases in resolution and suffers a large in-plane dimensional variation. Referring further to coating techniques, such as when an electrically conductive polymer based on an organic solvent is coated on a water-soluble resist by means of spin coating, it is required to use a water-soluble intermediate layer formed as of polyvinyl alcohol at an additional separate step; this results in an increase in film thickness and hence a deterioration of the resolution of the resist layer. To avoid these, the electrically conductive layer 56 may be coated on the resist layer by means of the Langmuir-Blodgett technique (the LB technique). Fig. 5 shows the structure of N-docosylpyridinium·(TCNQ) 2 that is one example of electrically conductive compounds used to this end. Other organic, electrically conductive materials may also be used, including polyacetylene, polythiophene, polypyrrole, polythiadyl, polyazulenium, polyindene, polyindole, poly-para-phenylene, polynaphthylene, polyanthracene, polyaniline, polyphthalocyanine and polyferrocene. Referring to how to make an LB conductive film used as the conductive layer 56, such an electrically conductive compound shown in in Fig. 5 is spread on the surface of water in the form of a chloroform solution to form a monolayer. This monolayer is deposited by such a vertical dipping method as shown in Fig. 6 or such a horizontal lifting method as shown in Fig. 7 on the resist layer 55 on which the shifter layer 54 is to be patterned, thereby forming a multilayer. Referring first to the vertical dipping technique shown in Figs. 6a to 6c, a substrate 65 made hydrophobic with iron stearate, etc. is vertically dipped in a subphase, while piston pressure 64 is loaded to the surface of an underlying water 63 in which a monolayer consisting of hydrophobic and hydrophilic groups 61 and 62 has been formed, whereby the monolayer is transferred on the side of the hydrophobic group 61 onto the substrate 65. But the monomolecular film is not transferred onto the substrate, while it is drawn up. Such a film is called the X film. According to the technique shown in Figs. 6d to 6f, the film is transferred onto the substrate during both periods of dipping and drawing-up - called the Y film, and according to the technique depicted in Figs. 6g to 6i, the film is not deposited onto the substrate during dipping but transferred onto the substrate during drawing-up - referred to as the Z film. Referring further to the horizontal deposition technique shown in Figs. 7a to 7c, piston pressure 64 is applied to a monolayer formed on the surface of water divided by a first partition 66 to bring a substrate 64 into horizontal contact with the monolayer for deposition of hydrophobic groups 61 onto the surface of the substrate 65 - see Fig. 7a. After that, a second partition 67 is moved to the portion of the substrate 65 in no contact with the first partition 66 to draw up the substrate 65 - see Figs. 7b and 7c. Then, the operations (a) to (c) are repeated to form a multilayer having a given thickness - see Fig. 7d. In this case, only the X film is formed.

Claims: A process for producing a phase shift layer-containing photomask by forming a thin resist film (55) on a layer of phase shift layer forming material (54) on a substrate (51), forming a pattern on the thin resist film (55) with ionizing radiation (57), developing the thin resist film (55) to form a resist pattern (58), etching an exposed portion of the phase shift layer (54) using the resist pattern (58) as a mask and removing the remainder of the resist after the completion of etching, characterized in that said pattern formation is carried out with the ionizing radiation (57) after an electrically conductive thin film (56) has been formed above said thin resist film (55). A process as claimed in claim 1, characterized in that said electrically conductive thin film (56) is obtained by spreading and depositing a Langmuir-Blodgett film.

Inventors: FUJITA HIROSHI, KURIHARA MASA-AKI, MIKAMI KOICHI, MIYASHITA HIROYUKI, TAKAHASHI YOICHI, FUJITA, HIROSHI, KURIHARA, MASA-AKI, MIKAMI, KOICHI, MIYASHITA, HIROYUKI, TAKAHASHI, YOICHI, Fujita, Hiroshi, c/o Dai Nippon, Kurihara, Masa-aki, c/o Dai Nippon, Mikami, Koichi, c/o Dai Nippon, Miyashita, Hiroyuki, c/o Dai Nippon, Takahashi, Yoichi, c/o Dai Nippon
Applicants: DAINIPPON PRINTING CO LTD, DAI NIPPON PRINTING CO., LTD.
Application year: 1991
Main classification: G03F1
IPC codes: G03F1