TW200805003A - Developer composition for photosensitive organic membrane - Google Patents

Abstract

Disclosed is a photographic developer composition for a photosensitive organic film (mainly, a photoresist), which has an excellent anticorrosion property against Al and a good developing property. The photographic developer composition comprises 0.5 to 5% by weight of a tetraalkylammonium hydroxide, 10 to 40% by weight of a sugar alcohol such as sorbitol or xylitol and 3 to 19% by weight of a water-soluble organic solvent such as a sulfoxide, a glycol ether or an amide, with the remainder being water. The composition is characterized in that the ratio between a dissolution rate at a light-exposed area and a dissolution rate at a light-unexposed area on a photosensitive organic film (mainly, a photoresist) is 50 or greater.

Description

200805003 IX. OBJECTS OF THE INVENTION: 1. Field of the Invention The present invention relates to a green-sensitive organic film (photoresist is "photoresist" instead of "photosensitive organic film"), and it will be described in more detail below. __ Composition of A1. Photosensitive organic film (four) liquid-liquid composition for producing a semiconductor integrated circuit or a liquid crystal panel. v body element circuit, etc. [Prior Art] Photosensitive organic film, for example The representative is used for developing a light-based system for producing a semiconductor composition H semiconductor device circuit or the like for a photoresist. The manufacture of the panel circuit or the attached electrode portion is carried out in the following manner: First, the upper surface of the A1 sub-substrate (4) substrate is irradiated by chemical oxygen phase deposition (CVD) or sputtering. After the film is exposed to ultraviolet light or the like, it is exposed to light, and then used to smear Wenzhou and use the composition of the liquid to develop; = patterned; the patterned photoresist is used as the material, The metal film is etched; and after the last name, the unnecessary photoresist is stripped and removed using the stripper composition. By repeating these operations, a semiconductor element circuit or the like is formed. Here, as the metal film, for example, an aluminum alloy such as aluminum (Α1); aluminum-bismuth-copper (A _si-Cu); titanium (Ti); titanium alloy such as titanium nitride (TiN); or w, p is used. ~ Si is equal. These metal films form a single layer or a plurality of layers on the substrate. Conventionally, such a developer composition for photoresist has been widely used as an aqueous solution of an organic base or an inorganic base for θ, in particular, a metal tetraalkylammonium hydroxide-free aqueous solution. 5 200805003 However, the above-mentioned developer composition for photoresist is highly corrosive to gossip. Therefore, the above-mentioned photoresist (four) f is not suitable for a substrate in which the characteristics of the A1 wiring are formed and the characteristics are deteriorated. In particular, as described in Patent Documents 3 and 4, a photosensitive organic film (here, a photoresist) pattern formed by exposure and development is subjected to a second development process (hereinafter referred to as redevelopment). Deformation (also in the case of additional re-development treatment and deformation of dissolved reflow) is used as a base film (here, W, A1 alloy or two)

When the mask of the multilayer film (such as the base film is again engraved), it is difficult to use a developer for a photoresist. For the reason of the re-development treatment, the base layer = film or the like (A1 or A1 alloy monolayer film or multilayer film of a1/m〇/ai) is formed as a wiring, etc., and the side of the wiring is also Sad in the form of exfoliation. Further, in the case of the first ilf 彡 treatment, the area of the rot is changed from a solid film (i.e., a 'blank wafer) state to a wiring such as wiring. Therefore, if the (re-) development processing is carried out, the rot will be concentrated, and the shape of the cross-section side of the "A1 m" will be greatly controlled. Also, it is more likely to cause a disconnection. ", "111" to suppress the Corrosion of A1 Corrosion' has been studied in various ways: for example, 'Patent Literature", describing a developer for resist, liver polyphenol 2 0~s η to e heavy It is blended in a developing solution for anti-agents in which the main component is water containing no metal ions. Further, Patent Document 2 describes a developer composition for an elixir which contains an organic 351 to 10 weight: two: : 1 to 10% by weight, and 1 to 10% by weight of the polyol. However, the developer composition for several doses is still insufficient in the corrosion resistance of A1. [Patent Document 1] Japanese Patent No. 3417432 6 200805003 曰Japanese Patent Laid-Open Publication No. 2003-330204, JP-A-2005-159294, JP-A-2005-159292

Therefore, the present invention is not intended to provide a developing solution for photoresist which is excellent in developability. " The inventor of the case, etc., in order to solve the above problems, the results of the re-examination, found such as the strike 〇 a 疋仃 various shell

