TWI465838B - Multi-tone photomask, photomask blank, and pattern transfer method - Google Patents
Multi-tone photomask, photomask blank, and pattern transfer method Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- 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
- G03F1/54—Absorbers, e.g. of opaque materials
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- 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
- G03F1/54—Absorbers, e.g. of opaque materials
- G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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Description
本發明係關於一種多色調光罩、光罩基底及圖案轉印方法等。The present invention relates to a multi-tone mask, a mask substrate, a pattern transfer method, and the like.
近年來，於大型FPD(Flat Panel Display，平板顯示器)用光罩之領域中，嘗試使用具有半透光性區域(所謂之灰色調部)之多色調光罩(所謂之灰色調光罩)而削減光罩數量(例如，參照月刊FPD Intelligence、p.31-35、1999年5月)。In recent years, in the field of large-scale FPD (Flat Panel Display) reticle, attempts have been made to use a multi-tone mask (so-called gray dimming cover) having a semi-transparent region (so-called gray tone portion). Reduce the number of masks (for example, refer to the monthly FPD Intelligence, p.31-35, May 1999).
此處，如圖11(1)及圖12(1)所示，多色調光罩於透光性基板5上具有將曝光之光遮蔽之遮光部1、使曝光之光透過之透光部2、以及使曝光之光之一部分透過的半透光部3。半透光部3係用以獲得遮光部與透光部之中間透射率之區域，例如係如圖11(1)所示之形成有具有遮光部與透光部之中間透射率之半透光膜3a'的區域，或者係如圖12(1)所示之形成有使用(搭載)多色調光罩而進行圖案轉印之大型FPD用曝光機之解像極限以下的微細遮光圖案3a、及微細透射部3b(所謂之灰色調圖案)之區域。形成半透光部3之目的在於：降低透過該等區域之曝光之光的透射量，以降低該區域之照射量，將與相關區域相對應之光阻劑顯影之後所減少之膜厚控制為所期望之值。Here, as shown in FIGS. 11(1) and 12(1), the multi-tone mask has a light-shielding portion 1 that shields the exposed light, and a light-transmitting portion 2 that transmits the exposed light to the light-transmitting substrate 5. And a semi-transmissive portion 3 that transmits a portion of the exposed light. The semi-transmissive portion 3 is used to obtain a region of intermediate transmittance between the light-shielding portion and the light-transmitting portion, for example, a semi-transmissive light having an intermediate transmittance having a light-shielding portion and a light-transmitting portion as shown in FIG. 11 (1). As shown in Fig. 12 (1), the thin light-shielding pattern 3a having a resolution limit of a large-sized FPD exposure machine that is patterned and transferred using a multi-tone mask as shown in Fig. 12 (1), and A region of the fine transmissive portion 3b (a so-called gray tone pattern). The purpose of forming the semi-transmissive portion 3 is to reduce the amount of light transmitted through the exposed regions to reduce the amount of exposure of the region, and to reduce the film thickness after developing the photoresist corresponding to the relevant region to The expected value.
當將大型多色調光罩搭載於鏡面投影方式、或使用有透鏡之透鏡投影方式之大型曝光裝置而使用之情形，透過半透光部3的曝光之光整體之曝光量不足，因此，對於經由該半透光部3而曝光之正型光阻劑而言，僅是膜厚變薄，且會殘留於基板上。亦即，因曝光量之差異，於與通常之遮光部1相對應之部分、及與半透光部3相對應之部分，光阻劑相對於顯影液之溶解性產生差異，因此顯影後之光阻劑形狀如圖11(2)及圖12(2)所示，與通常之遮光部1相對應之部分1'例如約為1μm，與半透光部3相對應之部分3'例如約為0.4~0.5μm，與透光部2相對應之部分則成為無光阻劑之部分2'。而且，於無光阻劑之部分2'進行被加工基板之第1蝕刻，藉由灰化等而除去與半透光部3相對應之較薄之部分3'之光阻劑，於該部分進行第2蝕刻，藉此，利用1個光罩而實施先前由2個光罩實施之步驟，從而削減光罩數量。When a large-sized multi-tone mask is used in a mirror projection method or a large exposure apparatus using a lens projection method, the exposure amount of the entire light that has passed through the semi-transmissive portion 3 is insufficient, and therefore, In the positive type resist which is exposed by the semi-transmissive portion 3, only the film thickness is reduced and remains on the substrate. That is, the difference between the exposure amount and the portion corresponding to the normal light-shielding portion 1 and the portion corresponding to the semi-light-transmitting portion 3 cause a difference in solubility of the photoresist with respect to the developer, and thus the image is developed. The shape of the photoresist is as shown in Fig. 11 (2) and Fig. 12 (2), and the portion 1' corresponding to the normal light shielding portion 1 is, for example, about 1 μm, and the portion 3' corresponding to the semi-light transmitting portion 3 is, for example, about When it is 0.4 to 0.5 μm, the portion corresponding to the light transmitting portion 2 becomes a portion 2' without a photoresist. Further, the first etching of the substrate to be processed is performed on the portion 2' of the photoresist-free portion, and the thin portion 3' of the photoresist corresponding to the semi-transmissive portion 3 is removed by ashing or the like, in which the portion is removed. By performing the second etching, the steps previously performed by the two masks are performed by one mask, and the number of masks is reduced.
然而，用以製造微處理器、半導體記憶體、系統LSI(Large Scale Integration，大型積體電路)等之半導體裝置之LSI用光罩相對較小，最大僅為6吋見方左右，多數情況下，其搭載於步進(單步投影曝光)方式之縮小投影曝光裝置而使用。又，LSI用光罩中，自藉由透鏡系統而排除色差及藉此提高解像性之觀點考慮，使用單色之曝光之光。與該LSI用光罩相關之單色之曝光波長之短波長化，係朝超高壓水銀燈之g線(436nm)及i線(365nm)、KrF準分子雷射(248nm)、ArF準分子雷射(193nm)發展。However, LSI reticle for manufacturing semiconductor devices such as microprocessors, semiconductor memories, and system LSIs (Large Scale Integration) is relatively small, and is only about 6 吋 square, and in most cases, It is used in a step-down (single-step projection exposure) reduction projection exposure apparatus. Further, in the LSI photomask, a single-color exposure light is used from the viewpoint of eliminating the chromatic aberration by the lens system and thereby improving the resolution. The short-wavelength of the single-color exposure wavelength associated with the LSI reticle is a g-line (436 nm) and an i-line (365 nm), KrF excimer laser (248 nm), ArF excimer laser toward an ultrahigh pressure mercury lamp. (193nm) development.
又，用以製造LSI用光罩之小型遮罩基底需要高蝕刻精度，因此，藉由乾式蝕刻而使形成於遮罩基底上之薄膜圖案化。Moreover, since the small mask substrate for manufacturing the LSI photomask requires high etching precision, the thin film formed on the mask substrate is patterned by dry etching.
相對於此，FPD用大型光罩相對較大，例如為330mm×450mm至1220mm×1400mm，多數情況下，其搭載於鏡面投影方式或使用有透鏡之透鏡投影方式之曝光裝置而使用。又，當將FPD用大型光罩搭載於鏡面投影(基於掃描曝光方式之等倍投影曝光)方式之曝光裝置而使用之情形，(I)由於僅利用反射光學系統而經由光罩進行曝光，故因介設有如LSI用光罩之透鏡系統而產生之色差不會成為問題；以及(II)目前，雖擔心多色波曝光之影響(因透射光或反射光而產生之干涉或色差之影響等)，但可確保比單色波曝光更大之曝光光強度之多色波曝光於綜合生產方面較有利，因此，利用超高壓水銀燈之i~g線之寬頻帶而實施多色波曝光。又，即便當將FPD用大型光罩搭載於透鏡方式之大型曝光裝置而使用之情形，根據上述(II)所記載之理由等，仍同樣地實施多色波曝光。複數個波長之曝光(多色波曝光)處理之優點在於：與單一波長之曝光(單色波曝光)之情形相比較，曝光光強度可更大。例如，與僅利用i線或g線之單色波曝光相比較，當利用包含h線在內之自i線遍及g線之波長帶之光而進行曝光時，曝光光強度較大。因此，可提高裝置之生產性。又，例如，於多數情況下，FPD裝置等之大型之顯示裝置係利用等倍曝光法而製造。與LSI裝置等之製造中所使用之縮小曝光法相比較，等倍曝光法具有如下優點：因照射至裝置面之曝光之光的入射強度較小，故而可藉由利用複數個波長而彌補照射至裝置面之曝光之光的入射強度。On the other hand, the large-sized photoreceptor for FPD is relatively large, and is, for example, 330 mm × 450 mm to 1220 mm × 1400 mm. In many cases, it is mounted on a mirror projection method or an exposure apparatus using a lens projection method using a lens. In addition, when the FPD is mounted on a large-sized photomask by an exposure apparatus of a mirror projection (double-projection exposure by a scanning exposure method), (I) exposure is performed via a photomask only by the reflection optical system, The chromatic aberration caused by the lens system such as the LSI reticle is not a problem; and (II) at present, the influence of the multicolor wave exposure (the influence of interference or chromatic aberration due to transmitted light or reflected light) However, it is advantageous to ensure that the multi-color wave exposure of the exposure light intensity larger than the monochromatic wave exposure is advantageous in terms of integrated production. Therefore, multi-color wave exposure is performed using the wide band of the i~g line of the ultrahigh pressure mercury lamp. In addition, even when the FPD is mounted on a large-sized exposure apparatus using a large-sized photomask, the multi-color wave exposure is performed in the same manner as described in the above (II). The advantage of multiple wavelength exposure (multi-color wave exposure) processing is that the exposure light intensity can be greater compared to the single wavelength exposure (monochrome exposure). For example, the exposure light intensity is large when exposure is performed using light of a wavelength band of the g-line from the i-line including the h-line, compared to the monochromatic wave exposure using only the i-line or the g-line. Therefore, the productivity of the device can be improved. Further, for example, in many cases, a large display device such as an FPD device is manufactured by a double exposure method. Compared with the reduced exposure method used in the manufacture of an LSI device or the like, the double exposure method has an advantage that since the incident intensity of the light irradiated to the device surface is small, the irradiation can be compensated by using a plurality of wavelengths. The incident intensity of the exposed light on the device surface.
又，FPD用大型光罩之製造中，難以製作大型之乾式蝕刻裝置，即便已製成該大型之乾式蝕刻裝置，價格亦非常高，且技術上難以實現均一之蝕刻。因此，就用以製造FPD用大型光罩之大型遮罩基底而言，多數情況下，重視成本方面及生產量而採用使用有蝕刻液之濕式蝕刻，使形成於遮罩基底上之薄膜圖案化。Further, in the manufacture of a large-sized photomask for FPD, it is difficult to produce a large-sized dry etching apparatus, and even if the large-sized dry etching apparatus is manufactured, the price is extremely high, and it is technically difficult to achieve uniform etching. Therefore, in the case of a large-sized mask substrate for manufacturing a large-sized photomask for an FPD, in many cases, a wet etching using an etching solution is applied to a film pattern formed on a mask substrate in consideration of cost and throughput. Chemical.
