TWI306184B - Thinner composition for removing photosensitive resin - Google Patents

Description

1306184 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明Conductor device or liquid crystal display device release composition. In particular, the invention can effectively remove the invention during the preparation process.

[Prior Art] A microcircuit pattern such as a circuit, a thin layer of its analog, a drawer, is uniformly coated on a surface, and the photoresist is exposed and developed to become a *^ a photoresist pattern, after which the mask is selectively etched to a thin layer under the photoresist pattern, and finally the photoresist is completely removed. When photolithographic etching is used to form a semiconductor product or a TFT-LCD circuit, it must be diluted. The agent may completely form the glass substrate or the remaining undesired photoresist and the exposure to the substrate before exposure and development. The film is completely removed. Traditionally, ethers and acetates, such as cellosolve, acetate, a propylene-alcohol ether, a propylene glycol ether acetate, etc.; a ketone such as propylene-ethyl S, methyl isobutyl ketone, cyclohexanone, etc.; and an ester such as ethyl lactate, methyl acetate, ethyl acetate, acetic acid Butyl esters, etc., have been used as diluents. For example, '曰 专利 Patent Publication No. Hei 4-4993 8 discloses alcohol monomethyl ether acetate (pr〇pylene glyC〇l monomethyl-LCD and subsequent photoresist base) Insoluble ketones on the board, and milk as the propylene Ther

1306184 acetate, PGMEA) is used as a diluent; and Japanese Patent Publication No. 4-42523 discloses the use of alkoxypropionic acid vinegar as a diluent. These use a single solvent, for example, ethylene glycol monomethyl ether acetate (EMMAA)' alcohol monodecyl ether acetate, ethyl lactate or the like. It has the following limitations. Although ethylene glycol monoethyl ether acetate (EGMEA) has an excellent degree, it is highly volatile and flammable, and more importantly, EGMEA is reduced in white blood cells, abortion, and the like. In the preparation of PGMEA, the β-form PGMEA is known to cause fetal malformation and inevitable poisoning. As for the use of ethyl lactate alone due to its high viscosity and low solubility, it does not provide sufficient cleaning effect. Solvents such as acetone, ketone, etc. are not used because of their low flashing point. In order to solve the above problems, a conventional solvent mixing method has been developed. Japanese Patent Publication No. Hei 4-130715 discloses a mixture of methyl ethyl ketone as a diluent; Japanese Patent Publication No. 7-1 46 5 62 discloses a thinner composition comprising propylene glycol alkyl propionate alkyl-3 - alkoxylate. A thinner composition comprising propylene glycol alkyl ether, butyl acetate and ethyl ester, or a mixture of butyl acetate, ethyl lactate and propylene glycol alkyl ether ester is disclosed in Japanese Patent Publication No. Hei 7-128867. mixture. Japanese Patent Publication No. Hei 7-1 60008 discloses a thinner composition comprising a mixture of propylene glycol alkyl ether propionate and hydrazine, or a propylene glycol alkyl ether propionate and a

The Hei method acid ester is dissolved in the form of a mixture of a parent salt, a salt which is often difficult to form, and a Hei ether and a lactic acid acetic acid as a methyl methacrylate 6 1306184 ester. U.S. Patent No. 4,9,8,3,0,0,0, discloses a diluent composition comprising a mixture of propylene glycol alkyl ether acetate and propylene glycol alkyl ether. U.S. Patent No. 4,886,728 discloses a thinner composition comprising a mixture of ethyl lactate and acetophenone. However, these mixtures are also limited in the manufacture of semiconductor devices and liquid crystal display devices, which are more integrated and bulky.

