JPS59181535A - Pattern formation of negative resist - Google Patents

Abstract

PURPOSE:To draw a pattern, which has excellent dry-etching resistance and heat resistance and fine resolution, with a high sensitivity by a method wherein a film of polymer which contains specific quinone diazide is formed on a substrate and irradiated by far ultraviolet rays and developed by a solution containing acetic acid ester or the like. CONSTITUTION:A pattern resist film, composed of quinone diazide ester oligomer whose degree of polymerization is less than 10, is formed on a substrate and, after being irradiated selectively by far ultraviolet rays of 180-300nm wavelength, developed by a solution containing acetic acid ester or alkyl ketone. For instance, naphthoquinone-1,2-diazide-5-sulfonic acid ester novolack resin is dissolved in methyl cellsolve acetate and applied on the silicon substrate by spin-coating. Then, after being baked at 60 deg.C for 30min, the resist is subjected to the contact exposure by an Xe-Hg lamp for 10sec and developed by isoamylacetate for 20sec and the resist pattern is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a method for forming a fine negative pattern, which is suitable for manufacturing semiconductors, magnetic bubble resistors, parts for use in magnetic bubbles, etc.

(Prior Art) In recent years, the demand for higher integration of semiconductor integrated circuits has been increasing.4. - Along with this, in the field of lithography, light sources with short wavelengths such as electron beams, X-rays, or deep ultraviolet rays have been used instead of the conventional sources (mostly ultraviolet rays).

With technology that is an extension of American photolithography! However, it is easy to make Zabmicron's transfer k ''TI positive, and it is said to have great potential for future microfabrication.

Lennost used in such far-UV i 1J lithography is required to have daytime sensitivity in the far-UV region, high 1-image power, high 1-ljl heat resistance, and excellent dry etching resistance.

By the way, polymethyl methacrylate (hereinafter abbreviated as PMMA) has been used as a renost for far ultraviolet rays, and has an excellent resolving power of 0.2 μm or less using close path light using a conformable mask. . However, on the other hand, this PMMA has low sensitivity and sufficient dry etching resistance.

In addition, methacrylic acid ester polymers and methacrylic ester copolymers are also known as resists for deep ultraviolet rays, but these also have the same problem with regard to dry etching resistance.

And also vinylphenol and cyanodiphenyl sulfone (hereinafter MR8 and 111i',
Although it is intuitive and has good dry etching properties and conforms to the characteristics, it has one drawback: it does not have sufficient heat resistance.

(Objective of the invention) That is, it has high sensitivity and high resolution to far ultraviolet rays, and also has high dry etching resistance and heat resistance. The reality is that it is desirable to establish a method for forming turns.

Here, the present inventors (as a result of intensive research in response to the above-mentioned Yasugi), formed a polymer skin Bp containing quinone diat on the 4th layer, irradiated it with far ultraviolet rays, and treated it with an acetate ester or an acetate ester. The present invention has been devised to show that by imaging with a bath solution containing luketone, the above-mentioned dry etching resistance and heat resistance can be significantly improved and a Lenost pattern with good imageability can be formed at a commercial rate. It was reached.

(Structure of the Invention) That is, the present invention forms a film of a polymer containing a quinone noanodide on a substrate, irradiates it with deep ultraviolet rays with a wavelength of 180 to 300 nm, and then irradiates the film with a polymer containing a This is a method of oxidation using a bath solution.

In this invention, as a resist material, Ii 41 i is used as the resist material. Naphthoquinone-1,2-noazito-S-sulf'-
Benzoquinone diazide and naphthoquinone esters (hereinafter abbreviated as LMR) are preferred, and the quinone diazide groups include benzoquinone diazide and naphthoquinone noaside, both of which are used in the present invention. With this, I can achieve my goal.

The above LMR has a sensitivity of more than 10,000 tones of PMMA to far ultraviolet rays, and one convex image of submicron;
Furthermore, it has excellent dry etching resistance (g, 0), and no sag occurs even at baking temperatures of about 200"0. Furthermore, it has excellent dry etching resistance (g, 0), and no sagging occurs during development.
By reducing the resistivity, a "bar hang" shape can be obtained, and thus the LMR can be suitably used as a dry etching resist or as a lift-off resist by deep ultraviolet lithography.

In this way, the present invention can be used to improve
P-turn f6: The reason why it can be formed well is thought to be as follows: L iVf R is a comparative example described later; and the known A Z b
7J with T image solution? ) A mold/setan is formed. However, in this light irradiation reaction, arm turning cannot be formed even when acetate is used as a developer.