近年來，FPD用大型多色調光罩之需求精度(規格值)變得嚴格。與此同時，業者亦期望削減成本。In recent years, the demand accuracy (specification value) of large-sized multi-tone masks for FPD has become strict. At the same time, the industry also expects to cut costs.
因此，本發明者等人關於FPD用大型多色調光罩基底及光罩，就如下課題進行了檢討，該課題之目的在於，於藉由濕式蝕刻而於半透光膜及遮光膜上實施圖案化之情形，滿足變得嚴格之需求精度(規格值)。Therefore, the inventors of the present invention have reviewed the following problems regarding a large-sized multi-tone mask base and a photomask for FPD, and the object of the present invention is to perform a wet etching on a semi-transmissive film and a light-shielding film. In the case of patterning, the demand accuracy (specification value) that becomes strict is satisfied.
結果發現難以同時滿足如下三個方面，即，It was found that it is difficult to simultaneously satisfy the following three aspects, namely,
(1)抑制半透光膜之遍及i線~g線之波長帶之透射率變化量，(1) suppressing the change in transmittance of the semi-transmissive film across the wavelength band of the i-line to the g-line,
(2)將透過半透光膜之曝光之光的透射率調整為所期望之值(尤其是容易進行微調整)；以及(2) adjusting the transmittance of the light that has passed through the semi-transmissive film to a desired value (especially, easy to fine-tune);
(3)可採用缺陷少之製程。(3) A process with few defects can be used.
以下，對於上述情況進行詳細說明。Hereinafter, the above will be described in detail.
首先，作為前提，使用濕式蝕刻而製作之FPD用大型多色調光罩中之遮光膜通常係使用Cr系遮光膜。First, as a premise, a light-shielding film in a large-sized multi-tone mask for FPD produced by wet etching is generally a Cr-based light-shielding film.
於將MoSiN用作半透光膜之FPD用大型多色調光罩基底及光罩中，可使用自基板側起具有基板\MoSiN半透光膜\Cr系遮光膜之積層構造之光罩基底(先前例1)。此時，對於MoSiN半透光膜而言，其i線-g線間之透射率變動相對較大，但用以獲得特定之透射率之膜厚相對較厚(例如約20~35nm)，因此，容易藉由膜厚而調整及控制透射率。又，當將MoSiN用作半透光膜之情形，可採用先形成半透光膜(圖10(1))及後形成半透光膜(圖10(2))之兩種製程。In the large-sized multi-tone mask base and the reticle for FPD using MoSiN as a semi-transmissive film, a reticle substrate having a laminated structure of a substrate \MoSiN semi-transmissive film/Cr-based light-shielding film from the substrate side can be used ( Previous example 1). At this time, for the MoSiN semi-transmissive film, the transmittance between the i-line and the g-line varies relatively large, but the film thickness for obtaining a specific transmittance is relatively thick (for example, about 20 to 35 nm), It is easy to adjust and control the transmittance by the film thickness. Further, in the case where MoSiN is used as the semi-transmissive film, two processes of forming a semi-transparent film (Fig. 10 (1)) and then forming a semi-transparent film (Fig. 10 (2)) can be employed.
於將CrN用作半透光膜之FPD用大型多色調光罩基底及光罩(先前例2)中，對於CrN半透光膜而言，其i線-g線間之透射率變動相對較小，但用以獲得特定之透射率之膜厚相對較薄(例如約10nm以下之非常薄之厚度)，因此，難以藉由膜厚而調整或控制透射率。又，CrN半透光膜幾乎不具有與Cr系遮光膜之蝕刻選擇性，因此，必需首先使Cr系遮光膜成膜並使之圖案化，其後，使CrN半透光膜成膜並使之圖案化(必需採用所謂之後形成半透光膜之製程)。於後形成半透光膜之製程之情形時，必需將成膜與使所形成之膜圖案化之一系列步驟分成2次進行，因此與先形成半透光膜之製程相比較，缺陷增加。In the large multi-tone mask substrate and the photomask for the FPD using CrN as a semi-transmissive film (previous example 2), the transmittance variation between the i-line and the g-line is relatively high for the CrN semi-transmissive film. Small, but the film thickness for obtaining a specific transmittance is relatively thin (for example, a very thin thickness of about 10 nm or less), and therefore, it is difficult to adjust or control the transmittance by the film thickness. Further, since the CrN semi-transmissive film hardly has etching selectivity with the Cr-based light-shielding film, it is necessary to first form and pattern the Cr-based light-shielding film, and then form a CrN semi-transmissive film. The patterning (required to use a process of forming a semi-transmissive film later). In the case of the process of forming the semi-transmissive film, it is necessary to divide the film formation and the series of steps of patterning the formed film into two, so that the defects are increased as compared with the process of forming the semi-transparent film first.
如上所述，尚未提出具有先前例1及先前例2該兩者之優點且可消除兩者之缺點之技術。亦即，尚未提出可同時滿足上述(1)~(3)之技術。As described above, the technique having the advantages of both the former example 1 and the previous example 2 and eliminating the disadvantages of both has not been proposed. That is, a technique that satisfies the above (1) to (3) has not been proposed yet.
本發明係關於一種FPD用大型多色調光罩基底及光罩，其目的在於提供一種可同時滿足以下之(1)~(3)之技術。The present invention relates to a large multi-tone mask substrate for a FPD and a photomask, and an object thereof is to provide a technique capable of simultaneously satisfying the following (1) to (3).
(1)抑制半透光膜之遍及i線~g線之波長帶之透射率變化量。(1) The amount of change in transmittance of the wavelength band across the i-line to the g-line of the semi-transmissive film is suppressed.
(2)將透過半透光膜之曝光之光的透射率調整為所期望之值(尤其是容易進行微調整)。(2) The transmittance of the light that has passed through the semi-transmissive film is adjusted to a desired value (especially, it is easy to perform fine adjustment).
(3)可採用缺陷少之製程。(3) A process with few defects can be used.
本發明者等人為解決上述問題而進行了銳意研究開發。結果發現：The inventors of the present invention have made intensive research and development in order to solve the above problems. turn out:
(i)將半透光膜設為相對於遍及i線~g線之波長帶之曝光之光的透射率光譜互不相同之2層以上之半透光膜的積層膜，藉此(i) the semi-transmissive film is a laminated film of two or more semi-transmissive films having different transmittance spectra of light exposed in the wavelength band of the i-th to g-g lines, thereby
(ii)包含上述積層膜之半透光膜係藉由2層以上之半透光膜之積層，而可恰當地控制透過相對於包含上述積層膜之半透光膜且遍及i線~g線之波長帶的曝光之光之透射率變化量；且包含上述積層膜之半透光膜係藉由2層以上之半透光膜之積層，而可恰當地控制透過包含上述積層膜之半透光膜的曝光之光的透射率。藉此，本發明者等人發現可獲得可同時滿足上述(1)~(3)之FPD用大型多色調光罩基底及光罩。(ii) The semi-transmissive film including the laminated film is laminated by a semi-transmissive film of two or more layers, and can be appropriately controlled to be transmitted through the semi-transparent film including the laminated film and over the i-g-g line. The amount of change in transmittance of the exposed light in the wavelength band; and the semi-transmissive film including the laminated film is laminated by a semi-transmissive film of two or more layers, and can be appropriately controlled to transmit through the semipermeable film including the laminated film. The transmittance of the exposed light of the light film. As a result, the inventors of the present invention have found that a large-sized multi-tone mask base and a photomask for FPD which can simultaneously satisfy the above (1) to (3) can be obtained.
進而，本發明者發現，即便構成上述積層膜之各半透光膜之材料相同，亦會由於各半透光膜之膜厚而可獲得抑制遍及i線~g線之波長帶之透射率變化量的效果，或無法獲得該效果。據此，本發明者發現：Further, the inventors have found that even if the materials of the semi-transmissive films constituting the laminated film are the same, the transmittance of the wavelength band across the i-g-g line can be suppressed due to the film thickness of each semi-transmissive film. The effect of the amount, or the effect cannot be obtained. Accordingly, the inventors found that:
(iii)對於以「包含上述積層膜之半透光膜係可藉由2層以上之半透光膜之積層，而控制透過相對於包含上述積層膜之半透光膜且遍及i線~g線之波長帶的曝光之光的透射率變化量(抑制為所期望之值)，且包含上述積層膜之半透光膜係可藉由2層以上之半透光膜之積層，而控制透過包含上述積層膜之半透光膜的曝光之光之透射率(控制為所期望之值)」之方式而構成上述積層膜的各半透光膜之材料及膜厚進行選擇(調整)，藉此，可獲得可同時滿足上述(1)~(3)之FPD用大型多色調光罩基底及光罩，從而完成本發明。(iii) controlling the transmission of the semi-transmissive film comprising the laminated film by a semi-transmissive film comprising two or more layers, and controlling the permeation with respect to the semi-transparent film comprising the laminated film, and extending over the i-line to the g The amount of change in transmittance of the exposed light in the wavelength band of the line (suppressed to a desired value), and the semi-transmissive film including the laminated film can be controlled by the lamination of two or more layers of the semi-transmissive film. Selecting (adjusting) the material and film thickness of each of the semi-transmissive films constituting the laminated film, including the transmittance of the exposed light of the semi-transmissive film of the laminated film (controlled to a desired value), Thus, a large-sized multi-tone mask base and a photomask for FPD which can satisfy the above (1) to (3) can be obtained, and the present invention has been completed.
本發明之多色調光罩、光罩基底及圖案轉印方法具有如下構成。The multi-tone mask, the mask substrate, and the pattern transfer method of the present invention have the following constitution.
一種光罩基底，其特徵在於：其係用以製作多色調光罩者，該多色調光罩係於透光性基板上，依序具有使曝光之光之一部分透過之半透光膜及將曝光之光遮蔽之遮光膜，且藉由對上述半透光膜及上述遮光膜分別實施圖案化而形成有使曝光之光透過之透光部、使曝光之光之一部分透過之半透光部、以及將曝光之光遮蔽之遮光部，上述半透光膜包含相對於遍及i線~g線之波長帶之曝光之光的透射率光譜互不相同之2層以上之半透光膜的積層膜，包含上述積層膜之半透光膜係藉由2層以上之半透光膜之積層，而控制相對於透過包含上述積層膜之半透光膜且遍及i線~g線之波長帶之曝光之光的透射率變化量，且包含上述積層膜之半透光膜係藉由2層以上之半透光膜之積層，而控制透過包含上述積層膜之半透光膜的曝光之光之透射率。A reticle substrate, characterized in that it is used for fabricating a multi-tone mask, which is attached to a light-transmissive substrate, and has a semi-transparent film that partially transmits the exposed light and a light-shielding film that is shielded by light, and by patterning the semi-transmissive film and the light-shielding film, respectively, forming a light-transmitting portion through which the exposed light is transmitted, and a semi-transmissive portion through which a part of the exposed light is transmitted And a light-shielding portion that shields the exposed light, wherein the semi-transmissive film includes a layer of two or more semi-transmissive films having different transmittance spectra of light exposed to a wavelength band extending from the i-th to the g-line. The film, the semi-transmissive film including the laminated film is laminated by a semi-transmissive film of two or more layers, and is controlled to pass through a wavelength band of the semi-transmissive film including the laminated film and extending over the i-g-g line. The amount of change in the transmittance of the exposed light, and the semi-transmissive film including the laminated film is controlled by a laminate of two or more semi-transmissive films to control the light transmitted through the semi-transmissive film including the laminated film. Transmittance.
