JPH04109252A - Developer for photoresist - Google Patents

Abstract

PURPOSE:To improve the leaking property to a photoresist and the developing speed of the photoresist by compounding a specific compd. with an aq. alkaline soln. CONSTITUTION:The compd. expressed by formula I is compounded at 1 to 5,000ppm with the aq. alkaline soln. In the formula I, straight chain or branched chain satd. or unsatd. aliphat. hydrocarbon groups are usable without limitation as the aliphat. hydrocarbon or R insofar as 4 to 14C; n is 3 to 7 integer. The developer for the photoresist which has the good leaking property and foams less is obtd. without lowering the developing speed of the photoresist and the formation of patterns with high definition is possible.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a developer for photoresist.

[The problems that the prior art and inventions try to solve] In recent years,
In the field of microelectronics, progress is being made to improve the degree of integration of integrated circuits. Therefore, the resist used for pattern formation must have high resolution, and generally a positive resist is used, which is a combination of an alkali-soluble resin and a naphthoquinonediazide compound as a photodegrading agent. Also, ne, v
M-resists have also been developed that are soluble in alkaline aqueous solutions and have improved resolution.

An alkaline aqueous solution is used as a developer for this type of resist, but when the pattern is fine, the alkaline aqueous solution cannot be immersed up to the base for t minutes, resulting in poor hem cutting at the base. It has its drawbacks. Therefore,
It has been proposed to add various surfactants to the aqueous alkaline solution to improve the wettability of the resist. However, in that case, the added surfactant
It reduces the resist development speed and impairs productivity. In addition, foaming tends to occur, which is not only inconvenient during liquid transfer during pouring into a container, but also during development, the generated foam adheres to the surface of the resist F, causing poor development.

Therefore, there has been a strong desire to develop a developer for the present tresist, which has good water resistance and less foaming without reducing the development MFI of the tresist.

Means for Solving ``1''] The present inventors have conducted extensive research V* in order to solve the above problem.
It's coming. As a result, they discovered that the problem could be solved by blending a specific compound into the alkaline water Il-box and proposed the present invention.

That is, the present invention provides an alkali water injection l# solution with - general formula % formula % (wherein R is an aliphatic hydrocarbon group having 4 to 14 carbon atoms, and n is an integer of 3 to 7). The compound represented by l~s
This is a photoresist developer containing o o op.

In the present invention, as the alkaline aqueous solution, any of the conventionally known developing solutions can be used without limitation. Specifically, aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; aqueous solutions of amines such as pouvylamine, butylamine, dibutylamine, and triethylamine; or trimethyl (2-hydroxy ethyl)
Examples include aqueous solutions of quaternary ammonium compounds such as ammonium hydroxide, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. Among these, it is particularly preferable to use an aqueous solution of trimethyl(2-hydroxyethyl)ammonium hydroxide or tetramethylammonium and droxide.Also, an aqueous solution containing a combination of two or more of the above alkali compounds may be used. The concentration of the alkali compound used is preferably in the range α] to 10% by weight, preferably 1 to 5% by weight.

The most important feature of the present invention is that the above alkaline aqueous solution is prepared using the general formula % (in the formula, R is an aliphatic hydrocarbon group having 4 to 14 carbon atoms, and is an integer of 3 to 7). The reason is that the indicated compounds are included. In the above general formula, the aliphatic hydrocarbon group represented by CR may be a straight-chain flexible or branched saturated or unsaturated aliphatic hydrocarbon group as long as it has 4 to 14 carbon atoms. However, the aliphatic hydrocarbon group has 4 carbon atoms.
If the number of carbon atoms is smaller, the wettability of the developing solution for the present photoresist will not be sufficient. On the other hand, if the number of carbon atoms is greater than 14, the wettability will not be sufficient, and foaming will also increase.

Further, in the general formula, the base is an integer from 3 to 7.

When the value of #n is less than 3, the compound represented by the above general formula becomes difficult to dissolve in an alkaline aqueous solution, and when it is larger than 7, the above-mentioned wettability becomes insufficient. Here, among the compounds represented by the general formula, polyoxyethylene (* = 3
) octyl ether, polyoxyethylene (rh =
3) Nonyl ether.