Ah is a water-soluble organic solvent containing a specific range of content of the fourth floor of the oxidizer, the number of slaves is more than 5, and the water-soluble organic solvent of the Banpan^, not the 70 alcohol: 2 = making the photoresist When the ratio of the dissolution rate of the dissolution rate of the exposure portion is _^ ==, the developer solution for the photoresist Si is very small in terms of 1 rot (4), and the developability is also good, and the present invention is completed. a developer composition for a photosensitive organic film, comprising A) tetramethylammonium hydroxide ^^ 〇 〇 5 5~5 wt%, B) carbon number 5 or more

[Patent Document 2] [Patent Document 3] [Patent Document 4] [Draft Content] Sugar alcohol 10~4 〇番旦〇 / a weight %, more preferably 12 to 30% by weight, C) water-soluble without polyol The organic solvent is 3 to 〇丄9 wt%, more preferably 11 to 17 wt% and water of the remainder of Dm, and the solubility in the exposed portion of the photosensitive organic film and the unexposed portion of the photosensitive organic film. The ratio of dissolution rates is 50 or more. In the aspect of the invention, the content of the component 3) is 80% or more of the content of the component c). The above-mentioned component A) is at least one selected from the group consisting of tetramethylammonium hydroxide and tetraethylammonium hydroxide. 7 200805003 In another aspect of the invention, the first $B) component is at least one selected from the group consisting of sorbitol and xylitol. In still another aspect of the present invention, the component "c" is at least one selected from the group consisting of a smectite, a diol ether, and a guanamine. In still another aspect, the C is The composition is selected from the group consisting of disulfoxide, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, N, N-dimethylacetamide and n-methyl-2 - at least the species of pyrrolidone. [Effects of the Invention] According to the present invention, the following effects can be obtained: (1) The composition of the present invention, the dissolution rate of the exposure portion of the oblique portion and the photoresist, and the dissolution rate of the unexposed portion of the photoresist The ratio of 50 or more, the development of the photoresist is easier to operate than the good rot. (2) The composition of the present invention does not control the development process because the dissolution rate of the photoresist is too large, and it is easy to control the development process, and it is not carried out after the exposure is completed. The central solution is too small and it takes a long time to process it quickly on (4). [Functional Example] The component A), for example, may be a base, a sputum, a dry ww, a squirting, a scent, a sulphur, a sulphur, a sulphur, a dimethyl bis(2-hydroxyethyl) Ammonium and the like. Anyone with emulsified tetramethylamine, _ used alone, also ... human ethyl ammonium is preferred. These may be used singly or in combination of two or more. When the content of the component A) is % by weight, since it is two: slow weight, ^ more than 5% by weight of the Japanese, the mountain is not. Further, the content of the component A) is such that the difference in the dissolution rate between the exposed portion where the photoresist cannot be obtained and the portion of the unexposed portion 8 200805003 'cannot form a pattern' and the austemporal residue cannot be suppressed, and thus is not preferable. The above components are as long as (4) 5 or more. The sugar alcohol (the carbonyl group of the sugar is reduced by the chain polyol. The oligosaccharide is contained), for example, a sugar alcohol having a carbon number of 5 to 7 is not particularly limited, and is, for example, arabitol, & sorbitol, xylose Alcohol, mannitol, ribitol, aldolitol (alUt〇1), glucose alcohol (glucit〇1), iditol, galactitol, altitol (10) 〇ι), heptose Alcohol, maltitol (maltitoi#. This stupid is especially good for sorbitol or xylitol. These can be used alone or in combination of two or more kinds of ingredients.) The content of the ingredients is 1G to 4G% by weight. , when the content of the component is less than 1% by weight, the content of the component is less than 1% by weight, and the content of the component is higher than that of the photoresist. It is too small, so it is also not good. The inner DW' is not particularly limited due to the aforementioned component C), and is preferably, for example, Ethers, guanamines, etc. Sulfoxides, such as ', B-milling, etc., glycol ethers, for example, may be diethylene glycol: sub-wind _ - Ethylene monoethyl ether, diethylene glycol monobutyl hydrazine , - early squama, diethylene glycol scales, etc., guanamines such as 4 singular, propylene glycol monomethyl acetamide, Nn ... carbamide, N, N - dimethyl 2 - pyrrolidone Etc. & 笙 Α Α dimethyl sulfoxide, diethylene glycol monobutyl ether 'especially alcohol monomethyl ether, hydrazine, hydrazine dimethyl dimethyl acetamide di-ol monoethyl ether, diethylene Preferably, these can be used alone, and the content of the methyl-2-pyrrolidone C) component is 3~丨乂. The weight of the core is preferably U~17% by weight. 9 200805003 C) The content of the component is less than 3% by weight When the developing speed of the photoresist is too small, it is not preferable. When the content of the component C) exceeds 19% by weight, the ratio of the dissolution rate of the exposed portion of the photoresist to the dissolution rate of the unexposed portion is small, and several methods are formed. The pattern B) has the effect of suppressing the corrosiveness of A1, and on the other hand, the solubility and developability of the photoresist are also remarkably lowered. The solubility of the photoresist can be improved, and the effect of reducing the developability due to the component B) can be prevented. However, if a component c) which greatly exceeds the content of the component B) is added, the solubility of the photoresist will be Excessively improved, and there may be no difference in the dissolution rate between the exposed portion and the unexposed portion of the photoresist. Therefore, the composition of the component B) contains more than 1% of the content of the component c). The ratio of the dissolution rate of the exposed portion of the photoresist to the dissolution rate of the unexposed portion of the photoresist is $5 G or more. If the ratio is less than 50, the unexposed photoresist is also dissolved during development, and the developability is poor. If the dissolution rate ratio is large (5G or more), the unexposed photoresist has almost no solution, and only the exposed photoresist is dissolved, so the developability is good. It is preferably 80 or more. Moreover, regardless of the dissolution rate ratio, the dissolution rate of the unexposed photoresist is large, and the unexposed photoresist is completely dissolved (4), since the dissolution rate of the photoresist domain is too large to control the development process, it is not preferable, In the case where the dissolution rate of the exposed photoresist is too small, development takes a long time, so it is not appropriate. Therefore, the dissolution rate of the unexposed photoresist is preferably 1 〇 〆 sec or less. Further, it is preferable that the dissolution rate of the exposure to the tomb is 100 Å/sec or more. 10 200805003 'Additional addition of the composition of the present invention to a composition for a general photoresist composition such as a surfactant which does not impair the object of the present invention 0. The composition of the present invention may be as described above. ~c) Each component, and optionally other additives, and the remainder of the water are formulated. The present invention = the concentration of the solute of the composition, which can be suitably used in a developing device or the like, but usually can be made into an aqueous solution of 36 to 85% by weight.