如構成1之光罩基底，其特徵在於：構成上述積層膜之至少一方之半透光膜係具有抑制遍及i線~g線之波長帶之透射率變化量之功能的膜，且藉由調整構成上述積層膜之至少一方之半透光膜的膜厚，而將透過包含上述積層膜之半透光膜的曝光之光的透射率調整為所期望之值。In the reticle substrate of the first aspect of the invention, the semi-transmissive film constituting at least one of the laminated films has a function of suppressing a change in transmittance of a wavelength band extending from the i-th to the g-line, and is adjusted by The film thickness of the semi-transmissive film constituting at least one of the laminated films is adjusted to a desired value by the transmittance of the light transmitted through the semi-transmissive film including the laminated film.
如構成1或2之光罩基底，其特徵在於：包含上述積層膜之半透光膜之相對於遍及i線~g線之波長帶之曝光之光的透射率變化量為2.0%以下。In the mask base of the first or second embodiment, the amount of change in transmittance of the light of the semi-transmissive film including the laminated film with respect to the wavelength band passing through the i-g to g-line is 2.0% or less.
如構成1至3中任一項之光罩基底，其特徵在於：於透光性基板上依序積層半透光膜之積層膜、及包含含有鉻之材料之遮光膜而成，上述半透光膜之積層膜係依序積層包含含有鉻與氮之材料之半透光膜、以及包含含有鉬與矽之材料或含有鉬、矽及氮之材料的半透光膜而成。The reticle substrate according to any one of the first to third aspect, wherein the laminated film of the semi-transmissive film and the light-shielding film containing a material containing chromium are sequentially laminated on the light-transmitting substrate, and the semi-transparent film is formed. The laminated film of the light film is formed by sequentially laminating a semi-transmissive film containing a material containing chromium and nitrogen, and a semi-transmissive film containing a material containing molybdenum and niobium or a material containing molybdenum, niobium and nitrogen.
一種多色調光罩，其特徵在於：於透光性基板上，依序具有使曝光之光的一部分透過之半透光膜及將曝光之光遮蔽之遮光膜，藉由對上述半透光膜及上述遮光膜分別實施圖案化，而形成有使曝光之光透過之透光部、使曝光之光之一部分透過之半透光部、以及將曝光之光遮蔽之遮光部，上述半透光膜包含相對於遍及i線~g線之波長帶之曝光之光的透射率光譜互不相同之2層以上之半透光膜的積層膜，包含上述積層膜之半透光膜係藉由2層以上之半透光膜之積層，而控制相對於透過包含上述積層膜之半透光膜且遍及i線~g線之波長帶之曝光之光的透射率變化量，且包含上述積層膜之半透光膜係藉由2層以上之半透光膜之積層，而控制透過包含上述積層膜之半透光膜之曝光之光的透射率。A multi-tone mask characterized in that a semi-transmissive film that transmits a part of exposed light and a light-shielding film that shields exposed light are sequentially provided on the light-transmitting substrate, by the semi-transparent film And the light-shielding film is patterned, and a light-transmissive portion that transmits the exposed light, a semi-transmissive portion that partially transmits the exposed light, and a light-shielding portion that shields the exposed light are formed. a laminated film comprising two or more semi-transmissive films having different transmittance spectra of light exposed to wavelength bands of the i-line to the g-line, wherein the semi-transmissive film comprising the laminated film is composed of two layers The semi-transmissive film is laminated to control the amount of change in transmittance with respect to the light transmitted through the wavelength band of the semi-transmissive film including the laminated film and across the i-g to g-line, and includes half of the laminated film The light-transmissive film controls the transmittance of the light transmitted through the semi-transmissive film including the laminated film by a laminate of two or more semi-transmissive films.
如構成5之多色調光罩，其特徵在於：上述半透光部係於透光性基板上，形成有由積層構造之半透光膜所構成之半透光部。In the multi-tone mask of the fifth aspect, the semi-transmissive portion is formed on a light-transmissive substrate, and a semi-transmissive portion composed of a semi-transmissive film having a laminated structure is formed.
如構成5之多色調光罩，其特徵在於：上述半透光部具有曝光之光的透射率不同之第1半透光部與第2半透光部，上述第1半透光部係於透光性基板上，形成有僅由積層構造之半透光膜之下層膜所構成之半透光部，上述第2半透光部係於透光性基板上，形成有由積層構造之半透光膜之下層膜及上層膜之積層膜所構成的半透光部。In the multi-tone mask of the fifth aspect, the semi-transmissive portion has a first semi-transmissive portion and a second semi-transmissive portion having different transmittances of exposed light, and the first semi-transmissive portion is attached to On the light-transmissive substrate, a semi-transmissive portion composed of a semi-transmissive film underlying film having a laminated structure is formed, and the second semi-transmissive portion is formed on the light-transmissive substrate, and a half of the laminated structure is formed. a semi-transmissive portion formed by a laminated film of the underlying film of the light transmissive film and the upper film.
一種圖案轉印方法，其包括如下步驟：使用構成5至7中任一項之多色調光罩，且藉由遍及i線~g線之波長帶的曝光之光，而將光罩上所形成之多色調圖案轉印至被轉印體上。A pattern transfer method comprising the steps of: forming a photomask by using a multi-tone mask of any one of 5 to 7 and exposing light through a wavelength band of an i-line to a g-line; The multi-tone pattern is transferred onto the object to be transferred.
根據本發明，可提供一種可同時滿足下述(1)~(3)之FPD用大型多色調光罩基底及光罩、以及其等之製造方法。According to the present invention, it is possible to provide a large-sized multi-tone mask base and a photomask for FPD which can simultaneously satisfy the following (1) to (3), and a method of manufacturing the same.
(1)抑制半透光膜之遍及i線~g線之波長帶之透射率變化量。(1) The amount of change in transmittance of the wavelength band across the i-line to the g-line of the semi-transmissive film is suppressed.
(2)將透過半透光膜之曝光之光的透射率調整為所期望之值(尤其是容易進行微調整)。(2) The transmittance of the light that has passed through the semi-transmissive film is adjusted to a desired value (especially, it is easy to perform fine adjustment).
(3)可採用缺陷少之製程。(3) A process with few defects can be used.
以下，對本發明進行詳細說明。Hereinafter, the present invention will be described in detail.
本發明之特徵在於：其係多色調光罩、或用以製作該多色調光罩之光罩基底，該多色調光罩係於透光性基板上，依序具有使曝光之光的一部分透過之半透光膜及將曝光之光遮蔽之遮光膜，且藉由對上述半透光膜及上述遮光膜分別實施圖案化，而形成有使曝光之光透過之透光部、使曝光之光之一部分透過之半透光部、以及將曝光之光遮蔽的遮光部，上述半透光膜包含相對於遍及i線~g線之波長帶的曝光之光之透射率光譜互不相同之2層以上的半透光膜之積層膜，包含上述積層膜之半透光膜係藉由2層以上之半透光膜之積層，而控制相對於透過包含上述積層膜之半透光膜且遍及i線~g線之波長帶的曝光之光之透射率變化量，且包含上述積層膜之半透光膜係藉由2層以上之半透光膜之積層，而控制透過包含上述積層膜之半透光膜的曝光之光的透射率(構成1、構成5)。The invention is characterized in that it is a multi-tone mask or a mask base for fabricating the multi-tone mask, the multi-tone mask is attached to the light-transmissive substrate, and sequentially has a part of the exposed light transmitted through a semi-transmissive film and a light-shielding film that shields the exposed light, and each of the semi-transmissive film and the light-shielding film is patterned to form a light-transmitting portion that transmits the exposed light and exposes the light. a part of the semi-transmissive portion and the light-shielding portion that shields the exposed light, wherein the semi-transmissive film includes two layers having different transmittance spectra of the exposed light in the wavelength band of the i-g to g-line. In the laminated film of the above semi-transmissive film, the semi-transmissive film including the laminated film is laminated by a semi-transmissive film of two or more layers, and is controlled to pass through the semi-transparent film including the laminated film. The amount of change in the transmittance of the exposed light in the wavelength band of the line to the g line, and the semi-transmissive film including the laminated film is controlled by the layer of the semi-transmissive film of two or more layers, and is controlled to pass through the half of the laminated film. Transmittance of exposed light of a light-transmissive film (constitution 1, composition 5) .
根據上述構成1、構成5之發明，可提供可同時滿足下述(1)~(3)之FPD用大型多色調光罩基底及光罩、以及該等之製造方法。According to the invention of the above-described configuration 1 and configuration 5, it is possible to provide a large-sized multi-tone mask base and a photomask for FPD which can simultaneously satisfy the following (1) to (3), and the manufacturing methods thereof.
(1)抑制半透光膜之遍及i線~g線之波長帶之透射率變化量；(1) suppressing a change in transmittance of a semi-transmissive film across a wavelength band of an i-line to a g-line;
(2)將透過半透光膜的曝光之光的透射率調整為所期望之值(尤其是容易進行微調整)；(2) adjusting the transmittance of the exposed light transmitted through the semi-transmissive film to a desired value (especially, it is easy to perform fine adjustment);
(3)可採用缺陷少之製程。(3) A process with few defects can be used.
可以說，本發明之光罩基底及光罩如上所述，其特徵在於：對於以「包含上述積層膜之半透光膜可藉由2層以上之半透光膜之積層，而控制相對於透過包含上述積層膜之半透光膜且遍及i線~g線之波長帶的曝光之光之透射率變化量(抑制為所期望之值)，且包含上述積層膜之半透光膜可藉由2層以上之半透光膜之積層，而控制透過包含上述積層膜之半透光膜的曝光之光的透射率(抑制為所期望之值)」之方式而構成上述積層膜的各半透光膜之材料及膜厚進行選擇(調整)。It can be said that the reticle base and the reticle of the present invention are characterized in that "the semi-transmissive film including the laminated film can be laminated by a semi-transparent film of two or more layers, and the control is relative to a semi-transmissive film containing the semi-transmissive film of the laminated film and having a wavelength change of light exposed to a wavelength band of the i-line to the g-line (suppressed to a desired value), and the semi-transparent film including the laminated film can be borrowed The half of the laminated film is formed by laminating two or more layers of the semi-transmissive film and controlling the transmittance of the light that is transmitted through the semi-transmissive film including the laminated film (suppressed to a desired value). The material and film thickness of the light-transmissive film are selected (adjusted).
藉此，可獲得可同時滿足上述(1)~(3)之FPD用大型多色調光罩基底及光罩。Thereby, a large-sized multi-tone mask base and a photomask for FPD which can satisfy the above (1) to (3) can be obtained.