Polyoxyethylene (n = 3) lauryl ether, polyoxyethylene (!L = 5) octyl ether, polyoxyethylene (!k = 5) lauryl ether, polyoxyethylene (!1 = 5) tetradecyl ether, polyoxy Ethylene (n = s) octyl ether, polyoxyethylene (!l = 6)
lauryl ether.

Examples include polyoxyethylene (x==7) nonyl ether, polyoxyethylene (n=7)) 9-decyl ether, and the like.

In the present invention, the compounding amount of the compound of the general formula is A/I/
1 to 5000-1 or 5 to 5000-1 for potassium aqueous solution
It is 1000-. If this amount is less than 1, the leakage of the developer to the present resist will not be sufficient, while if it is greater than 5,000 jfa, the performance of the present resist will be poor and foaming will be negligible.

The developer of the present invention can be applied to both positive I11 and negative resists without any limitations as long as the resist is soluble in alkali aqueous solution. It is preferably applied to a positive resist comprising a combination of an alkaline reversible resin and a naphthonondiazide compound. As the alkali-soluble resin,
Examples thereof include Noborafuku*m, polyhydrobystyrene or derivatives thereof.

Examples of the negative resist include those in which an alkali-soluble resin is combined with a bisazide compound such as 4,4'-diazidiphenyl sulfide or 4,42-diazidiphenylmethane.

The developing method using the developing solution of the present invention is % especially 1IIIli
Known methods such as the dipping method and the paddle method can be applied.

The developer of the present invention may contain additives commonly used in conventional glue developers, if desired. Examples of such additives include wetting agents, stabilizers, dissolution aids, and cationic surfactants for improving the dissolution selectivity between exposed and unexposed areas of the photoresist. Each can be added alone or in combination of two or more.

〔effect〕

The photoresist developer of the present invention has good wettability to photoresist and good photoresist development speed. Therefore, for example, when the developer is used for a positive resist, a pattern can be formed with high resolution without causing the base of the pattern to fall below ILV or developing undeveloped within the development time. can do. In addition, since the developer has little foaming, it is easy to operate when pouring into a container or transferring the solution, and it is extremely useful because there are no development defects caused by the generation of bubbles during the development time.

〔Example〕

EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples at all.

Examples 1 to 10 and Comparative Examples 1 to 5 'L4 weight of tetramethylammonium hydrobeef ≦
A developing solution was prepared by adding the compound represented by the general formula in the amount shown in Table 1 to an ice solution. The prepared developer was shaken and the degree of foaming was observed.

Next, to the silicone sea urchin, we applied a positive resist, which is a combination of Noporafuku resin and Naphtocoat nondiazide compound, on top.
After applying SMR-8900 (manufactured by Tokyo Ohka Co., Ltd.) to a film thickness of 1.3 μm, it was
Prebaked for 0 minutes. Apply a pattern to this silicone sea urchin using a contact liner through a photomask! 2
After adhesion, development was performed using the developer prepared above by dipping at a solution temperature of 22° C. for 1 minute. The photoresist pattern thus obtained was observed using a scanning electron microscope,
The presence or absence of development residue and the state of the hem cut at the base of the pattern were observed.

Separately, a silicon wafer which had been subjected to only the prebaking process was prepared, and the developer was dropped onto the prebaked photoresist of the wafer. Next, in order to check the degree of wetting of the dropped developer onto the photoresist,
The tablet antennae of the wrinkle developer was measured using a contact angle meter.

The above results are shown in Table 1. In addition, in Table 181, the shape of the pattern is defined as ○ if the hem of the pattern base was well cut and the shape was good in the sudden observation of the hem breakage of the pattern base. Those with defective shapes are indicated as "X".

Claims (1)

[Claims] In the alkaline aqueous solution, there are general formulas, mathematical formulas, chemical formulas, tables, etc. A photoresist developer containing 1 to 5000 ppm of the compound represented by