For example, a mixture comprising an alkyl pyruvate solvent and an acetophenone has a lower solubility for the 1,2-naphthyl diazide sensitizer (1,2-naph. thoquinone diazide), which is the main component of the photopolymer layer. . Further, when a highly volatile solvent such as a mixture of propylene glycol alkyl ether propionate and butyl acetate is used, the thickness of the cooling photoresist layer varies greatly with the substrate. When a low volatility solvent such as a mixture of ethyl lactate and methyl ethyl ketone is used, the edges of the substrate may not be cleaned. In particular, it is known that such as methyl pyruvate, ethyl pyruvate or the like can corrode metal portions in the container. In addition, when these mixtures are used on a large-color glass substrate required for the manufacture of liquid crystal displays, it may not be possible to completely remove the undesired photoresist. The remaining photoresist may form a band after development. SUMMARY OF THE INVENTION An object of the present invention is to provide a thin film composition capable of removing photosensitivity, which can effectively remove adhesion to a substrate in a short time (especially for large color glass required for manufacturing liquid crystal displays). Substrate) edge and back 7 1j〇6184 do not want photoresist. The present invention provides a dilute material capable of removing photosensitive photoresist, which can be effectively cleaned by reducing the gap at the interface. [Embodiment] The preparation agent f achieves the above object, and the present invention Provided is a dilute composition capable of removing photosensitive wax, which comprises a) a monoalkylamine and b) a ketone. The diluent composition may further comprise c) a perfluoroalkylamine oxide. Preferably, the thinner composition for removing the photosensitive resin of the present invention =: a) from 1 part to 90 parts by weight of alkylguanamine, b) from 1 part to 9 parts by weight of ruthenium. Class '纟c) 〇. 〇〇 1 part to 1 part by weight of perfluoroalkylamine oxide. Hereinafter, the present invention will be described in detail. The invention is characterized in that a thinner combination capable of removing photosensitive photoresist: the utility model can effectively remove the edge and the back of the substrate (especially the large-color glass substrate required for manufacturing the liquid crystal display) in a short time. The photoresist composition is not desired, and thus the thinner composition can be used to manufacture a semiconductor device or a liquid crystal display device. In the diluent conjugate of the present invention, a) the alkyl decylamine; b) the oxime and c) each of the perfluoroalkylamine oxides are selected from the ultrapure semiconductor grade at the VLSI stage. 'The system is selected to pass the 〇1 (four) filter. The alkylguanamine gives the solubility of the improved composition. The alkyl group of the alkylamine has at least 1 carbon atom, preferably 2 to 5 carbon atoms. In particular, 1306184 is preferably at least one selected from the group consisting of N-methylethylamine, dimethyl decylamine and dimethylacetamide. If it is considered from the viewpoint of solubility, it is preferred to use dimercaptoacetamide.

Preferably, the alkylamine is contained in an amount of from 10 parts by weight to 9 parts by weight per 100 parts by weight of the composition. If the weight fraction of the alkylguanamine is less than 10 parts, it will not dissolve the colored photoresist, so that the photoresist remains in the final layer of the substrate. On the contrary, if the weight fraction of the alkylguanamine exceeds 90 parts, the volatility thereof will be lowered, so that the EBR line becomes uneven, and in a more extreme case, a color light-blocking interface may be infiltrated. Preferably, the ketone selected is at least one selected from the group consisting of cyclic ketones and a compound having the formula RkOR2 wherein Ri and R2 are a group having at least one carbon atom, preferably 2 to 5 carbon atoms. Compounds in the group consisting of. In particular, the ketone is preferably at least one selected from the group consisting of acetone, mesopropylamine, methyl-acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl copper, cyclopentanone, cyclohexanone, and cycloheptane. The material in the group of people. Preferably, the ketone is contained in an amount of from 1 part to 90 parts by weight per 100 parts by weight of the composition. If the ketone is less than 10 parts by weight, the volatility will be lowered, making the EBR line uneven. On the contrary, if the ketone is more than 90 parts by weight, the ability to dissolve the colored photoresist will be lowered, so that the photoresist remains on the edge of the substrate. The diluent composition of the present invention may further comprise a perfluoroalkylamine oxide. The perfluoroxylamine oxide has a fairly good solubility for water and many solvents. Preferably, the alkyl group of the perfluoroalkylamine oxide has from about 5 to 30 carbon atoms. 9 1306184 An example of a commercially available perfluoroalkylamine oxide commodity is Ashahi Glass S-141. Preferably, the perfluoroalkylamine oxide is contained in an amount of from 0.001 part by weight to 1 part by weight per 100 parts by weight of the composition. If the parts by weight of the perfluoroalkylamine oxide is less than 0.001 part, the scavenging effect will be lowered. On the contrary, if the parts by weight of the perfluoroalkylamine oxide exceeds 1 part, the ability to dissolve the photoresist will decrease.