具體而言，例如，半透光膜係自基板側起積層有CrN\MoSiN之積層膜。當MoSiN之膜厚恰當之情形(膜厚相對較小之情形)，可獲得將遍及i線~g線之波長帶之透射率變化量抑制為1.5%以下之效果。又，可利用MoSiN之膜厚而對透射率進行微調整。相對於此，當MoSiN之膜厚不恰當之情形(膜厚相對較大之情形)，無法獲得抑制遍及i線~g線之波長帶之透射率變化量之效果。Specifically, for example, the semi-transmissive film is a laminated film of CrN\MoSiN laminated from the substrate side. When the film thickness of MoSiN is appropriate (in the case where the film thickness is relatively small), the effect of suppressing the change in transmittance in the wavelength band of the i-line to the g-line to 1.5% or less can be obtained. Further, the transmittance can be finely adjusted by using the film thickness of MoSiN. On the other hand, when the film thickness of MoSiN is not appropriate (in the case where the film thickness is relatively large), the effect of suppressing the amount of change in transmittance of the wavelength band extending from the i-th to g-lines cannot be obtained.
本發明之光罩基底及光罩之特徵在於：構成上述積層膜之至少一方之半透光膜係具有抑制遍及i線~g線之波長帶之透射率變化量之功能的膜，且藉由調整構成上述積層膜之至少一方之半透光膜的膜厚，而將透過包含上述積層膜之半透光膜的曝光之光的透射率調整為所期望之值(構成2)。The reticle base and the reticle of the present invention are characterized in that the semi-transmissive film constituting at least one of the laminated films has a function of suppressing a change in transmittance of a wavelength band extending from the i-th to the g-line, and The film thickness of the semi-transmissive film constituting at least one of the laminated films is adjusted, and the transmittance of the light that has passed through the semi-transmissive film including the laminated film is adjusted to a desired value (Configuration 2).
根據上述構成2之發明，可提供可同時滿足下述(1)~(3)之FPD用大型多色調光罩基底及光罩、以及其等之製造方法。According to the invention of the above configuration 2, it is possible to provide a large-sized multi-tone mask base and a photomask for FPD which can satisfy the following (1) to (3), and a method of manufacturing the same.
(1)抑制半透光膜之遍及i線~g線之波長帶之透射率變化量，(1) suppressing the change in transmittance of the semi-transmissive film across the wavelength band of the i-line to the g-line,
(2)將透過半透光膜的曝光之光的透射率調整為所期望之值(尤其是容易進行微調整)；(2) adjusting the transmittance of the exposed light transmitted through the semi-transmissive film to a desired value (especially, it is easy to perform fine adjustment);
(3)可採用缺陷少之製程。(3) A process with few defects can be used.
上述構成2之發明包含以下態樣。The invention of the above configuration 2 includes the following aspects.
該態樣1係利用如下兩種膜之積層膜而構成半透光膜之態樣，上述兩種膜係：i線-g線間之透射率變動相對較大，但用以獲得特定之透射率之膜厚相對較厚，因此易於對透射率進行調整、控制之膜；以及i線-g線間之透射率變動相對較小，但用以獲得特定之透射率之膜厚相對較薄，因此難以於對透射率進行調整、控制之膜。This aspect 1 is a configuration in which a semi-transparent film is formed by using a laminate film of two types of films: the transmittance between the i-line and the g line is relatively large, but used to obtain a specific transmission. The film thickness of the film is relatively thick, so it is easy to adjust and control the transmittance of the film; and the transmittance variation between the i-line and the g line is relatively small, but the film thickness for obtaining a specific transmittance is relatively thin, Therefore, it is difficult to adjust and control the transmittance of the film.
作為上述態樣1之具體例，例如可列舉利用自基板側起積層有CrN\MoSiN之積層膜而構成半透光膜之態樣。Specific examples of the above-described aspect 1 include a laminate film in which CrN\MoSiN is laminated from the substrate side to form a semi-transmissive film.
該態樣2係利用如下兩種膜之積層膜而構成半透光膜之態樣，上述兩種膜係：i線-g線間之透射率變動相對較小，且用以獲得特定之透射率之膜厚相對較厚，因此易於對透射率進行調整、控制之膜；以及i線-g線間之透射率變動相對較小，但用以獲得特定之透射率之膜厚相對較薄，因此難以對透射率進行調整、控制之膜。This aspect 2 is a state in which a semi-transparent film is formed by using a laminated film of two films, the transmittance of the two film systems: i-line-g line is relatively small, and is used to obtain a specific transmission. The film thickness of the film is relatively thick, so it is easy to adjust and control the transmittance of the film; and the transmittance variation between the i-line and the g line is relatively small, but the film thickness for obtaining a specific transmittance is relatively thin, Therefore, it is difficult to adjust and control the transmittance of the film.
作為上述態樣2之具體例，例如可列舉利用自基板側起積層有CrN\MoSi之積層膜而構成半透光膜之態樣。於該情形時，可利用CrN膜、MoSi膜中之任一方之膜或雙方之膜之膜厚而調整透射率。又，亦可根據MoSi膜之成膜條件而調整MoSi膜之透射率，藉此，調整包含積層膜之半透光膜的透射率。進而，可利用MoSiN之膜厚而對透射率進行微調整。As a specific example of the above-described aspect 2, for example, a laminate film of CrN\MoSi laminated from the substrate side is used to form a semi-transmissive film. In this case, the transmittance can be adjusted by using the film thickness of either the CrN film or the MoSi film or both of the films. Further, the transmittance of the MoSi film can be adjusted according to the film formation conditions of the MoSi film, whereby the transmittance of the semi-transmissive film including the build-up film can be adjusted. Further, the transmittance can be finely adjusted by using the film thickness of MoSiN.
再者，於上述態樣1、2中，可將如下之膜設為下層(基板側之層)，亦可設於上層(遮光膜側之層)，該膜係i線-g線間之透射率變動相對較小，但用以獲得特定透射率之膜厚相對較薄，因此難以對透射率進行調整、控制之膜。Further, in the above aspects 1 and 2, the following film may be a lower layer (a layer on the substrate side) or an upper layer (a layer on the light shielding film side), and the film may be between the i-line and the g-line. The transmittance variation is relatively small, but the film thickness for obtaining a specific transmittance is relatively thin, so that it is difficult to adjust and control the transmittance.
本發明之光罩基底及光罩中，對於包含積層膜之半透光膜而言，以遍及i線~g線之波長帶之透射率變化量為2.0%以下為佳(構成3)。In the reticle base and the reticle of the present invention, it is preferable that the semi-transmissive film including the laminated film has a transmittance change amount of 2.0% or less in a wavelength band extending from the i-th to the g-line (constitution 3).
其原因在於用以滿足變得嚴格之需求精度(規格值)。又，其原因在於，可大幅度地獲得藉由將半透光膜之遍及i線~g線之波長帶之透射率變化量抑制得較小而產生的效果。The reason for this is to satisfy the demanding accuracy (specification value) that becomes strict. Moreover, the reason for this is that the effect of suppressing the amount of change in the transmittance of the wavelength band of the semi-transmissive film over the i-th to g-lines can be greatly obtained.
自同樣之觀點考慮，對於包含積層膜之半透光膜而言，更好的是，遍及i線~g線之波長帶之透射率變化量為1.5%以下。From the same viewpoint, it is more preferable that the semi-transmissive film including the laminated film has a transmittance change amount of 1.5% or less in the wavelength band of the i-line to the g-line.
本發明之光罩基底及光罩中，對於構成上述積層膜之至少一方之半透光膜而言，包含相對於遍及i線~g線之波長帶之曝光之光的透射率變化量(i線~g線之波長帶中之透射率之最大值與最小值之差)宜為1.5%以下之材料。In the reticle base and the reticle of the present invention, the semi-transmissive film constituting at least one of the laminated films includes a change in transmittance of light irradiated with respect to a wavelength band extending from the i-th to the g-line (i) The difference between the maximum value and the minimum value of the transmittance in the wavelength band of the line ~g line is preferably 1.5% or less.
作為此種材料，可列舉MoSi、CrN等。其中，自下述(a)~(d)等之方面考慮，最好的是CrN。As such a material, MoSi, CrN, etc. are mentioned. Among them, from the following aspects (a) to (d), etc., the most preferable is CrN.
(a)相對於遍及i線~g線之波長帶之曝光之光的透射率之波長依存性較小。(a) The wavelength dependence of the transmittance of the light exposed to the wavelength band of the i-line to the g-line is small.
(b)耐化學性(耐沖洗性)及耐光性優良。(b) Excellent chemical resistance (washing resistance) and light resistance.
(c)可控制蝕刻速度。(c) The etching rate can be controlled.
(d)相對於他方之半透光膜(例如MoSiN、MoSi等)之蝕刻液，蝕刻選擇性充分，因此，當對他方之半透光膜(例如MoSiN、MoSi等)進行蝕刻之情形，半透光膜所受之損傷較小。(d) The etching selectivity is sufficient with respect to the etching liquid of the semi-transmissive film (for example, MoSiN, MoSi, etc.) of the other side, and therefore, when etching the other semi-transparent film (for example, MoSiN, MoSi, etc.), half The light-transmissive film is less damaged.
本發明之光罩基底及光罩例如包含如下態樣，即，於透光性基板上，依序積層有半透光膜之積層膜、及包含含有鉻之材料之遮光膜而成，上述半透光膜之積層膜係由包含含有鉻與氮之材料之半透光膜、以及包含含有鉬與矽之材料、或含有鉬、矽及氮之材料的半透光膜依序積層而成(構成4)。The reticle base and the reticle of the present invention include, for example, a laminated film in which a semi-transmissive film is laminated on a light-transmitting substrate, and a light-shielding film containing a material containing chromium. The laminated film of the light-transmissive film is formed by sequentially laminating a semi-transparent film containing a material containing chromium and nitrogen, and a semi-transmissive film containing a material containing molybdenum and niobium or a material containing molybdenum, niobium and nitrogen ( Composition 4).
本發明之光罩基底及光罩中，當使用包含自基板側起積層有CrN\MoSiN之積層膜之半透光膜之情形，可獲得以下效果。In the case of the reticle base and the reticle of the present invention, when a semi-transmissive film including a laminated film of CrN\MoSiN laminated from the substrate side is used, the following effects can be obtained.
1)藉由將MoSiN之膜厚設為恰當之厚度，可獲得將遍及i線~g線之波長帶之透射率變化量抑制為1.5%以下之效果。1) By setting the film thickness of MoSiN to an appropriate thickness, it is possible to suppress the amount of change in transmittance in the wavelength band of the i-line to the g-line to 1.5% or less.
2)與使用CrN單層膜之情形(先前例2)相比較，易於調整、控制為所期望之透射率，尤其容易對透射率進行微調整。2) Compared with the case of using a CrN single layer film (Previous Example 2), it is easy to adjust and control to a desired transmittance, and it is particularly easy to finely adjust the transmittance.
