KR930009525B1 - Developing solution - Google Patents

Abstract

This new developer for the positive photosensitive resin has good inhibition ability of forming scum after developing. The developed positive photosensitive resin is composed of a quinone diazide photoactive material and a novolac binder resin. The developer comprises 1-10 pts. tertiary ammonium base organic base of formula (I); and 0.01-5 pts. one or two kinds of oxazine compd of (II). In the formula, R1,R2,R3,R4 is C1-C4 alkyl; m+n=4; n=0,1,2; m=2,3,4; y=m-1 or 2m-1. Non-ion detergent, stabilizer, dissolution aids, et al can be included as additives.

Description

Positive photosensitive resin developer

The present invention relates to a positive photosensitive resin developer. In particular, the present invention relates to a positive photosensitive resin developer having an excellent effect of suppressing the development of undeveloped photosensitive resin residues after development as a developer suitable for forming a pattern of a quinonediazide-based positive photosensitive resin.

Positive type photosensitive resin utilizes the property that the solubility to the developing solution of the part exposed by the mixture of a photoactive material and binder resin becomes larger than the solubility of the unexposed part which was not exposed.

Herein, a quinonediazide compound is used as the photoactive material of the positive photosensitive resin, and a phenol-aldehyde resin, that is, a novolak resin, is used as the resin. By the way, pure novolak resin is melt | dissolved in a suitable organic solvent or aqueous alkali solution, but when a photoactive substance is added, it is very insoluble in aqueous alkali solution.

However, upon exposure, the solubility in aqueous alkali solution rises rather than the solubility of pure novolak resin. This is because the photoactive material is changed into a carboxylic acid form soluble in an aqueous alkali solution by light, thereby promoting the solubility of the mixture.

The positive photosensitive resins are widely used in photolithography, which is a major process for manufacturing LSI or VLSI semiconductor devices.

The photolithography process is summarized as follows.

First, an inorganic film such as SiO ₂ , polysilicon, or SiO ₃ N _{4 is} formed on the silicon wafer substrate, spin-coated the photosensitive resin to about 1-2 μm, and the solvent is evaporated through a thermal drying process. After the ultraviolet light exposure through a mask of, and then treated with an aqueous alkali solution developer, it is formed on the inorganic film as described above in the circuit shape of the mask used by the photosensitive resin pattern.

When this is dry etched with a fluorocarbon / oxygen plasma or the like, the inorganic film of the part not covered with the photosensitive resin is removed by plasma plasma, and the pattern of the inorganic film having the same shape as the photosensitive resin pattern of the same pattern as the circuit of the mask is reproduced. .

The processed wafer is removed by using sulfuric acid, hydrogen peroxide, and the like through ashing, which burns organic photosensitive resin, to leave only a desired semiconductor device circuit.

However, if the photosensitive resin is not completely removed by the phenomenon and remains slightly between the patterns, the inorganic film during the plasma dry etching is protected by the undeveloped photoresist residue (Scum), and the semiconductor cannot be etched to the desired shape and depth. The device circuit may not be formed properly.

Accordingly, an object of the present invention is to provide a positive photosensitive resin developer that can enhance the scum removal effect that may occur when developing such a quinonediazide-based positive photosensitive resin.

Such an object of the present invention was achieved by adding an oxazine compound to a nonmetallic positive photosensitive resin developer containing a quaternary ammonium salt aqueous solution as a main component.

The present invention relates to a positive photosensitive resin developer comprising a photoactive material as a quinonediazide compound and a binder resin as a novolak resin, wherein the quaternary ammonium compound of the general formula (I)

The positive photosensitive resin developer characterized by containing 1-10 weight part of organic bases, and 0.01-5 weight part of 1 type, or 2 or more types of mixtures of the oxazine type compound of following General formula (II).

In the above, R ₁ , R ₂ , R ₃ , R ₄ are C ₁ -C ₄ alkyl groups (where R ₁ is absent when n = 0 in II), m + n = 4, n = 0,1,2, m = 2,3,4 y = m-1 or 2m-1 (where x = 0 if n = 0, x = n-1 or 2n-1 if n ≠ 0).

In the present invention, in addition to the above components, nonionic surfactants, stabilizers, dissolving aids and the like may be included as additives.

For example, the present invention will be described in more detail as follows.

Example 1

The developer was prepared as follows.

Tetramethylamnonium hydroxide 25% aqueous solution 109,382 g

1,2-oxazine 0.6 g

After distillation, distilled water was poured so that the total composition volume was 1 liter.

On the other hand, the positive photosensitive resin S1400-27 (trade name, manufactured by Shipley, USA) or TSMR-8800 (trade name, manufactured by Tokyo Okoka, Japan) on a 6-inch silicon wafer substrate coated with a silicon oxide film of 3000 Å was 1.42 thick. 436nm ultraviolet exposure (exposure machine; Nikon Corporation NSR1505G4C) through spin coating with a mask of 1.0 μm Line / Space pattern followed by immersion at room temperature for 1 minute using the developer of the present invention, followed by electron beam scanning microscope ( As a result of observing the 1.0 µm Line / Space pattern through SEM), it was found that the development of undeveloped photosensitive resin residue, that is, scum, was very suppressed.

As a result of this work, it was not possible to find a large scum with a diameter of 0.1 μm or more, which may adversely affect the dry etching process among a total of 25 wafers.

Example 2

It is the same as Example 1 except having used 1, 3- oxazine instead of a 1, 2- oxazine.

Example 3

Same as Example 1 except that 1,4-oxazine was used instead of 1,2-oxazine.

Example 4

Example 1 except that tetrahydro-1,2-oxazine was used instead of 1,2-oxazine.

Example 5

The same procedure as in Example 1 was conducted except that tetrahydro-1,3-oxazine was used instead of 1,2-oxazine.

Example 6

It is the same as Example 1 except having used N-methyl tetrahydro- 1, 4- oxazine instead of 1, 2- oxazine.

Example 7

The same procedure as in Example 1 was repeated except that 0.3 g of 1,2-oxazine and 0.3 g of tetrahydro-1,4-oxazine were used in place of 1,2-oxazine.

Comparative Example 1

It was the same as the developing solution prepared in Example 1 except that 1,2-oxazine was not used.

Scum with a diameter of 0.1 µm or more was found in only 25 wafers.

The above result is put together in the following table | surface.

Claims (2)

In a positive photosensitive resin developer consisting of a photoactive material as a quinone diazide compound and a binder resin as a novolak resin, 1 to 10 parts by weight of a quaternary ammonium organic base of the following general formula (I) and the following general formula (II) A positive photosensitive resin developer comprising: 0.01-5 parts by weight of an oxazine compound In the above, R ₁ , R ₂ , R ₃ , R ₄ are C ₁ -C ₄ alkyl groups, provided that R ₁ is absent when n = 0 in formula (II), m + n = 4, n = 0,1 Or 2, m = 2,3 or 4, y = m-1 or 2m-1 (where x = 0 if n = 0, x = n-1 or 2n-1 if n ≠ 0). The oxazine compound (II) according to claim 1, wherein the oxazine compound (II) is 1,2-oxazine, 1,3-oxazine, 1,4-oxazine, tetradihydro-1,2-oxazine, tetrahydro-1,3 Positive type photosensitive resin developing solution characterized by the 1 type (s) or 2 or more types chosen from -oxazine, tetrahydro-1,4-oxazine, and N-methyl tetrahydro-1,4-oxazine.