That is, in this case, the reaction with far ultraviolet rays is normal ultraviolet 11i,
(This is completely different from the reaction caused by radiation.

In the present invention, the resist in the area irradiated with deep ultraviolet rays has a structural structure and is insoluble in Nissdell, etc., and is patterned.9 In other words, although it is a negative resist, it does not undergo a crosslinking reaction, so the pattern does not swell and remains intact. Significant f=% j
It is thought that it shows 9'X image power.

The reason why the geo-mahang shape can be obtained by lengthening the development time is that the 1R has a large absorption in the far ultraviolet region, so light does not penetrate deeply in the r region. Only one layer exposed in the layer shown in the figure becomes insolubilized, so when it is developed, it is developed as shown in Figures 42 and 3, and the shape of the outer layer can be determined by over-development. be. In the plan view, 1 is a mask, 2 is an LMR layer, 3 is a substrate, and 2a is a reaction region.

Next, LMR is a compound in which a quinone noanodo and a novolak are bonded together with a sulfonic acid. For example, as in Comparative Example 4, the structural change under deep ultraviolet rays is thought to be due to the reaction of the quinone noanodo group rather than the reaction of the novolac. That is, the polymer that can be used in the present invention must have a quinonediazide base and be soluble in monoacid esters or alkyl ketones.

(Example) The invention will now be explained in detail with reference to Examples.

Example LMR was dissolved in methyl-Hilsolp acetate and applied to a thickness of 0.5 μm on a silicon substrate by spin coating. After baging at 60℃ for 30 minutes,
A 71 ir exposure was performed for 10 seconds using a 500W Xe-Hr lamp. After exposure, it was developed with in-amyl acetate for 20 seconds to obtain a line-and-space resist pattern with a width of 0.5 μm.

Example 2 Lennost pattern 'e200' made in Example 1
pH was added for 2'30 minutes at c and then analyzed using a scanning electron microscope (SEM).
As a result, the resist pattern showed no deformation such as blurring at all and was equivalent to the heated MiJ pattern.

Example: 3 Exposure was carried out in the same manner as in Example 1, and development was performed with in-amyl acetate for 130 seconds. When the developed pattern was observed using a SEM, the cross section of the IZ turn had an overhang shape.

Example 4 A film of LIVI R was formed on a plate in the same manner as in Example 1, and its dry etching resistance using an oxygen glazma was examined. A parallel plate type etching apparatus was used, and etching was carried out for 15 minutes at a power density of 0.08'w/, a gas flow of 0□ Cnt-i 20' ccM, and a gas pressure of 50 pa, and the etching amount was 50 nm. For comparison, the etching amount was 200 nmT6 under the same conditions except that PMMA' was used.

Comparative Example 1 LMR exposure was performed in the same manner as in Example 1, and AZ-13
After developing for 60 seconds using a 50J developer, no pattern was formed.

Comparative Example 2 PMMA was coated on a silicon substrate to a thickness of 0.5 μm and baked at 180° C. for 30 minutes.
When I developed it with MIBKr, I was able to get 9 turns in 120 seconds, but I couldn't get 7 turns in 60 seconds.

Comparative Example 3 LMR formed in the same manner as in Example 1 was developed with a mask aligner having a 250 W mercury run for 30 seconds using a Fukiko line and an AZ-1350J developer.
5 Noah! 12 /e turns are obtained and 1 is obtained. In addition, I used r + i acid isoamyl and solved 1 thing and all 10] / 6! I can't turn.

Example 5 When L MR exposed in the same manner as in Example 1 was developed with methyl isoamyl ketone for 20 seconds, a 0.5 μm Lenost P turn was obtained.

Example 6 Same as Example 1 1) - Developed with a mixed bath solution of LMR all n-propyl acetate and isochlorohexane 5:2, and a resist pattern of 0.5 μm was obtained. .

Example 7 In the same manner as in Example 1, Fukko Shiko LMR was developed with a mixed bath solution of isozolovir acetate and inglobil alcohol 5:1, and a resist of 0.5 μm was formed on each side.
I got one turn.

Comparative Example 4 Novolac was dissolved in methyl cellulose architate, and this was coated on a substrate to a thickness of 0.51 trn (this coating was applied).
T, f.