3)可使用先形成半透光膜之製程；3) A process of forming a semi-transparent film first can be used;
4)與使用MoSiN單層膜之情形(先前例1)相比較，可使MoSiN膜變薄，因此可縮短蝕刻時間。具體而言，與先前例1相比較，膜厚約為1/3，適量蝕刻時間約為1/5。4) Compared with the case of using a MoSiN single-layer film (Previous Example 1), the MoSiN film can be made thin, so that the etching time can be shortened. Specifically, the film thickness was about 1/3 as compared with the previous example 1, and the appropriate etching time was about 1/5.
5)與MoSi系單層膜(MoSi、MoSiN等)相比較，於積層膜之狀態下，薄片電阻較低。一般認為MoSi系膜雖然為非導電性，但可利用與下層接觸之CrN膜之穿遂效應而獲得導電性。5) Compared with the MoSi-based single-layer film (MoSi, MoSiN, etc.), the sheet resistance is low in the state of the laminated film. It is considered that the MoSi film is non-conductive, but conductivity can be obtained by the punching effect of the CrN film in contact with the lower layer.
6)與MoSi系單層膜(MoSi、MoSiN等)相比較，耐光性、耐化學性優良。CrN膜之耐光性‧耐化學性亦優良，故而包含積層膜之半透光膜之耐光性、耐化學性亦優良。6) It is excellent in light resistance and chemical resistance as compared with a MoSi single layer film (MoSi, MoSiN, etc.). Since the CrN film is excellent in light resistance and chemical resistance, the semi-transmissive film including the laminated film is also excellent in light resistance and chemical resistance.
7)於自基板側起積層有半透光性之CrN膜(下層)、與其接觸之半透光性之MoSi膜(上層)、以及與其接觸之Cr系遮光膜之積層構造中之各層之間，可獲得較高之蝕刻選擇比。7) Between the layers in the laminated structure in which the semi-transmissive CrN film (lower layer), the semi-transmissive MoSi film (upper layer) in contact therewith, and the Cr-based light-shielding film in contact therewith are laminated from the substrate side A higher etching selectivity ratio can be obtained.
本發明之光罩基底及光罩中，包含積層膜之半透光膜可設為2層構造(雙層膜)，亦可設為3層以上之多層構造(多層膜)。In the mask base and the mask of the present invention, the semi-transmissive film including the laminated film may have a two-layer structure (two-layer film), or may have a multilayer structure (multilayer film) of three or more layers.
本發明中，構成積層膜之各半透光膜可設為含有金屬之膜。In the present invention, each of the semi-transmissive films constituting the laminated film may be a film containing a metal.
本發明中，包含積層膜之半透光膜於積層膜之狀態下，宜呈現如下之導電性，即，電阻為薄片電阻值1kΩ/□以下。In the present invention, in the state of the laminated film, the semi-transmissive film including the laminated film preferably exhibits conductivity such that the electric resistance is 1 k?/? or less.
本發明之光罩基底及光罩中，作為半透光膜之材質，宜藉由選擇膜厚，使得當將透光部之透射率設為100%之情形，可獲得透射率20~60%左右(以40~60%為佳)之半透過性者，例如可列舉MoSi系材料、Cr化合物(Cr之氧化物、氮化物、氮氧化物、氟化物等)、Si、W、Al等。Si、W、Al等係由於其膜厚而可獲得較高之遮光性或半透過性之材質。In the reticle base and the reticle of the present invention, as the material of the semi-transmissive film, it is preferable to select a film thickness so that when the transmittance of the light transmitting portion is set to 100%, a transmittance of 20 to 60% can be obtained. Examples of the semi-transmissive property of the right and left (preferably 40 to 60%) include a MoSi-based material, a Cr compound (such as an oxide of Cr, a nitride, an oxynitride, or a fluoride), Si, W, and Al. Si, W, Al, etc. are materials which have a high light-shielding property or a semi-transmissive property because of the film thickness.
此處，半透光膜之材料並不限於由Mo與Si構成之MoSi系材料，可列舉金屬及矽(MSi，其中M係Mo、Ta、W、Ni、Zr、Ti、Cr等之過渡金屬)、經氧化氮化之金屬及矽(MSiON)、經氧化碳化之金屬及矽(MSiCO)、經氧化氮化碳化之金屬及矽(MSiCON)、經氧化之金屬及矽(MSiO)、以及經氮化之金屬及矽(MSiN)等。Here, the material of the semi-transmissive film is not limited to the MoSi-based material composed of Mo and Si, and examples thereof include metal and lanthanum (MSi), wherein M is a transition metal such as Mo, Ta, W, Ni, Zr, Ti, Cr, or the like. ), zirconia metal and lanthanum (MSiON), oxidized carbonized metal and lanthanum (MSiCO), oxidized carbonitride metal and lanthanum (MSiCON), oxidized metal and lanthanum (MSiO), and Nitrided metal and niobium (MSiN).
本發明之光罩基底及光罩中，遮光膜之材質宜為藉由選擇膜厚而可獲得高遮光性者，可列舉例如Cr、Si、W、Al等。In the reticle base and the reticle of the present invention, the material of the light-shielding film is preferably a film having a high light-shielding property by selecting a film thickness, and examples thereof include Cr, Si, W, and Al.
作為遮光膜之材質，可列舉例如CrN、CrO、CrC、CrON等將Cr作為主成分者。遮光膜可為該等之單層，亦可為將該等加以積層而成者。遮光膜宜為於包含Cr之遮光層上積層有包含Cr化合物(CrO、CrN、或CrC)之抗反射層者。Examples of the material of the light-shielding film include Cr as a main component such as CrN, CrO, CrC, or CrON. The light-shielding film may be such a single layer, or may be formed by laminating the layers. The light-shielding film is preferably one in which an anti-reflection layer containing a Cr compound (CrO, CrN, or CrC) is laminated on a light-shielding layer containing Cr.
本發明之多色調光罩中，如圖9(1)中之一例所示，含有如下態樣，即使上述半透光部係於透光性基板21上，形成有僅由積層有2個半透光膜22、23之構造之半透光膜所構成的半透光部(構成6)。In the multi-tone mask of the present invention, as shown in an example of Fig. 9 (1), the semi-transmissive portion is formed on the light-transmissive substrate 21, and two or more layers are formed only by the laminate. A semi-transmissive portion (constitution 6) composed of a semi-transmissive film having a structure of light-transmitting films 22 and 23.
本發明之多色調光罩中，如圖9(2)中之一例所示，含有如下態樣，即，上述半透光部具有曝光之光的透射率不同之第1半透光部與第2半透光部，上述第1半透光部係於透光性基板21上，形成有僅由上述積層構造之半透光膜之下層膜22所構成之半透光部，上述第2半透光部係於透光性基板21上，形成有由上述積層構造之半透光膜之下層膜22及上層膜23之積層膜所構成的半透光部(構成7)。於該情形時，使用具有固定透射率之半透光膜作為上層之半透光膜23，選擇性地保留上層之半透光膜23，藉此可獲得4色調光罩。In the multi-tone mask of the present invention, as shown in an example of Fig. 9 (2), the semi-transmissive portion has a first semi-transmissive portion having a different transmittance of light to be exposed and a first In the second semi-transmissive portion, the first semi-transmissive portion is formed on the light-transmitting substrate 21, and a semi-transmissive portion composed only of the semi-transmissive film underlayer film 22 having the laminated structure is formed, and the second half is formed. The light transmitting portion is formed on the light-transmitting substrate 21, and a semi-transmissive portion (constitution 7) composed of a laminated film of the semi-transmissive film underlayer film 22 and the upper layer film 23 having the above-described laminated structure is formed. In this case, a semi-transmissive film having a fixed transmittance is used as the semi-transmissive film 23 of the upper layer, and the upper semi-transmissive film 23 is selectively retained, whereby a 4-tone mask can be obtained.
本發明中，當將透光性基板之露出之透光部的曝光之光之透射率設為100%之情形，半透光膜之曝光之光的透射率以20~60%為佳，更佳為40~60%。此處，所謂透射率係指相對於使用多色調光罩之例如大型LCD用曝光機之曝光之光的波長之透射率。In the present invention, when the transmittance of the exposed light of the light-transmitting portion exposed to the light-transmitting substrate is set to 100%, the transmittance of the light of the semi-transmissive film is preferably 20 to 60%, and more preferably Good for 40~60%. Here, the transmittance refers to the transmittance of the wavelength of light which is exposed to an exposure machine such as a large LCD using a multi-tone mask.
本發明中，當所形成之光罩之遮光部係由半透光膜及遮光膜積層而成之情形，即便遮光膜單獨之遮光性不足，只要與半透光膜組合之後可獲得遮光性即可。In the present invention, when the light-shielding portion of the formed photomask is formed by laminating a semi-transmissive film and a light-shielding film, even if the light-shielding property of the light-shielding film alone is insufficient, the light-shielding property can be obtained by combining with the semi-transparent film. can.
本發明中，理想的是，當自基板側起，半透光膜之下層、與其接觸之半透光膜之上層、以及與其接觸之遮光膜成膜於基板上時，相互間之密著性良好。In the present invention, it is desirable that when the lower layer of the semi-transmissive film, the upper layer of the semi-transmissive film in contact therewith, and the light-shielding film in contact therewith are formed on the substrate from the substrate side, the adhesion therebetween good.
本發明中，具有於透光性基板上形成半透光膜、遮光膜之步驟，但成膜方法可適當地選擇適合於膜之類型之方法，例如濺鍍法、蒸鍍法、CVD(Chemical Vapor Deposition，化學氣相沈積)法等。In the present invention, the semi-transparent film and the light-shielding film are formed on the light-transmitting substrate. However, the film-forming method can appropriately select a method suitable for the type of the film, such as sputtering, evaporation, and CVD (Chemical). Vapor Deposition, chemical vapor deposition).
本發明中，作為包含含有金屬及矽之材料之半透光膜之蝕刻液，可使用含有選自氫氟酸、矽氫氟酸、氫氟銨中之至少一種氟化合物、以及選自過氧化氫、硝酸、硫酸中之至少一種氧化劑的蝕刻液。In the present invention, as the etching liquid containing the semi-transmissive film containing the metal and the ruthenium, at least one fluorine compound selected from the group consisting of hydrofluoric acid, hydrazine hydrofluoric acid, and hydrofluoroammonium may be used, and from the group consisting of peroxidation. An etching solution of at least one of hydrogen, nitric acid, and sulfuric acid.
本發明中，作為含有Cr之材料之蝕刻液，可使用含有硝酸鈰銨之蝕刻液。In the present invention, as the etching liquid of the material containing Cr, an etching solution containing cerium ammonium nitrate can be used.
本發明之多色調光罩係TFT(Thin Film Transistor，薄膜電晶體)製造用之多色調光罩及光罩基底，半透光部可較好地用作對相當於該薄膜電晶體之通道部之部分的圖案進行轉印者。In the multi-tone mask-type TFT (Thin Film Transistor) manufacturing method of the present invention, the semi-transmissive portion can be preferably used as a channel portion corresponding to the thin film transistor. Part of the pattern is carried on.