The composition of the present invention is used as a resist for developing a photoresist when a semiconductor integrated circuit or a semiconductor element circuit of a liquid crystal panel is manufactured. The temperature of the use, the development processing time, etc., may be appropriately set, and there is no particular limitation, and it is usually set to a normal temperature of ~5 (rc, 2 sec. to several minutes. Further, the development processing method is not particularly limited. ^, can be processed using a commonly used development device. The composition of the present invention, the A1 etch rate is small. That is, the composition rate of the present invention can be 3 Å/sec from the listening process. According to the above, the photoresist composition for photoresist of the present invention can develop an exposed photoresist on a half (four) substrate or a liquid crystal glass substrate without causing A. The present invention will be described below based on examples, but the present invention is not limited to the examples. Embodiment 1 (1) A1 etching rate is formed on a wafer having a 1 Å ai solid film on the surface (ie, 11 200805003 A1 single-layer film masking wafer) is immersed in the photoresist developing solution at 5〇〇c. The substrate is taken out every 60 seconds, 120 seconds, and 18 seconds, and washed with pure water to use N2 gas. The air gun blows off the pure water to dry it. Immediately after drying, the probe is 4 points. The film thickness of A1 was determined. The immersion time and the ai film thickness were plotted, and the A1 etch rate was obtained from the slope of the pattern. The results are shown in Table 1. In the case where the A1 etch rate is small, the corrosion of A1 is also small. On the other hand, in the case where the etching rate of A1 is large, the corrosion of μ is also large. (2) Developability