Baked at 100° C. for 30 minutes using the same device as in Example 1: 30 seconds. After developing it with isoamyl acetate, only seven turns were formed.

(Effects of the Invention) As is clear from the above description, the present invention uses far ultraviolet rays and has excellent dry etching properties and heat resistance.
It is possible to form a resist pattern with good resistance to the cylinder sensitivity, and by increasing the development time, it is possible to form a resist pattern of 46 conductors and magnetic bubble elements. Its industrial value is extremely large as it can be used for manufacturing.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the four reaction regions of the light of scolding ultraviolet irradiation + 1'f in the present invention, and FIG.
FIG. 3 is a diagram showing a resist pattern after image formation. 1...Mask, 2...LMR layer, 3...Substrate. Fraud Agency Director Kazuo Nasugi L. N1 Special Request for Imprisonment for Case 1'l! 18-5367: (No. 2 Name of Invention #) j Munost's putter 7 type IA 75? 1<3? +
(02!T)
) L+L+Electricity”-Gyo Co., Ltd. 4th generation 1g
Person 5? Mountain ] 1 Sentence j % (5'1 Claims 1ift, Detailed Description of the Invention, Brief Explanation of Drawings, and Drawings (1) Claims shall be revised according to the attached sheet 1, (
2) Page 2, line 5 [7) before the details] dera)ro, 5
．． 1 [is considered to be a thing. 1-Kiku Zhong 1 Kacho is-ζ
There are two methods: the first method and the first method, which is 1, in this case, 1, and 1. '(3) Add the following between lines 6 and 7 on page 3:
Mat:, in the case of the method by Rifts 7,! , strict conditions are required regarding the cross-sectional shape of the list film, heat resistance, melting/V properties, adhesion, etc. For example, in order to be able to easily form a pattern by lift-off, Renos J.
There is another layer of adhesion! -Easy to dissolve with rest 1
・It is necessary to have two layers that can be removed, and for this purpose, the pattern is formed and the cross-sectional shape of the resist film is 2-Barr,
It must be in the shape of a At present, in order to form this overhang shape, it is convenient to use a multi-layered photoresist or a bomb-shaped photoresist, for example, chlorbenoceno treatment of AZ-1350J (trade name of photoresist manufactured by Sh+play). [ing. These processes (r complicated, s+: ---f7
1- is inferior, and January current quantity is also necessarily /+ l; l-<
Nagat/, : ,, jfil 1iil 3 self 9?
r"i-";ij [i! l! l<, present (look at Meng)
``It is possible to form a bar hang.'' (51bi13Pt] 9~20iIr Tekiruko and l
/i! J, and its cross-sectional shape is /1-, with an overhang, and KJ stops at -4. f61 1+'tl 4 animals 2 lines 1 and I J no Ue 1 ko'',
``Substrate) t'' of Religoma with a polymerization degree of IO or less. As shown in the example,
ζ Add a nap of novolac resin having a weight of 8 degrees or more to 10 degrees: quinol-1,2-reacto-5-through-7 acid. (8) Same 4 [L20 line to page 5 line 1 “Moreover, development
- Obtain ζ doga'' should be corrected as follows. 1, and there is no need to develop it! The shape of the bar hanger II
) Words: (9) Same line 5020 - page 6 line 1 [As a result, I can think about it. Also, each time the above development time is lengthened, the stiffness] and the color are as follows? 111 Stop. ）゛Rustful (This remarkable high resolution can be considered as a small item.Also, Mle is -(l; Sesame molecule-ht
(small) is also effective in not showing the above-mentioned high resolution lJ
<1゜Then, 1-Memorization (() に Jsu1 [!O] On page 6, lines 5-7, “to insolubilize”
Seaver bag” and Aro as follows? ill +F 1
``It becomes insolubilized, and after complete development, it is developed as shown in Figure 2, and the following is corrected for the sentence ``obtained'' on page 7, line 8. Observation with a scanning electronic microscope (abbreviated as SE-1) revealed that the direction toward the rest 1ffi had an overhanging shape. 1. The overhang shape was larger than that in Example J." A. See the following: Figures and 34'+E-4 1゜2, Claims

Claims (1)

[Claims] A film made of a polymer containing quinonediazide is formed on the substrate, and deep ultraviolet rays with a wavelength of 180 to 300 nm are irradiated.
Next, what about acetic acid ester (or Negalenost, which is characterized by developing with a solution containing an alkyl ketone)? How to make a turn.