圖13中表示TFT基板製造用之光罩圖案之一例。TFT基板製造用之圖案100包括：遮光部101，其包含與TFT基板之源極及汲極相對應之圖案101a、101b；半透光部103，其包含與TFT基板之通道部相對應之圖案；以及透光部102，其形成於上述圖案之周圍。Fig. 13 shows an example of a mask pattern for manufacturing a TFT substrate. The pattern 100 for manufacturing a TFT substrate includes a light shielding portion 101 including patterns 101a and 101b corresponding to the source and the drain of the TFT substrate, and a semi-light transmitting portion 103 including a pattern corresponding to the channel portion of the TFT substrate. And a light transmitting portion 102 formed around the above pattern.
本發明之圖案轉印方法可較好地用作包含如下步驟之圖案轉印方法，於該步驟中，使用上述構成5至7中任一項之光罩，且藉由遍及i線~g線之波長帶的曝光之光，而將形成於光罩之多色調圖案轉印至被轉印體(構成8)。The pattern transfer method of the present invention can be preferably used as a pattern transfer method comprising the following steps, in which the photomask of any one of the above configurations 5 to 7 is used, and by the i-line to the g-line The multi-tone pattern formed in the photomask is transferred to the object to be transferred (constitution 8) by the exposure light of the wavelength band.
本發明中，作為遍及i線~g線之波長帶的曝光之光源，例示有超高壓水銀燈等，但本發明並不限定於此。In the present invention, an ultrahigh pressure mercury lamp or the like is exemplified as a light source for exposure in a wavelength band of the i-th to g-lines, but the present invention is not limited thereto.
以下，基於實施例對本發明進行更詳細之說明。Hereinafter, the present invention will be described in more detail based on examples.
準備由各種半透光膜分別以單層、積層之形式而形成於基板上所得之試樣(下述(1)~(3))。A sample obtained by forming a plurality of semi-transmissive films in a single layer or a laminate on a substrate (the following (1) to (3)) is prepared.
使用Cr靶，將Ar與N2 (8：2sccm)氣體作為濺鍍氣體，將CrN膜(半透光膜)以相對於曝光之光源之波長之透射率為40%的膜厚(約88埃)而成膜於基板上。Using a Cr target, an Ar and N 2 (8:2 sccm) gas was used as a sputtering gas, and a CrN film (semi-transmissive film) having a transmittance of 40% with respect to a wavelength of an exposure light source (about 88 Å) ) filming on the substrate.
圖1(1)表示所獲得之CrN膜之、i線(365nm)、h線(405nm)、g線(436nm)的透射率(%)、反射率(%)、i線~g線之波長帶上之透射率、反射率的最大值與最小值之差。又，圖1(2)表示所獲得之CrN膜之膜厚及薄片電阻(kΩ/□)。進而，所獲得之CrN膜之透射率光譜表示於圖2中，相對反射率光譜表示於圖3中。Fig. 1 (1) shows the transmittance (%), reflectance (%), and wavelength of the i-line to the g-line of the obtained CrN film, i-line (365 nm), h-line (405 nm), g-line (436 nm), reflectance (%) The difference between the maximum and minimum values of transmittance and reflectance on the tape. Further, Fig. 1 (2) shows the film thickness and sheet resistance (kΩ/□) of the obtained CrN film. Further, the transmittance spectrum of the obtained CrN film is shown in Fig. 2, and the relative reflectance spectrum is shown in Fig. 3.
使用Mo:Si=20:80(原子百分比)之靶，將Ar與N2 作為濺鍍氣體(流量比為Ar 5:N2 50sccm)，將包含鉬及矽之氮化膜之半透光膜(MoSiN膜)分別以約120埃之膜厚、及約330埃之膜厚而形成於基板上。Using a target of Mo:Si=20:80 (atomic percent), Ar and N 2 as sputtering gases (flow ratio: Ar 5 : N 2 50 sccm), a semi-transparent film containing a nitride film of molybdenum and niobium The (MoSiN film) was formed on the substrate by a film thickness of about 120 angstroms and a film thickness of about 330 angstroms.
將所獲得之MoSiN膜中之膜厚較薄者記作MoSiN-1，將膜厚較厚者記作MoSiN-2。The film thickness of the obtained MoSiN film is referred to as MoSiN-1, and the film thickness is referred to as MoSiN-2.
圖1(1)表示所獲得之MoSiN膜(MoSiN-1、MoSiN-2)之、i線(365nm)、h線(405nm)、g線(436nm)之透射率(%)、反射率(%)、i線~g線之波長帶上之透射率、反射率的最大值與最小值之差。又，圖1(2)表示所獲得之MoSiN膜(MoSiN-1、MoSiN-2)之膜厚及薄片電阻(kΩ/□)。進而，圖2表示所獲得之MoSiN膜(MoSiN-1、MoSiN-2)之透射率光譜，圖3表示相對反射率光譜。Fig. 1 (1) shows the transmittance (%) of the obtained MoSiN film (MoSiN-1, MoSiN-2), i-line (365 nm), h-line (405 nm), g-line (436 nm), and reflectance (%) ), the difference between the maximum and minimum values of the transmittance and reflectance in the wavelength band of the i-line to the g-line. Further, Fig. 1 (2) shows the film thickness and sheet resistance (kΩ/□) of the obtained MoSiN film (MoSiN-1, MoSiN-2). Further, Fig. 2 shows the transmittance spectrum of the obtained MoSiN film (MoSiN-1, MoSiN-2), and Fig. 3 shows the relative reflectance spectrum.
將於基板上依序形成有與上述相同之CrN膜、膜厚較薄之MoSiN膜(MoSiN-1)的試樣記作CrN+MoSiN-1。A sample in which a CrN film having the same thickness as above and a MoSiN film (MoSiN-1) having a small film thickness were sequentially formed on the substrate was designated as CrN+MoSiN-1.
將於基板上依序形成有與上述相同之CrN膜、膜厚較厚之MoSiN膜(MoSiN-2)的試樣記作CrN+MoSiN-2。A sample in which a CrN film having the same thickness as above and a MoSiN film (MoSiN-2) having a thick film thickness were sequentially formed on the substrate was designated as CrN+MoSiN-2.
圖1(1)表示所獲得之試樣(CrN+MoSiN-1、CrN+MoSiN-2)之、i線(365nm)、h線(405nm)、g線(436nm)之透射率(%)、反射率(%)、i線~g線之波長帶上之透射率、反射率的最大值與最小值之差。又，圖1(2)表示所獲得之試樣(CrN+MoSiN-1、CrN+MoSiN-2)之膜厚及薄片電阻(kΩ/□)。進而，圖2表示所獲得之試樣(CrN+MoSiN-1、CrN+MoSiN-2)之透射率光譜，圖3表示相對反射率光譜。Fig. 1 (1) shows the transmittance (%) of the obtained sample (CrN + MoSiN-1, CrN + MoSiN-2), i-line (365 nm), h-line (405 nm), g-line (436 nm), The reflectance (%), the transmittance on the wavelength band of the i-line to the g-line, and the difference between the maximum value and the minimum value of the reflectance. Further, Fig. 1 (2) shows the film thickness and sheet resistance (k?/?) of the obtained sample (CrN + MoSiN-1, CrN + MoSiN-2). Further, Fig. 2 shows the transmittance spectrum of the obtained sample (CrN + MoSiN-1, CrN + MoSiN-2), and Fig. 3 shows the relative reflectance spectrum.
再者，於上述成膜步驟中，使用有大型玻璃基板(厚度為10mm、尺寸為850mm×1200mm之合成石英(QZ))，且使用有大型連續式濺鍍裝置。Further, in the above film forming step, a large glass substrate (synthetic quartz (QZ) having a thickness of 10 mm and a size of 850 mm × 1200 mm) was used, and a large continuous sputtering apparatus was used.
又，圖1(1)及圖3中之「相對反射率」表示以鋁(Al)之反射率為基準(100%)而測定之反射率。Further, the "relative reflectance" in Fig. 1 (1) and Fig. 3 indicates the reflectance measured based on the reflectance of aluminum (Al) (100%).
關於CrN/MoSiN之積層膜，當MoSiN之膜厚恰當之情形(於CrN+MoSiN-1之試樣之情形之情形)，可獲得將遍及i線~g線之波長帶之透射率變化量抑制為1.5%以下的效果。又，可利用MoSiN之膜厚而對透射率進行微調整。相對於此，當MoSiN之膜厚不恰當(於CrN+MoSiN-2之試樣之情形時)，無法獲得抑制遍及i線~g線之波長帶之透射率變化量的效果。Regarding the laminated film of CrN/MoSiN, when the film thickness of MoSiN is appropriate (in the case of the sample of CrN+MoSiN-1), it is possible to suppress the change in the transmittance of the wavelength band across the i-g line. It is less than 1.5%. Further, the transmittance can be finely adjusted by using the film thickness of MoSiN. On the other hand, when the film thickness of MoSiN is not appropriate (in the case of a sample of CrN+MoSiN-2), the effect of suppressing the amount of change in transmittance in the wavelength band of the i-line to the g-line cannot be obtained.
準備由各種半透光膜分別以單層、積層之形式而形成於基板上所得之試樣。A sample obtained by forming a plurality of semi-transparent films on a substrate in the form of a single layer or a laminate is prepared.
使用Cr靶，將Ar與N2 (8:2sccm)氣體作為濺鍍氣體，將CrN膜(半透光膜)以相對於曝光之光源之波長的透射率為40%之膜厚(約78埃)而成膜於基板上。Using a Cr target, an Ar and N 2 (8:2 sccm) gas was used as a sputtering gas, and a CrN film (semi-transmissive film) having a transmittance of 40% with respect to the wavelength of the light source to be exposed (about 78 angstroms) ) filming on the substrate.
圖4(1)表示所獲得之CrN膜之、i線(365nm)、h線(405nm)、g線(436nm)之透射率(%)、反射率(%)、i線~g線之波長帶上之透射率、反射率的最大值與最小值之差。又，圖4(2)表示所獲得之CrN膜之膜厚及薄片電阻(kΩ/□)。進而，圖5表示所獲得之CrN膜之透射率光譜，圖6表示相對反射率光譜。4(1) shows the transmittance (%) of the i-line (365 nm), the h-line (405 nm), the g-line (436 nm), the reflectance (%), and the wavelength of the i-line to the g-line of the obtained CrN film. The difference between the maximum and minimum values of transmittance and reflectance on the tape. Further, Fig. 4 (2) shows the film thickness and sheet resistance (kΩ / □) of the obtained CrN film. Further, Fig. 5 shows the transmittance spectrum of the obtained CrN film, and Fig. 6 shows the relative reflectance spectrum.
使用Mo:Si=20:80(原子百分比)之靶，將Ar作為濺鍍氣體，將包含鉬及矽之半透光膜(MoSi膜)以約220埃之膜厚而形成於基板上。Using a target of Mo:Si=20:80 (atomic percent), Ar was used as a sputtering gas, and a semi-transmissive film (MoSi film) containing molybdenum and tantalum was formed on the substrate at a film thickness of about 220 angstroms.