HMDS (hexamethyldisilazane) was spin-coated on a Si wafer and baked at 100 C for 2 minutes. Next, a positive-working photoresist NPR3510PG (manufactured by Nagase Chemtex Co., Ltd.) was spin-coated at 1 Torr.匚 Pre-bake for 2 minutes. Next, the photoresist was fully exposed using PLA (made of Ca) and completely sensitized. Finally, the main supply was baked at 12 Gt for 2 minutes to form a full-length film substrate having an average film size of 15 Å and an exposed film (i.e., masking the wafer. The same applies hereinafter). After HMDS is spin-coated on the W wafer, (10). C for Xiao 2 minutes. Next, a positive-working photoresist NPR3510PG (manufactured by Nagasechemtex Co., Ltd.) was spin-coated, and pre-baked for 2 minutes at 1 〇. Finally, the main baking was performed for 2 minutes, and the average film thickness was 15_$. An unexposed full-resistance substrate. After the substrate is formed, the initial film thickness of the photoresist of the two substrates is measured by an optical film thickness measuring device. The two substrates are respectively immersed in the photoresist developing solution at room temperature. After immersing, 'take the substrate out', after washing with pure water, use pure air to blow off the pure water and let it dry naturally. After natural drying; measure the residual anti-(4) (four) thickness with a film thickness measuring device. The film thickness and the residual film 12 200805003 thickness difference divided by the soaking time, calculate the resist dissolution rate (A / sec). In addition, the exposure rate of the comprehensive photoresist substrate of the resist dissolution rate, divided by the unexposed The resist dissolution rate of the full-resistance substrate, and the ratio of the dissolution rate of the resist due to the presence or absence of exposure (hereinafter referred to as the dissolution rate ratio) is calculated. The result is as shown in the figure, regardless of the dissolution rate ratio, if it is not exposed. Dissolution of photoresist When the solution speed is 500 angstroms/second or more, since the dissolution rate of the entire photoresist is too large, the development process cannot be controlled, so it is not suitable. Moreover, regardless of the dissolution rate ratio, if the exposure speed of the exposed photoresist is less than 100 angstroms ^/ In the second case, it is not suitable for the length of the Jia. It is also inappropriate for the comparative examples 2, 3, 4 ^ 、 , and 12, because the dissolution rate of the unexposed photoresist is below i Å / sec. Umbrella - 觅 1 ^ The exposure rate of the photo-resistance of the first exposure is 500 = so the correct (four) solution speed ratio cannot be calculated. Therefore, the dissolution is not calculated = 2::: A: refers to each side B 1: sorbitol B2 · Xylitol C1: dimethyl sulphate C2: N, N~ dimercaptoacetamide C3: diethylene glycol monoethyl ether C4 · a 7 • monoethylene glycol monomethyl ether D1: pure water E1 · Glycerol E2: propylene glycol 13 200805003 Examples 2 to 6 The same procedures as in Example 1 were carried out except that the release agent compositions shown in Table 1 were used. Comparative Examples 1 to 12 In addition to the use of the release agent composition shown in Table 1, The rest are the same as in the first embodiment.

[Table 1]

From Table 1, the composition for developing a photoresist of the present invention (embodiments 1 to 6) has a small magical rate and a sufficiently large dissolution rate ratio. Moreover, the anti-recession J of the exposure is sufficiently high, and the dissolution rate of the unexposed anti-rice is sufficiently small. On the other hand, in the tetraalkylammonium hydroxide aqueous solution (Comparative Example i), the dissolution rate ratio was sufficiently large, but the A1 etching rate was large. Further, the aqueous solution containing 2% by weight of tetraalkylammonium hydroxide and 15% by weight of a sugar alcohol having 5 or more carbon atoms and containing no c-forming knife (Comparative Example 2), although the etching rate of A1 is small, the exposure cannot be dissolved. Light resistance. Further, an aqueous solution containing 2% by weight of tetraalkylammonium hydroxide, 15% by weight of a water-soluble organic solvent, and *B-containing component (Comparative Example 14 200805003 3乂 and containing tetramethylammonium hydroxide up to 1% by weight and carbon Number = 15% by weight of water/complex organic solvent 15% by weight of aqueous solution (Comparative Example A1 (IV) has a high rate and can completely dissolve the unexposed photoresist. Further, it contains 2% by weight of tetraalkylammonium hydroxide, s. On the other hand, a water-soluble organic solvent-containing aqueous solution (Comparative Example 5) containing up to 50% by weight of a sugar alcohol having 5 or more carbon atoms hardly dissolves the exposed photoresist.

$2% by weight of tetraalkylammonium hydroxide and 15% by weight of sugar alcohol having a carbon number of 5 or more. In addition, an aqueous solution containing a water-soluble organic solvent of 5% by weight (Comparative Example 6), and containing hydrogen 2,5 wt% of tetraalkylammonium oxide, on the other hand, only a small amount of an aqueous solution containing 7 wt% of a carbon number of 5 or more but up to 70 wt% of a water-soluble organic solvent (Comparative Example 12) Fully dissolve unexposed photoresist. Further, the composition described in Japanese Patent No. 3,417,432 (Comparative Examples 7 and 8) and the composition described in JP-A No. 2,3,3,3,2,4 (Comparative Example 9, No. 1) have a large etching rate of Α1. Further, an aqueous solution containing 0.5% by weight of tetraalkylammonium hydroxide and only 1% by weight of a sugar alcohol having 5 or more carbon atoms but containing up to 4% by weight of a water-based organic solvent (Comparative Example 11) ), the dissolution rate ratio is small, and is not suitable as a developer. The compositions of Comparative Examples u and 12 contained the components of A to D, but they were compositions of the resist stripping agent, and it was clearly impossible to use them as a developing composition. Further, in the case where the developer of the present invention having the compositions of the above Examples 1 to 6 is used, and the base film is a multilayer film of Al, Al alloy or Al/Mo/A1, as described in the aforementioned Patent Documents 3 and 4, an attempt is made. Used for redevelopment processing of photoresist patterns. As a result, it was confirmed that the A1 wiring or the like (A A1 alloy single layer film or a multilayer film such as Al/Mo/A1) has almost no change in cross-sectional shape, 15 200805003 and can be used only for the purpose of the original purpose. Only develop the photoresist pattern. β - L-seat utilization]