The thinner composition of the present invention can be used to remove a photoresist. That is, by soaking or spraying the thinner composition, the undesired photoresist adhered to the edges and the back of the substrate can be removed. The amount of the diluent composition soaked or sprayed is controlled depending on the type of the photoresist and the thickness of the film. Hereinafter, the details will be described by way of examples. However, the examples are for illustrative purposes, and the scope of the invention is not limited to the disclosed embodiments. Examples A substrate sample was prepared in the following manner. A 5 inch diameter cerium oxide substrate was used. The substrate was washed in two solutions including hydrogen peroxide and sulfuric acid, each immersed in each solution for 5 minutes' and then washed with ultrapure water. This process is performed with special cleaning equipment. Thereafter, the substrate was spin-dried by a spin dryer (VERDQ SRD 1 800-6). A predetermined thickness of photoresist was applied to the substrate by a spin coater (EBR TRACKER of the Korean semiconductor system). The spin coating process is as follows. 10 ml of the photoresist layer composition was dropped in the center of the stationary 10 1306184 substrate. Thereafter, the spin coater was applied by spinning at 300 rpm for 3 seconds. Next, it was rotated at a speed of 500 rpm to obtain a photoresist layer having a desired thickness, and the rotation time was 25 seconds. Examples 1 to 5 The composition and content of each of the thinner compositions are shown in Table 1 (unit: parts by weight).

[Table 1] Classification DMAc Acetone CXN PGME PGMEA nBA S Example 1 70 30 - - - - - 2 70 30 - - - - 0.5 3 10 - 90 - - - 4 10 - 90 - - 0.5 Comparative Example 1 - - 50 - 50 - 2 - 70 30 _ - 3 - - - - 50 50 - 4 - 50 - 50 - - - 5 50 - - - 50 - Note) 1. DMAc = dimercaptoacetamide 2. CXN = ring Hexanone 3. PGME = propylene glycol monoterpene ether 4. PGMEA = propylene glycol monomethyl ether acetate 5. nBA = butyl glycolate 6. S = perfluoroalkylamine oxide (S-141 of Ashahi glass) 1306184 - ^L Undesirable 弁. A dye layer composition is coated on a 5 inch leaf dioxide dioxide substrate. The release layer compositions of Examples 1 to 4 and Comparative Examples 5 to 9 were respectively used to remove the photoresist layer at the edge of the substrate (Edge bead removal test: hereinafter referred to as EBR test). In the EBR test, the same spin coater was used when applying the photoresist layer. Each of the thinner compositions of Table 1 was sprayed onto the coated table via an EBR nozzle

On the substrate of the two photoresist layer compositions, the spherical photosensitive material at the edge of the substrate was removed under the conditions shown in Table 3. Each thinner composition is made up of one

The pressurized barrel is fed into the nozzle. The flow rate was set to 1 _ 〇 Kgf and the flow rate of the diluent composition leaving the EBR nozzle was set to 1 Torr to 2 Torr per minute. The EBR test results for each photosensitive resin composition are shown in Table 4. [Table 2]

1306184 [Table 3] EBR test conditions Classification Spin coating speed (rpm) Time (seconds) Suspended type 300 3 Spin coating type 500 25 EBR 1 150 13 EBR 2 150 15 Drying 700 7 Development Depending on the photoresist layer