圖4(1)表示所獲得之MoSi膜之、i線(365nm)、h線(405nm)、g線(436nm)之透射率(%)、反射率(%)、i線~g線之波長帶上之透射率、反射率的最大值與最小值之差。又，圖4(2)表示所獲得之MOSi膜之膜厚及薄片電阻(kΩ/□)。進而，圖5表示所獲得之MoSi膜之透射率光譜，圖6表示相對反射率光譜。4(1) shows the transmittance (%) of the i-line (365 nm), the h-line (405 nm), the g-line (436 nm), the reflectance (%), and the wavelength of the i-th to g-line of the obtained MoSi film. The difference between the maximum and minimum values of transmittance and reflectance on the tape. Further, Fig. 4 (2) shows the film thickness and sheet resistance (kΩ / □) of the obtained MOSi film. Further, Fig. 5 shows the transmittance spectrum of the obtained MoSi film, and Fig. 6 shows the relative reflectance spectrum.
將基板上依序形成有與上述相同之CrN膜、MoSi膜之試樣記作CrN+MoSi。A sample in which a CrN film or a MoSi film similar to the above was sequentially formed on the substrate was designated as CrN+MoSi.
圖4(1)表示所獲得之試樣(CrN+MoSi)之、i線(365nm)、h線(405nm)、g線(436nm)之透射率(%)、反射率(%)、i線~g線之波長帶上之透射率、反射率的最大值與最小值之差。又，圖4(2)表示所獲得之試樣(CrN+MoSi)之膜厚及薄片電阻(kΩ/□)。進而，圖5表示所獲得之試樣(CrN+MoSi)之透射率光譜，圖6表示相對反射率光譜。4(1) shows the transmittance (%), reflectance (%), and i-line of the obtained sample (CrN+MoSi), i-line (365 nm), h-line (405 nm), g-line (436 nm), and reflectance (%). The difference between the maximum and minimum values of the transmittance and reflectance in the wavelength band of the ~g line. Further, Fig. 4 (2) shows the film thickness and sheet resistance (kΩ / □) of the obtained sample (CrN + MoSi). Further, Fig. 5 shows the transmittance spectrum of the obtained sample (CrN + MoSi), and Fig. 6 shows the relative reflectance spectrum.
再者，於上述成膜步驟中，使用有大型玻璃基板(厚度為10mm、尺寸為850mm×1200mm之合成石英(QZ))，且使用有大型連續式濺鍍裝置。Further, in the above film forming step, a large glass substrate (synthetic quartz (QZ) having a thickness of 10 mm and a size of 850 mm × 1200 mm) was used, and a large continuous sputtering apparatus was used.
又，圖4(1)及圖6中之「相對反射率」係表示以鋁(Al)之反射率為基準(100%)而測定之反射率。Moreover, the "relative reflectance" in FIG. 4 (1) and FIG. 6 shows the reflectance measured based on the reflectance (100%) of aluminum (Al).
若利用「i線-g線間之透射率變動相對較小，且用以獲得特定之透射率之膜厚相對較厚，因此易於對透射率進行調整、控制」之CrN膜、與「i線-g線間之透射率變動相對較小，但用以獲得特定之透射率之膜厚相對較薄，因此難以對透射率進行調整、控制」之MoSi膜之積層膜而構成半透光膜，則可獲得將遍及i線~g線之波長帶之透射率變化量抑制為2.0%以下的效果。When the "i-line-g line transmittance variation is relatively small, and the film thickness for obtaining a specific transmittance is relatively thick, it is easy to adjust and control the transmittance", and the "I-line" The transmittance change between the -g lines is relatively small, but the film thickness for obtaining a specific transmittance is relatively small, so that it is difficult to adjust and control the transmittance of the MoSi film to form a semi-transmissive film. The effect of suppressing the amount of change in transmittance in the wavelength band of the i-line to the g-line to 2.0% or less can be obtained.
於實施例2中，可利用CrN膜、MoSi膜中之任一方之膜或雙方之膜之膜厚而調整透射率。又，根據MoSi膜之成膜條件而調整MoSi膜之透射率，藉此，亦可調整包含積層膜之半透光膜之透射率。進而，可利用MoSiN之膜厚而對透射率進行微調整。In the second embodiment, the transmittance can be adjusted by using the film thickness of either the CrN film or the MoSi film or both of the films. Further, the transmittance of the MoSi film is adjusted in accordance with the film formation conditions of the MoSi film, whereby the transmittance of the semi-transmissive film including the laminate film can be adjusted. Further, the transmittance can be finely adjusted by using the film thickness of MoSiN.
於大型玻璃基板(厚度為10mm、尺寸為850mm×1200mm之合成石英(QZ))上，利用大型連續式濺鍍裝置而形成多色調光罩用之半透光膜。具體而言，使用Cr靶，將Ar與N2 (8:2sccm)氣體作為濺鍍氣體，以相對於曝光之光源之波長之透射率為40%的膜厚(約88埃)而形成CrN膜(半透光膜)。A semi-transparent film for a multi-tone mask was formed on a large glass substrate (synthetic quartz (QZ) having a thickness of 10 mm and a size of 850 mm × 1200 mm) by a large continuous sputtering apparatus. Specifically, using a Cr target, an Ar and N 2 (8:2 sccm) gas is used as a sputtering gas, and a CrN film is formed at a film thickness (about 88 angstroms) with a transmittance of 40% with respect to the wavelength of the light source to be exposed. (semi-transparent film).
繼而，於上述半透光膜上，使用Mo:Si=20:80(原子百分比)之靶，將Ar與N2 作為濺鍍氣體(流量比為Ar 5:N2 50sccm)，以約120埃之膜厚而形成包含鉬及矽之氮化膜之半透光膜之上層膜(MoSiN)。Then, on the semi-transmissive film, a target of Mo:Si=20:80 (atomic percent) is used, and Ar and N 2 are used as a sputtering gas (flow ratio: Ar 5 : N 2 50 sccm) to about 120 Å. The film is thick to form a semi-transmissive film overlayer film (MoSiN) containing a nitride film of molybdenum and niobium.
積層有半透光膜之下層膜(CrN)與半透光膜之上層膜(MoSiN)之狀態下之積層膜之薄片電阻係呈現1kΩ/□以下之導電性。The sheet resistance of the laminated film in the state in which the semi-transmissive film underlayer film (CrN) and the semi-transmissive film overlayer film (MoSiN) are laminated exhibits conductivity of 1 k?/? or less.
繼而，於上述半透光膜之上層膜上，作為遮光膜，首先，將Ar與N2 氣體作為濺鍍氣體而形成150埃之CrN膜，繼而，將Ar與CH4 氣體作為濺鍍氣體而形成650埃之CrC膜(主遮光膜)，其後，將Ar與NO氣體作為濺鍍氣體而形成250埃之CrON膜(膜面抗反射膜)，以此方式連續成膜。再者，各膜分別係組成傾斜膜。Then, on the overlying film of the semi-transmissive film, as a light-shielding film, first, a Ar and N 2 gas is used as a sputtering gas to form a 150 Å CrN film, and then Ar and CH 4 gases are used as a sputtering gas. A 650 angstrom CrC film (main light-shielding film) was formed, and thereafter, a film of a 250 angstrom CrON film (film surface anti-reflection film) was formed by using Ar and NO gas as a sputtering gas, and the film was continuously formed in this manner. Further, each of the films constitutes a slanted film.
以上述方式，製作FPD用大型光罩基底。In the above manner, a large reticle base for FPD was produced.
準備如下之光罩基底(參照圖8(1))，該光罩基底中，參照圖7，以上述方式而於透光性基板21(QZ)上依序形成有包含半透光膜22(CrN)與半透光膜23(MoSiN)之積層膜的半透光膜24、以及遮光膜30(自基板側起為CrN膜31/CrC遮光膜32/CrON抗反射膜33)。A photomask substrate (see FIG. 8(1)) in which a semi-transmissive film 22 is sequentially formed on the translucent substrate 21 (QZ) in the above-described manner with reference to FIG. The semi-transmissive film 24 of the laminated film of CrN) and the semi-transmissive film 23 (MoSiN) and the light-shielding film 30 (the CrN film 31 / CrC light-shielding film 32 / CrON anti-reflection film 33 from the substrate side).
繼而，於該光罩基底上，例如利用CAP塗佈裝置而塗佈電子束或雷射描繪用之正型光阻劑，且將其進行烘乾，從而形成光阻膜。其次，使用電子束描繪機或雷射描繪機等而進行描繪。於描繪之後使其顯影，於光罩基底上之除透光部以外之區域(亦即與遮光部及半透光部相對應之區域)中形成光阻圖案50a(參照圖8(2))。Then, an electron beam or a positive photoresist for laser drawing is applied to the mask substrate by, for example, a CAP coating device, and dried to form a photoresist film. Next, drawing is performed using an electron beam drawing machine, a laser drawing machine, or the like. After the drawing, the photoresist pattern 50a is formed in a region other than the light transmitting portion (that is, a region corresponding to the light shielding portion and the semi-light transmitting portion) on the mask substrate (refer to FIG. 8 (2)). .
繼而，將所形成之光阻圖案50a作為光罩，對遮光膜30進行濕式蝕刻而形成遮光膜圖案30a(參照圖8(3))。所使用之蝕刻液係於硝酸鈰銨中添加有過氯酸者。Then, the formed photoresist pattern 50a is used as a mask, and the light-shielding film 30 is wet-etched to form a light-shielding film pattern 30a (see FIG. 8 (3)). The etching solution used is one in which perchloric acid is added to ammonium cerium nitrate.
繼而，於除去光阻圖案50a之後，將遮光膜圖案30a作為光罩，對上層之半透光膜23(MoSiN)進行濕式蝕刻，從而形成半透光膜(MoSiN)之圖案23a(參照圖8(4))。所使用之蝕刻液係於氫氟銨中添加有過氧化氫者。Then, after the photoresist pattern 50a is removed, the light-shielding film pattern 30a is used as a mask, and the upper semi-transmissive film 23 (MoSiN) is wet-etched to form a semi-transmissive film (MoSiN) pattern 23a (refer to the figure). 8(4)). The etching solution used is one in which hydrogen peroxide is added to the hydrofluoroammonium fluoride.
繼而，將遮光膜圖案30a作為光罩，對下層之半透光膜22(CrN)進行濕式蝕刻，從而形成半透光膜(CrN)之圖案22a(參照圖8(5))。所使用之蝕刻液係於硝酸鈰銨中添加有過氯酸者。Then, the light-shielding film pattern 30a is used as a mask, and the lower semi-transmissive film 22 (CrN) is wet-etched to form a semi-transmissive film (CrN) pattern 22a (see FIG. 8 (5)). The etching solution used is one in which perchloric acid is added to ammonium cerium nitrate.