The composition of the present invention has excellent A1 corrosion resistance and excellent development performance, and can produce a highly reliable product at a high yield when manufacturing a semiconductor integrated circuit, a semiconductor element circuit of a liquid crystal panel, and the like, and is therefore applicable. For manufacturing semiconductor component circuits and the like. In particular, in the case of performing the development processing for the first time = the development of the second appearance after the second development, that is, the green-sensitive organic film pattern after the initial application of the development treatment, the level of the invention is used = four times (four times) _ treatment, or for the first use::,, etch: the photosensitive organic film pattern after the mask, using the composition film of the present invention; slanting the sensitization after the mask of the multilayer film containing the A1 or A1 alloy When the organic matter is subjected to the development treatment of the second and subsequent times, the use of the present invention is particularly effective in the case where the photosensitive organic film is a photoresist. [Simple description of the diagram] (None) [Description of main component symbols] (none)

Claims (1)

200805003 X. Patent application: 1 · A developer composition for a photosensitive organic film containing: A) tetraalkylammonium hydroxide 0·5~5 wt%, B) a sugar alcohol having a carbon number of 5 or more 〜4〇% by weight, C) 3~19% by weight of the water-soluble organic solvent containing no polyol, and d) water of the residual portion, the dissolution rate of the exposed portion of the photosensitive organic film and the unexposed of the photosensitive organic film The ratio of the dissolution rate of the portion is 50 or more. 2. The developer composition for a photosensitive organic film according to the first aspect of the invention, wherein the component B) is at least 8 % by weight of the component c). 3. If you apply for a patent scope! The developer composition for a photosensitive organic film according to the invention, wherein the content of the component B) is 12 to 3 wt%, and the content of the fraction is 11 to 17 wt%. 4. The developer composition for a photosensitive organic film according to claim 2, wherein the component B) is contained in an amount of 12 to 3 % by weight, and the content of the component c) is 11 to 17 % by weight. The developer composition for a photosensitive organic film according to the above aspect of the invention, wherein the component A) is at least one selected from the group consisting of tetramethylammonium hydroxide and tetraethylammonium hydroxide. 6. The developer composition for a photosensitive organic film according to the scope of the invention, wherein the component B) is selected from at least one of sorbitol and xylitol. 7. The developer composition for a photosensitive organic film according to claim i, wherein the stomach C) component is at least one selected from the group consisting of sulfoxides, ethylene glycol scales, and guanamines. 8. If you apply for a patent letter! The photosensitive organic film developing solution group 17 200805003, wherein the component c) is selected from the group consisting of - 兀曰 兀曰 甲 甲, diethylene glycol monobutyl ether, diethyl ether monoethyl ether, diethylene glycol At least / of the monomethyl N-methyl-2-pyrrolidone and the early caller, N,N-dimethylacetamide 9. As in the first paragraph of the patent application, a + t A composition for developing a precursor organic film for sensation, wherein the sensitivity is _ is a photoresist. For example, if the patent application scope is 1st Q τ5 + 2, the film is made of strong-density film, the photosensitive organic film is used for the photosensitive liquid composition, which is used to sensitize the photosensitive film. The organic film pattern is subjected to development processing of the second person. For example, in the application of the patent scope 丨i 9 medium film developer composition, A is used in the _ raw organic use in the use of the etched mask after the use of the first organic film pattern, the second and subsequent development deal with. The photosensitive organic layer of the film of any of the first to ninth aspects of the invention, the read composition, which is used after the etching mask of the multilayer film of the single A1 or A1 alloy which is an ai or ai alloy is used. The first organic film is 感, 隹 〇 ^ A ^ ^, Koumu, and the development process after the second time. XI. Schema: None. 18