[Table 4] EBR test results of each photoresist layer composition classification example Comparative Example 1 2 3 4 1 2 3 4 5 Resin type black matrix EBR tail extension 0 ◎ 0 〇 XXX Δ Δ EBR uniformity ◎ ◎ 0 0 XXX Δ Δ EBR appears black layer ◎ ◎ Δ 0 XXXXX Development occurs peeling 0 ◎ Δ 0 XXXXX Red EBR tail extension 0 ◎ 0 0 XXX Δ Δ EBR uniformity ◎ ◎ 0 0 XXX Δ Δ EBR appears black layer ◎ ◎ Δ 0 XXXX Δ development occurs peeling 0 ◎ Δ 0 XXXX Δ Green EBR tail extension 0 ◎ 0 0 XXX Δ Δ EBR uniformity ◎ ◎ 0 〇 XXX Δ Δ EBR Black layer ◎ ◎ Δ 0 XXXX Δ Development peeling occurs 0 ◎ Δ 0 XXXX Δ 13 1306184 Tail extension after blue EBR 0 ◎ 0 0 XXX Δ Δ Uniformity after EBR ◎ ◎ 0 0 XXX Δ Δ Black after black Layer ◎ Δ Δ 0 XXXX Δ Development peeling occurs 0 ◎ Δ 〇 XXXX Δ In Table 4, development is performed by spin coating a dilution of a JSR developer 100 onto a substrate which has passed through the light. Resistance Coating, spraying thinner and pre-coating process for about 60 seconds

Note: ◎=The edge is very clean 〇=Linear edge (80% or more) △=Edge deformation due to dissolution of the diluent χ = The tail of the film occurs at the edge

As shown in Table 4, all of the thinner compositions of the present invention (Examples 4 to 4) exhibited excellent ebr capabilities for all of the photoresist layers (the edges were very clean) and the visible/post release material was completely Clear. Also, the thinner composition was sprayed without any residual film layer on the substrate. In particular, it comprises a full-ylamine = thinner composition (the effect of Example 2 and the sentence is far superior to that of Example 13. This result shows that the addition of the whole smashing agent can improve the composition thereof. The resistance of the material resist is dilute, and the second:: thinner thinner composition changes the condition of the crucible, and the cross section is better. This represents the dilution of the various 舳w + I The composition of the composition provides a better ability to remove light, and the diluent is finely entangled into the film, and the knives are also visibly stabilized by the conventional thinner composition of the present invention. The resistive thinner composition can effectively remove the undesired photoresist adhered to the edge and the back of the substrate during the manufacturing process of the liquid crystal 14 1306184 display device (especially the large-color glass substrate). In addition, it can also clear the interface. The remaining film layer and the reduced height difference between the interfaces enable more efficient removal of the substrate. Therefore, it can be used in various processes to provide economic benefits, simplify the process and improve the yield.

A person skilled in the art can readily appreciate the features of the present invention from the above description, and the present invention may be varied or modified to the same extent as disclosed in the present invention. Such changes or modifications are still considered to be within the scope of the invention as defined by the scope of the appended claims.

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Claims (1)

1306184 Pickup, Patent Application Range 1. A thinner composition for removing a photoresist layer, to a) alkanoguanamine; and b) a ketone. Less include: 2. The thinner composition according to claim 1 a) 10 to 90 parts by weight of a alkylguanamine; and b) 10 to 90 parts by weight of a ketone. And comprising: 3. The thinner composition as described in claim 1 containing c) a perfluoroindolylamine oxide. 4. The thinner composition as described in claim 3, a) from 10 parts to 90 parts by weight of alkylguanamine; b) from 10 parts to 90 parts by weight of ketone; and c) 0.001 Parts to 1 part by weight of perfluoroalkylamine oxide. , its more package, which contains: 5. The thin matter according to any one of claims 1 to 4, wherein the alkylguanamine is at least one selected from the group consisting of N-mercaptoacetamide, dimethylamine, and dimethylacetamide. At least one of the constituent groups of the composition, wherein the ketone of the release composition according to any one of claims 1 to 4 is at least one selected from the group consisting of acetone, methyl isopropanone, methyl-acetone, methyl isobutyl ketone, and A combination of isobutyl ketone, cyclopentanone, cyclohexanone and cycloheptanone, and a diterpene group. , wherein the methyl ethyl ketone, the group of substances in the group 16 1306184. 7. The release composition of claim 3, wherein the alkyl group of the perfluoroalkylamine oxide has from about 5 to about 30 carbon atoms. 17