繼而，再次將上述光阻劑塗佈於整個面上而形成光阻膜。接著，進行第2次描繪。於描繪之後使其顯影，形成與遮光部及透光部相對應之光阻圖案51a(參照圖8(6))。Then, the above photoresist is applied again over the entire surface to form a photoresist film. Next, the second drawing is performed. After the drawing, the film is developed to form a photoresist pattern 51a corresponding to the light shielding portion and the light transmitting portion (see FIG. 8 (6)).
繼而，將所形成之光阻圖案51a作為光罩，利用濕式蝕刻而除去成為半透光部之區域之遮光膜圖案30a。藉此，除去半透光部上之透光膜，並且形成遮光膜圖案30b(參照圖8(7))。Then, the formed photoresist pattern 51a is used as a photomask, and the light-shielding film pattern 30a which is a region of the semi-light-transmitting portion is removed by wet etching. Thereby, the light-transmissive film on the semi-transmissive portion is removed, and the light-shielding film pattern 30b is formed (refer to FIG. 8 (7)).
最後，利用濃硫酸等而除去殘存之光阻圖案51a(參照圖8(8))。Finally, the remaining photoresist pattern 51a is removed by concentrated sulfuric acid or the like (see FIG. 8 (8)).
以上述方式製成多色調光罩。A multi-tone mask is produced in the above manner.
根據上述實施例3之發明，確認可提供一種可同時滿足下述(1)~(3)之FPD用大型多色調光罩基底及光罩、以及其等之製造方法。According to the invention of the third embodiment, it has been confirmed that a large-sized multi-tone mask base and a photomask for FPD which can satisfy the following (1) to (3) can be provided, and a method of manufacturing the same.
(1)抑制半透光膜之遍及i線~g線之波長帶的透射率變化量；(1) suppressing a change in transmittance of a semi-transmissive film across a wavelength band of an i-line to a g-line;
(2)將透過半透光膜的曝光之光的透射率調整為所期望之值(尤其是容易進行微調整)；(2) adjusting the transmittance of the exposed light transmitted through the semi-transmissive film to a desired value (especially, it is easy to perform fine adjustment);
(3)可採用缺陷少之製程。(3) A process with few defects can be used.
繼上述實施例3中之圖8之步驟(8)之後，對於包含下層之半透光膜(CrN)圖案22a與上層之半透光膜(MoSiN)圖案23a之積層膜的半透光膜圖案24a之一部分，形成新的光阻圖案而進行保護。其後，利用蝕刻液(於氫氟銨中添加有過氧化氫者)，對不受光阻圖案保護之半透光膜圖案24a之上層的半透光膜(MoSiN)圖案23a進行蝕刻，形成僅包含下層之半透光膜(CrN)圖案22a之半透光部。After the step (8) of FIG. 8 in the above-described Embodiment 3, the semi-transmissive film pattern including the laminated film of the lower semi-transmissive film (CrN) pattern 22a and the upper semi-transmissive film (MoSiN) pattern 23a. A portion of 24a forms a new photoresist pattern for protection. Thereafter, the semi-transmissive film (MoSiN) pattern 23a on the upper layer of the semi-transmissive film pattern 24a not protected by the photoresist pattern is etched by an etching solution (when hydrogen peroxide is added to the hydrofluoroammonium) to form only A semi-transmissive portion including a lower semi-transmissive film (CrN) pattern 22a.
除去光阻圖案24a，製成如下之多色調(4色調)光罩，該多色調(4色調)光罩具有包含下層之半透光膜(CrN)圖案22a與上層之半透光膜(MoSiN)圖案23a之積層膜的半透光部、僅包含下層之半透光膜(CrN)圖案22a之半透光部、遮光部、以及透光部(參照圖9(2))。The photoresist pattern 24a is removed to produce a multi-tone (4-tone) mask having a semi-transmissive film (CrN) pattern 22a including a lower layer and a semi-transmissive film (MoSiN) of an upper layer. The semi-transmissive portion of the laminated film of the pattern 23a, the semi-transmissive portion including only the lower semi-transmissive film (CrN) pattern 22a, the light-shielding portion, and the light-transmitting portion (see FIG. 9 (2)).
評價結果與實施例3相同。The evaluation results were the same as in Example 3.
以上，以較佳實施例對本發明進行了說明，但本發明並不限定於上述實施例。The present invention has been described above by way of preferred embodiments, but the present invention is not limited to the above embodiments.
1、101．．．遮光部1, 101. . . Shading
1'．．．與遮光部1相對應之部分1'. . . a portion corresponding to the light shielding portion 1
2、102．．．透光部2, 102. . . Translucent part
2'．．．與透光部2相對應之部分2'. . . a portion corresponding to the light transmitting portion 2
3、103．．．半透光部3, 103. . . Semi-transparent part
3'．．．與半透光部3相對應之部分3'. . . a portion corresponding to the semi-transmissive portion 3
3a．．．微細遮光圖案3a. . . Fine shading pattern
3b．．．微細透射部3b. . . Micro-transmission
3a'、22、23、24．．．半透光膜3a', 22, 23, 24. . . Semi-transparent film
5、21．．．光性基板5, 21. . . Optical substrate
22a．．．半透光膜(CrN)圖案22a. . . Semi-transparent film (CrN) pattern
23a．．．半透光膜(MoSiN)圖案23a. . . Semi-transparent film (MoSiN) pattern
24a．．．半透光膜圖案24a. . . Semi-transparent film pattern
30．．．遮光膜30. . . Sunscreen
30a、30b．．．遮光膜圖案30a, 30b. . . Sun mask pattern
31．．．CrN膜31. . . CrN film
32．．．CrC遮光膜32. . . CrC light shielding film
33．．．CrON抗反射膜33. . . CrON anti-reflection film
50a、51a．．．光阻圖案50a, 51a. . . Resistive pattern
100．．．TFT基板製造用之圖案100. . . TFT substrate manufacturing pattern
101a、101b．．．圖案101a, 101b. . . pattern
圖1(1)、圖1(2)係表示本發明之實施例1中所得之各種半透光膜的光學特性等之圖；1(1) and 1(2) are views showing optical characteristics and the like of various semi-transmissive films obtained in Example 1 of the present invention;
圖2係表示本發明之實施例1中所得之各種半透光膜的透射率光譜之圖；Figure 2 is a graph showing the transmittance spectra of various semi-transmissive films obtained in Example 1 of the present invention;
圖3係表示本發明之實施例1中所得之各種半透光膜的反射率光譜之圖；Figure 3 is a graph showing the reflectance spectra of various semi-transmissive films obtained in Example 1 of the present invention;
圖4(1)、圖4(2)係表示本發明之實施例2中所得之各種半透光膜的光學特性等之圖；4(1) and 4(2) are views showing optical characteristics and the like of various semi-transmissive films obtained in Example 2 of the present invention;
圖5係表示本發明之實施例2中所得之各種半透光膜的透射率光譜之圖；Figure 5 is a view showing a transmittance spectrum of various semi-transmissive films obtained in Example 2 of the present invention;
圖6係表示本發明之實施例2中所得之各種半透光膜的反射率光譜之圖；Figure 6 is a graph showing the reflectance spectra of various semi-transmissive films obtained in Example 2 of the present invention;
圖7係表示本發明之實施例3中製作之光罩基底之模式性剖面圖；Figure 7 is a schematic cross-sectional view showing a reticle base fabricated in Example 3 of the present invention;
圖8(1)~圖8(8)係按照步驟而表示本發明之實施例3之製造方法的概略剖面圖；8(1) to 8(8) are schematic cross-sectional views showing a manufacturing method of a third embodiment of the present invention in accordance with steps;
圖9(1)、圖9(2)係用以說明半透光部之態樣之模式圖；9(1) and 9(2) are schematic diagrams for explaining a state of a semi-transmissive portion;
圖10(1)、圖10(2)係用以說明半透光膜與遮光膜之成膜順序之差異的圖，圖10(1)表示先形成半透光膜之類型之光罩，圖10(2)表示後形成半透光膜之類型之光罩；10(1) and 10(2) are diagrams for explaining the difference in film formation order between the semi-transmissive film and the light-shielding film, and FIG. 10(1) shows a photomask of a type in which a semi-transparent film is formed first. 10(2) denotes a photomask of a type in which a semi-transparent film is formed;
圖11(1)、圖11(2)係用以說明具有半透光膜之多色調光罩之圖，圖11(1)係局部平面圖，圖11(2)係局部剖面圖；11(1) and 11(2) are diagrams for explaining a multi-tone mask having a semi-transmissive film, FIG. 11(1) is a partial plan view, and FIG. 11(2) is a partial cross-sectional view;
圖12(1)、圖12(2)係用以說明具有解像極限以下之微細遮光圖案之多色調光罩之圖，圖12(1)係局部平面圖，圖12(2)係局部剖面圖；及12(1) and 12(2) are diagrams for explaining a multi-tone mask having a fine light-shielding pattern below the resolution limit, and FIG. 12(1) is a partial plan view, and FIG. 12(2) is a partial cross-sectional view. ;and
圖13係表示TFT基板製造用之光罩圖案之一例的圖。Fig. 13 is a view showing an example of a mask pattern for manufacturing a TFT substrate.
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| US5756235A (en) * | 1995-09-18 | 1998-05-26 | Hyundai Electronics Industries Co., Ltd. | Phase shift mask and method for fabricating the same |
| TW542943B (en) * | 2001-08-06 | 2003-07-21 | Shinetsu Chemical Co | Phase shift mask blank, phase shift mask, and manufacturing method thereof |
| TW200602803A (en) * | 2004-03-31 | 2006-01-16 | Shinetsu Chemical Co | Halftone phase shift mask blank, halftone phase shift mask, and pattern transfer method |
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| JP3262302B2 (en) * | 1993-04-09 | 2002-03-04 | 大日本印刷株式会社 | Phase shift photomask, blank for phase shift photomask, and method of manufacturing the same |
| JP4933753B2 (en) * | 2005-07-21 | 2012-05-16 | 信越化学工業株式会社 | Phase shift mask blank, phase shift mask, and manufacturing method thereof |
| JP4695964B2 (en) * | 2005-11-09 | 2011-06-08 | アルバック成膜株式会社 | Gray tone mask and manufacturing method thereof |
| JP4516560B2 (en) * | 2005-12-26 | 2010-08-04 | Ｈｏｙａ株式会社 | Mask blank and photomask |
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| KR100886802B1 (en) * | 2006-03-30 | 2009-03-04 | 주식회사 에스앤에스텍 | Blankmask and Transmittance Modulation Slit Mask using the same, and Manufacturing Method thereof |
| KR101329525B1 (en) * | 2006-10-04 | 2013-11-14 | 주식회사 에스앤에스텍 | Gray-tone Blank Mask and Gray-tone Photomask, the Manufacturing method of them |
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| TW542943B (en) * | 2001-08-06 | 2003-07-21 | Shinetsu Chemical Co | Phase shift mask blank, phase shift mask, and manufacturing method thereof |
| TW200602803A (en) * | 2004-03-31 | 2006-01-16 | Shinetsu Chemical Co | Halftone phase shift mask blank, halftone phase shift mask, and pattern transfer method |
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